Anal. Chem. 1905, 57,46 13-88 R (91) Kotecha, J.; Morgan, R. M. J. Pharm. fharmacoi. 1982, 34 (Suppl.), 113P.
(101) Kovar, K. A.; Langlouis, H.; Auterhoff, H. Pharm. Weekbl. Sci. Ed. 1983, 5(4),134. (111) Kovar, K. A.; Sakmann, A. J. Chromafogr 1982, 247(2),356. (121) Lake, 0.A.; Hulshoff, A.; Indemans, A. W. M. Pharm. Weekbl., Sci. Ed. 1982, 4 (2),43. (131) Lake, 0.A.; Hulshoff, A.; Van de Vaart, F. J.; Indernans, A. W. M. Pharm. Weekbl., Sci. Ed. 1983, 5 (I),15. (141) Lee, Y.-C.; Karnatz, N. N.; Baaske, D. M.; Ellason, M. S.; Alam, A. S. J. Chromatogr. 1983, 269 (l),28. (151) Liversidge, G. G.; Grant, D. J. W.; Padfield, J. M. Anal. Proc. (London) 1982, 19 (12),549. (161)Luedde, K. H.; Melson, F.; Wedei, R. Zenfralbl. Pharm., Pharmakofher, Laboratoriumsdiagn. 1982, 121 (9),891. (171) Nondek, L.; Chvaiovsky, V. J. Chromafogr. 1983, 268 (3),395.
(181) Padmanabhan, G. R.; Smith, J.; Mellish, N.; Fogel, G. J. Liq. Chromafogr. 1982, 5 (7),1357. (191) Radus, T. P.; Gyr, G. J. Pharm. Sci. 1983, 72(3),221. (201) Ramappa, P. G.; Nayak, A. N. Analysf (London) 1983, 108 (1289), 966. (211) Schieffer, G. W.; Palerrno, P. J.; Pollard-Walker, S. J. Pharm. Sci. 1984, 73 (l),128. (221) Smith, A. Anal. f r o c . (London) 1982, 19 (12),559. (231) Such, V.; Traveset, J.; Gonzalo, R.; Gelpl, E. J. Chromafogr. 1982, 234 (I),77. (241) Thieme, H.; Kurzik-Durnke, U. Pharmazie 1982, 37 (5),370. (251) Van de Vaart, F. J.; Hulshoff, A.; Indemans, A. W. M. Pharm. Weekbl., Sci. Ed. 1982, 4 (I), 16. (261) Van de Vaart, F. J.; Hulshoff, A,; Indemans, A. W. M. Pharm. Weekbl., Sci. Ed. 1983, 5 (3), 109. (27D) Winkel, D. R.; Hendrick, S. A. J . Pharm. Sci. 1984, 73 (l),115.
Water Analysis J. R. Garbarino,* T. R. Steinheimer, and H. E. Taylor
U.S. Geological Survey, M S 407, P.O. Box 25046, Denver Federal Center, Denver, Colorado 80225
This is the twenty-first biennial review of the inorganic and organic analytical chemistry of water. The format of this review differs somewhat from previous reviews in this series-the most recent of which appeared in Analytical Chemistry in April 1983 (1). Changes in format have occurred in the presentation of material concerning review articles and the inorganic analysis of water sections. Organic analysis of water sections are organized as in previous reviews. Review articles have been compiled and tabulated in an Appendix with respect to subject, title, author(s), citation, and number of references cited. The inorganic water analysis sections are now grouped by constituent using the periodic chart; for example, alkali, alkaline earth, 1st series transition metals, etc. Within these groupings the references are roughly grouped by instrumental technique; for example, spectrophotometry, atomic absorption spectrometry, etc. Multiconstituent methods for determining analytes that cannot be grouped in this manner are compiled into a separate section sorted by instrumental technique. References used in preparing this review were compiled from nearly 60 major journals published during the period from October 1982 through September 1984. Conference proceedings, most foreign journals, most trade journals, and most government publications are excluded. References cited were obtained using the American Chemical Society's Chemical Abstracts for sections on inorganic analytical chemistry, organic analytical chemistry, water, and sewage and waste. Cross-references of these sections were also included.
INORGANIC ANALYSIS ALKALI AND ALKALINE-EARTH METALS
Barium. Rollemberg and Curtius (IIA) have described a method for the determination of barium in lake water and seawater using a carbon rod atomizer-atomic absorption technique. They used Dowex 50W eluted with ethylenediaminetetraacetic acid to separate interfering ions. A detection limit of 9 pg/FL is reported. Barium was determined in the presence of calcium by Johnson et al. (6A), using a flame atomic emission procedure. They used an ion exchange procedure to separate the calcium at a 1OOO-foldconcentration excess. Detection limits of 5 ng/mL were easily achieved. Sugiyama, Fujino, and Matsui (15A) determined barium in seawater by graphite furnace atomic absorption spectrometry after proconcentration and separation by solvent extraction. After the pH was adjusted to 5 with acetic acid, the sample was extracted with benzene containing l-phenyl-3-methyl-4benzoylpyrazoi-5-one and trioctylphosphine oxide. The aqueous phase was adjusted to pH 6.4 with ammonium hy46 R
This article not subject to
U S . Copyright.
droxide and the barium was extractd with the benzene solution of complexing agents. The benzene was back extracted into dilute nitric acid and analyzed by Zeeman background corrected graphite-furnace atomic absorption, using a pyrolytically coated tube. Beryllium. Kuo et al. (8A) have reported a gas chromatonrar,hic method for the determination of bervllium in tar, wa'tei. A complex with trifluoroacetylacetone was formed cn ethanol and subsequently extracted into cyclohexane, followed by a wash with 0.1 M sodium bicarbonate solution. They reported that fluoride ion interferes to some degree. A polarographic determination of beryllium in water is described by Chen and He (3A). Wave form symmetry and sensitivity is improved by adding tetraethylnickel to the ammonium chloride, ammonium hydroxide, ethylenediaminetetraacetic acid, and Be-reagent supporting electrolyte. They report a linear calibration curve over the range of 0.0002-1.0 Fg/L and a recovery of 99% with a relative standard deviation of 1.69. Finally, an atomic absorption procedure is described by Burba et al. (2A), using an enrichment step cellulose ion exchanger. They show that nanogram quantities of beryllium can be enriched by a factor of 100 to 200 from tap water, river water, and seawater. Although calcium ion causes signal depression, detection limits for the complete procedure are 50 ng/L and 1ng/L, respectively, for flame atomic absorption and graphite furnace atomic absorption. Calcium. Bramall and Thompson (IA) reported a method for reducing the atomic absorption sensitivity for the determination of calcium, by using the 430.3-nm nonresonance spectral line. A nitrous oxide-acetylene flame was used and linear calibration curves up to 10.0 absorbance units were obtained, indicating that little self-absorption occurs. Recovery experiments were satisfactorally performed on sewage sludges. Calcium was determined in raw and potable water by Frend et al. (5A)using flow injection analysis and a tubular membrane flow-throu h potentiometric electrode. The calcium selective electrole was based on calcium bis(4-(1,1,3,3tetramethylbuty1)phenyl)phosphate with trioctyl phosphate in poly(viny1chloride). This electrode has improved resistance to interferences by anionic surfactants. They specified that M free calcium can be determined in the presence of moderate amounts of background detergents. Nakagawa, Wada, and Wei (9A) have reported the indirect determination of calcium in the range of 0.8-7.2 mg/L by a flow-injection spectrophotometric method. The procedure is based upon the exchange reaction between calcium and the zinc complex of ethylene glycol bis(2-aminoethyl ether)tetraacetic acid in the presence of 4-(2-pyridylazo)resorcinol (PAR). A sample analysis rate of 80 per hour was achieved. A spectrophoto-
Published 1985 by the American Chemical Society
WATER ANALYSIS
hated with a barium ethylenediaminetetraeticacid buffer while interferences from iron(I1). aluminum, copper, zinc, manganese, and cadmium were masked by cyanide and triethanolamine.
3r.
Qui and Zhu (IOA) used a complex with BeryUon I1 a t pH 11.8 to determine calcium and magnesium in river and well water. The apparent molar absorptivities at 603 nm were 309 and 865 L/(mol em) for the calcium and magnesium complexes, res ctively. Calcium and magnesium can also be determinecf&uentiaUy after destroying the calcium complex by the addition of lead ethylenediaminetetrascetate,after the total had been measured. Kagenow and Jensen (7A)reported the simultaneous determination of calcium and magnesium, based on the dissociation reactions of cryptand(2,2,2) complexes by a spectrophotometric stopped-flow injection technique. Absorption measurements of the phthalein complexone complexes were performed at the rate of 80 per hour. Yoshida et al. (17A) described a method for the determination of calcium and magnesium by the thermometric titration with sodium ethylenediaminetetraacetate in the presence of sulfosalicylic acid which changes the difference in conditional stability constants between calcium ethylenediaminetetraacetate and magnesium ethylenediaminetetraacetate. TRANSITION METALS
1st Series. Scandium. Scandium in wastewater was
collected and reconcentrated by using potassium salts of
octanoic acid, &canoic acid, or lauric acid a t 25 "C and a pH of 4.0 in a rocedure outlined by Ke and Li (318). Recoveries utilizing tRis procedure ranged from 96 to 98%. Titanium. A sensitive and selective method for the determination of titanium based on a direct photometric measurement was discussed by Menon and Agrawal(38). Results showed that the sensitivity of titanium(1V)-benzohydmxamic acid complex extracted with a liquid ion exchanger, Aliquat 336,in the presence of thiocyanate is 10 times greater than that of the same complex extracted with hexanol or isoamyl alcohol. C i k , Sulcek, and D o l e d (138)developed a method for determining titanium photometrically in water and water-soluble salts with diantipyrylmethane, after preconcentration by sorption as a 11 titanium-peroxide complex on a silica gel column. Following a specific workup procedure, the bound titanium is stripped off the column and reacted with the ligand, and the absorbance is measured at 385 nm. Chikryzova et al. (128)compared polarographic methods for determining titanium(IV) and chlorate ions in natural waters using the catalytic current in a titanium(1V)hrganic acidchlorate ion system. metric procedure for the determination of calcium w88 deVanadium. Determination of trace vanadium in water scribed by De la Rosa, Gomez h i m , and Pino (4A). By using a modified catalytiicphotometric p d u r e was reported react' 1,3-bi@pyridyI)methyleneamino)urea with calcium by Qiang (528). Optimization of method parameters greatly in media, a 11yellow complex ia formed which absorb increased precision, 1.1-5.470. shortened analysis time, ima t 430 nm. Interferences are minimized by the addition of proved the accuracy, recoveries ranged from 96 to 103%, and masking reagents and linearity obtained over the range of gave a detection limit of 0.2 @/L. Rueter and Schwedt (578) 0.54 pg/L was reported. conducted a comparative study of preconcentration methods Cesium. Shamaev and Chudinovskikh ( E A ) have deterapplied to the determination vanadium in various waters. mined cesium in aeawater by a radiochemical techni ue. They used a substoichiometric concentration with nic el hexaResults indicated that vanadium extracted with N-benzoylN-phenylhydroxylamine and adsorbed on Chelex 100 resin cyanoferrate(II) and tetraphenylborate coupled with selective was the most effective when compared to nine other enrichradiochemical procedures. They reported the determination ment procedures. Morgen and Dimova (358) showed that of cesium in Atlantic Ocean sam les as 0 74 f 0.03 pg/L. vanadium could be determined photometrically in the presLithium. Lithium has been jetermined spectrophotoence of titanium by using 4-(2-pyridylazo)resorcinol(I) in a metrically by Sitnikova et al. (13A). They have described a water-propanol medium. Measurement of vanadium in the new highly selective complexing reagent, 15,16-dihydro-7presence of 1Wfold excess titanium was based on the large cyano-5H,17H-dibenzo(b~)(l,l1.4.5.7.8)dioxatetr~cyclotedecrease in light absorption of the titanium-I complex relative tradiene (TMC-crownformazan). By measurement of the to the absorption of the vanadium-I complex a t 550 nm in absorbance a t 540 nm, a detection limit of 0.02 pg/mL WBB the presence of organic solvents. The detection limit is 0.04 achieved. Thorn son and Cummings (14A) reported some pg/mL vanadium and the methodology was applied to the problems in the xetermination of lithium in wastewater by analysis of settling pond waters. Vanadium was extracted atomic absorption spectrometry. They reported that the from seawater with capriquat in a method proposed by Shijo air/acetylene flame was prone to chemical interferences on et al. (618). The analyte complex was decomposed in acid some instruments and they suggested the use of the hotter prior to grajhite furan!, a%mic absorption spectroscopic nitrous oxidelacetylene flame to minimize these effects. analysis, an investigations indicated no interferences from Magnesium. Wada, Yuchi, and Nagagawa (16A) stated other cations common to seawater. Cole, Eckert, and Williams that l-(2-hydroxy-3-sulfo-5-chloro-l-phenyl~o~-2-napthol(148) proposed a method using X-ray fluorescence for the 3,6disulfonic acid can be used in a spectrophotometric flowdetermination of dissolved and particulate vanadium in seainjection system for the determination of magnesium in tap water. Vanadium was coprecipitated from seawater by trisand pond water over the concentration range of 0.2-2.4 mg/L (pyrrolidinedithiocarbamato)cobalt(III) at pH 4.0,collected a t a rate of 80 m p l e s / h . Interference by calcium was elim-
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ANALYTICAL CHEMISTRY. VOL. 57. NO. 5. APRIL 1985
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WATER ANALYSIS
as a thin film on a membrane filter, added to the particulate obtained from initial filtration, and analyzed directly. The detection limit for 100-mL water samples and a counting time of 400 s is 0.02 pg/L vanadium. Extraction efficiency in the vanadium concentration range of 0-5 pg/L range was 95%. Results show dissolved and particulate vanadium in seawater samples ranged from 1.4 $0 1.7 and 0.06 to 0.61 pg/L, respectively. Chromium. The transient oxidation of brucine in solution was used for the determination of chromium(V1)and brucine in a method developed by Yamane and Mottola (85B). The red intermediate of the reaction is photometrically monitored at 525 nm to permit the determination of both chromium(V1) and brucine in the concentration ranges from the detection limit to 7.5 and 197 pg/mL, respectively. The detection limits were 0.1 pg mL for chromium(V1) and 4 pg/mL for brucine. Other alka oids similar in structure to brucine were investigated as was the application of the method to chromium determinations in water, sludge, and steel. A method capable of determining chromium in wastewater containing reductive substances is discussed by Zhou (89B).Samples of this type were pretreated with peroxydisulfate before direct colorimetric measurement. Recovery experiments at 0.2 pg/mL chromium(V1) ranged from 95.7 to 100% with a relative standard deviation of 1.1% and the linear working range was 0-0.40 pg/mL chromium(V1). Wang et al. (81B)described a method for determining total chromium and chromium(II1) in natural waters. The method employs Chrome Azurol S, cetyltrimethylammonium bromide, and sodium sulfite (only for total chromium determinations) in preparation to spectrophotometric measurement at 620 nm. Beer’s law is observed at concentrations less than 0.28 pg/mL. Studies implementing the reaction of chromium(VI)wth 1,5-diphenylcarbazidewere presented by Reinhold (55B). The method was shown to be impervious to oxidation-reduction interferences present in wastewater and was effective for chromium(VI)concentrations greater than or equal to 0.05 mg/L. A method for the determination of total dissolved chromium in seawater by graphite-furnace atomic absorption spectrometry following preconcentration on a diphenylcarbazoneloaded silica column is described by Willie, Sturgeon, and Berman (83B). Total dissolved chromium is reduced to chromium(II1) by addition of sulfurous acid and the resulting solution is pH adjusted and passed through the column at a rate of less than 100 mL/min. Sequestered chromium is eluted with 0.2 N nitric acid prior to analysis. Isozaki, Kumagai, and Utsumi (25B)discussed a method for determination of parts per billion concentrations of chromium(II1) and chromium(V1)by electrothermal atomic absorption spectroscopy. Chromium(II1) is quantitatively adsorbed onto Chelex 100 from 250 mL of solution and the resin is collected on a membrane filter. An aqueous suspension of the resin is then prepared and 10 pL is injected into the furnace and the absorption peak area for chromium measured. Chromium(V1) remains in the filtrate and is reduced to chromium(II1) which is then determined by the same methodology. Relative standard deviations for 1pg/L chromium(II1) and chromium(V1)are 2.3% and 3.7%, respectively. Smith, Bezuidenhout, and Van Heerden (65B) found that cesium/lanthanum interference suppressant compared favorably with other common suppressants in the determination of chromium by flame atomic absorption spectroscopy. The authors showed that the cesium/lanthanum mixture exhibited better interference-suppressingability than previously recommended ammonium hydrogen fluoride-sodium sulfate solution, for determining 500 pg L chromium in the presence of magnesium, calcium, iron, co alt, or nickel in reducing air-acetylene or nitrous oxide-acetylene flames. Catalytic voltammetric determination of trace chromium(VI) in water using a flow-through cell with fixed mercury membrane electrode was investigated by Wan, Zhang, and Luo (80B).The linear working range for chromate in aqueous solution containing ethylenediamine and nitrite was 0.1-10 ng/mL. Recoveries ranged from 94 to 108% for chromium(VI) concentrations of 0.06 to 2 ng/mL. Total chromium was determined by oxidizing chromium(II1)to chromium(V1) with potassium permanganate prior to voltammetric analysis. Osaki, Setoyama, and Takashima (48B) studied the effects of sample storage, pH, and sodium chloride concentrations on the separations of trace amounts of chromium(V1) and hydrolyzed chromium(II1) from water using gel chromatog-
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ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
raphy. A sensitive method for the separation and determination of potassium chromate and potassium dichromate by paper chromatography is described by Rajendrababu, Kumar, and Nanguneri (53B). Succinate dehydrogenase inhibition with 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyltetrazolium chloride-phenazonium methosulfate-sodium succinate mixture was used as the chromogenic reagent. Two micrograms could be detected by a spot test or 5 pg directly from freshwater chromatographically. Low concentrations of chromium(II1) and chromium(V1)in natural waters were complexed with trifluoroacetylacetone and quantified by electron capture gas chromatography in a method proposed by Tanaka, Nakano, and Kanazawa (68B).The detection limit for total chromium was 0.03 pg/L. Sub-part-per-billionconcentrations of chromium in seawater were measured by isotope dilution gas chromatography-mass spectroscopy as discussed by Siu, Bednas, and Berman (64B). Care was taken to ensure all the chromium in the sample was completely reduced to chromium(II1) prior to extraction and concentration as tris(l,l,l-trifluoro-2,4-pentanedionato)chromium(III). Selected ion monitoring of the chromium complex mass fragment ions was used to measure the original chromium concentration with 5% precision. Chromium species were preconcentrated from water samples by coprecipitation with lead salts and measured using neutron-activation y spectrometry in a method discussed by Zhang, Holzbecher, and Ryan (88B). Both chromium(II1)and chromium(V1) are coprecipitated with lead phosphate, but only chromium(V1) coprecipitates as a lead sulfate thereby allowing individual species measurement. The 320.1-keV y-ray peak of 51Cr ( t y z = 27.7 days) was used for the measurement to give a detection limit of 0.1 pg/L for chromium in seawater when 800-mL samples were used. Manganese. The determination of manganese based on the formation of a ternary complex of o-hydroxyhydroquinonephathlein (I),zephiramine, and manganese(I1)was discussed by Mori et al. (37B). The difference in absorbance between the ligand and I-manganese(I1) solutions was largest in the presence of zephiramine at pH 9.0 and was measured at 535 nm. Beer’s law was obeyed for concentrations from the detection limit to 0.4 pg/mL manganese. Interferences were identified and eliminated. Recoveries of manganese from tap water and wastewater ranged from 97 to 103% and the variation coefficients for eight determinations of 1.4 pg manganese(I1)was 1.2%. Zeinalova, Guseinov, and Rustamov (87B) used the complexation reaction of manganese with 2,2’-bipyridyl and (2,4-dinitrobenzeneazo)pyrocatecholand extraction into chloroform as the basis of a method for determining manganese in water and soil. The properties of the ligand and its 0-and p-nitro analogues were identified in an attempt to optimize the method’s sensitivity. Manganese was complexed with dibenzyldithiocarbamate and extracted into methyl isobutyl ketone at pH 5-9 prior to analysis by atomic absorption spectroscopy in a method developed by Ichijo (22B). Absorbance was measured at 279.5 nm with an air-acetylene flame and resulted in a linear working range for 1-20 pg of manganese. Interferences from iron and aluminum were identified. Differential-pulse anodic stripping voltammetry at a mercury-film electrode was implemented by O’Halloran (47B) for ultratrace determinations of manganese(I1) in seawater. Interference effects from other trace metals were found to be negligible in open ocean water, partly because zinc interacts with copper to minimize the formation of the copper-manganese intermetallic. Manganese concentrations down to 0.01 wg L could be attained. Dzhafarova, Zhdanov, and Sharafieva (1 B ) used direct polarography for the determination of manganese in natural waters. The analysis was conducted at 70° to eliminate interference by organic substances and used the technique of standard additions. At manganese concentrations between 1 and 10 pg/L, the relative standard deviation was less than 8%. Iron. A spectrophotometric method for the determination of iron in potable water was proposed by Wada, Nakagawa, and Ohshita (78B) using 2-(3,5-dibromo-2-pyridylazo)-5-Nethyl-N-(3-sulfopropyl)aminophenolto form a water soluble chelate with iron(I1). Interferences from other metals are eliminated using EDTA and N-(dithiocarboxy)sarcosine. Implementation with a flow injection system gave a linear working range of 20-440 pg/L iron at 750 nm and an analysis
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WATER ANALYSIS
rate of 30 samples h. Ueda, Yoshimura, and Yamamoto (74B) outlined a metho using 4-(4-methyl-2-thiazolylazo)resorcinol to selectively form a brown complex with iron(I1) that had an absorption maximum at 735 nm. The absorbance is constant throughout the pH range of 8.s11.6, Beer’s law is obeyed a t concentrations less than 2 ppm iron, and the molar absorptivity is 2.5 x lo4L/(mol cm). Transition metals of the 3d configuration do not interfere, and the method was successfully applied to the analysis of river water and other substances. Iron was determined in natural water and plants by flow injection analysis with spectrophotometric measurement a t 512 nm of the complex formed with 1,lOphenanthroline in a method outlined by Mortatti et al. (38B). Method operating parameters were optimized and interferences identified. With this technique, iron was determined in the range of 0.1-30 ppm at a rate of 180 samples/h. Itoh (26B)found that iron(I1) could be complexed with a zinc(I1) complex of the Schiff base derived from pyridine-2-aldehyde and diethylenetriamine and quantified photometrically. Iron(I1) reacts with the zinc complex to form a red complex having an absorption maximum at 525 nm and a molar absorptivity equal to 1.2 X lo4L (mol cm). The absorbance of the complex is constant at p 5.4-6.0 and Beer’s law was obeyed for 0.14 to 2.8 pg/mL iron. Interferences from copper(I1) and silver(1) were identified. The complexation reaction of 1-phenyl-3-thiobenzoylthiocarbamide with iron(I1) was utilized by Ilyas and Joshi (2323)in the spectrophotometric determination of iron in water and other substances. Absorption measurements were made at 410 nm and satisfied Beer’s law in the range of 2-20 ng/mL iron; the Sandell sensitivity was 0.0266 ng/cm2 iron. The tolerance limit of various ions was determined and ethylenediaminetetraacetic acid, copper, cobalt, palladium, and cadmium showed serious interference. Katami et al. (30B) presented an extractionspectrophotometric method for the determination of iron based on its extraction into chloroform with 2-2-(3,5-dibromopyridyl)azo-5-dimethylaminobenzoicacid from a weakly acidic medium. The absorbance maximum was recorded at 615 nm and the apparent molar absorptivity of the iron(I1) complex was 9.4 X lo4L/(mol cm). The method was applied to well water analysis as well as other materials. Humic acid and iron in natural waters were determined simultaneously in a method outlined by Carpenter and Smith (1OB).The method required two absorbance measurements, one on an untreated sample aliquot, and the other on an aliquot treated to enhance iron absorptivity. The method required less than 15 mL of sample and the detection limits of 0.01 mg L of humic acid and 0.04 pM iron could be achieved. esults obtained by using this method were compared on the basis of results obtained for six natural waters and sources of interferences were discussed. A catalytic method for the determination of nanogram amounts of total iron, iron(II), and iron(II1) is outlined by Nakano et al. (42B). The method is based on the catalytic effect of iron(II1) on the color reaction of N,N-dimethylaniline in the resence of peroxide activated with acetate. As little as 10- M of iron(11,111) can be measured at 728 nm. Przeszlakowski and Habrat (51B) used a mixture of Aliquat 336 and Ferron in chloroform to extract iron(II1) from aqueous solution. The absorbance of iron complexes with Ferron and Aliquat 336 was greater than that obtained for iron complexes with Ferron alone, and three absorbance maximums were found 370 nm, 465 nm, and 610 nm. The absorbances a t 465 and 610 nm were employed in the method to satisfy Beer’s law in the concentration range 0.1-10 mg/L iron. The method was found to be selective for iron, only copper at concentrations greater than that of iron interfered, and results correlated well with other methods. Iron flotation-spectrophotometric determination of trace amounts of iron in water was proposed by Yamada et al. (84B). Ferric ion was reduced to iron(II), complexed with 1,lO-phenanthroline, and concentrated into sodium lauryl sulfate prior to analysis. Optimal method conditions were used to give the highest sensitivity and a linear calibration curve from 30 to 600 nM iron(II1) and a total analysis time of 30 min. Various other cations were shown to interfere with the analysis. Iron-dimercaptomaleonitriletetrabutylammonium complex in solution with acetate buffer and tetrabutylammonium bromide was extracted into methyl isobutyl ketone and the iron complex measured at 248.3 nm using atomic absorption
d
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spectrometry in a procedure described by Inoue and Sasaki (24B). Interference limits were set for several constituents and results were compared to the conventional 1,lOphenanthroline method. Anodic alternating current voltammetry with a rotating platinum or glassy-carbon electrode was implemented by Ulakhovich, Postnova, and Budnikov (75B) in the determination of iron in potable water. Iron was reduced to iron(II), reacted with 0.01 M potassium amylxanthate, and extracted with 2,2’-bipyridyl in benzene prior to measuring the peak current at 0.95 V vs. standard calomel electrode. The Calibration curve was linear for concentrations from 5 X lo-’ to 1X M. The oxidation process is discussed and the selectivity of the method indicates wide applicability. Waite and Morel (79B) suggested that one way of improving the specificity of coulometric analysis is through electrochemical masking using strong, selective complexing agents. As a result they described a controlled potential coulometric procedure combined with 1,lO-phenanthroline that is applied to the measurement of low concentrations of iron(I1) in seawater. The method is particularly appropriate to studies of iron redox processes in seawater since redox dynamics have little effect on the analysis procedure. Iron(II1) was determined by the oxidation of 1,2phenylenediamine at pH 8 in the presence of sodium tartrate, extraction of the resulting 2,3-diaminophenazine, and measurement of the luminescenceat 540 nm in a method described by Gladilovich and Stolyarov (20B). The detection limit was 0.01 pg/mL iron and the method was applied to analysis of potable water and wastewater. Box (7B) discussed observations on the use of iron(I1) complexing agents to fractionate the total filtrable iron in natural waters. Iron(I1) complexing agents bathophenanthrolinedisulfonic acid, 2,2-dipyridyl,ferrozine, TPTZ, and acetic acid-sodium acetate buffer showed that the absorbance of the iron(I1) complex increased with time both in the presence and absence of a reducing agent. Exposure of the samples to 0.1 M hydrochloric acid prior to the addition of the complexin agents resulted in a stable iron concentration, designatel as the acid-extractable fraction of the total filterable iron. A report on the analytical implications of the presence of iron(I1) in oxygenated surface waters was published by Macalady et al. (32B). Analyses based on iron(I1) complexation with bathophenanthroline were influenced by small positive interference when the pH is less than 6.5 and iron(II1) is present. The interference, due to a colored complex formed in the presence of ferric hydroxide and bathophenanthroline, varied in magnitude in proportion to the amount of ferric hydroxide present. This interference obviates published claims that low levels of stable iron(I1) exist in oxygenated natural waters. Nickel. Nickel was determined by Sawamoto (59B)using an electrochemical stripping technique in which preconcentration was achieved by the adsorption of a nickel-2,2’-bipyridine complex on a mercury electrode. Optimum experimental and instrumental conditions were determined in a fundamental study. Following adsorption preconcentration, differential-pulse polarography was used to monitor the stripping process. The linear concentration range of the to 5 X lo-’ M nickel(II), and 2 x method was from 5 X lo-* M nickel(I1) can be detected using a preconcentration time of 10 min. Only cobalt(I1) was found to interfere with this method. Nagaosa and Sana (40B) investigated methylene chloride as the solvent for the differential pulse polarographic determination of nickel after solvent extraction with dimethylglyoxime. As little as 20 ng of nickel in solution could be determined and the method was applied to the analysis of a wide range of materials. Copper. A method describing the extraction-spectrophotometric determination of copper(I1)was published by Nonova and Stoyanov (46B). The ion-pair formed between copper(11)-442- yridy1azo)resorcinol (PAR) anion and tetradecyldimethyl!enzylammonium (TBDA) chloride was extracted using chloroform. The absorption maximum for CU(PAR)~(TDBA)2 is at 510 nm and the molar absorptivity is 8.05 x lo4 L/(mol cm). Beer’s law is satisfied in the concentration range of 0.1-0.56 pg/mL copper and the interferences due to some cations and anions are outlined. Watanabe, Tachikawa, and Ohmori (82B)studied the ion-pair extraction of copper(II)-3,4,6,5-tetrakis(l-methylpyridinium-4-yl)porphin ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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complex with dodecylbenzenesulfonate. The complex was extracted using polyoxyethylene nonylphenyl ether and 4methylpyridine to give a recovery yield of 95%. This extraction procedure in combination with dual-wavelength spectroscopic measurement was applied to the determination of copper(I1) in water at the parts-per-billion levels. The oxidation of bis(2,4-diaminophenyl)phosphonateby copper(I1) was implemented by Mori, Fujimura, and Takegami (36B)in the determination of copper(I1) in river water. The oxidation product is measured at 500 nm and Beer's law is obeyed for 0.04-0.2 pg/mL copper. Sandell's sensitivity was 1.25 X pg/cm2 copper. Anions such as thiosulfate, iodate, chromate, and iron(II1) produced serious interferences. Nanogram amounts of copper(I1) could be determined using a catalytic effect of copper(I1) on the coupling reaction of N-phenyl-pphenylenediamine with N,N-dimethylaniline in the presence of peroxide in a method proposed by Nakano et al. (41B). Concentrations of copper (11) greater than or equal to lo4 M are determined from the increase in the absorbance of the colored product at 728 nm following a predetermined delay period. Pilipenko, Karetnikova, and Trachevskii (49B)studied the copper 1:l and 1:2 complexes of 4-methyl-242-h droxy1-naphthy1azo)thiazole(I) and 4-adamantyl-2-(2-hydoxy-lnaphthy1azo)thiazole (11). The 1:2 complexes were isolated as solids and their properties studied. The determination of cop er in water was based on the extraction of the 1:2 copper-I an copper-I1 complexes and their absorbance measurement a t 600 and 565 nm, respectively. Using agent I1 ermitted determinations of 0.004 pg mL copper. Tsin areti, Gaidadymov, and Tabakova (73 ) proposed a metghod for determining copper at concentrations between 0.04 and 1.6 mg/L photometrically or ionometrically in natural water following hotochemical mineralization of interfering organic substances y ultraviolet irradiation and oxidation. Bilikova (4B) described a sensitive, 0.05-0.1 mg/L, and specific extractionphotometric method for the determination of copper in water using dicupral as the complexing agent. The effects of acid and iron concentrations on the determination of copper using electrothermal-Zeeman atomic absorption spectrometry were investigated by Atsuya, Ito, Otomo (2B). Conditions were established where the effects of these variables were negligible. In addition, the implementation of a miniature inner cup and the preconcentration of copper from water by coprecipitation with lead sulfide provided increased sensitivity. Liquid-liquid extraction was coupled with atomic absorption spectrometry for the determination of copper in water as proposed by Silva and Valcarcel (62B). Copper was complexed with 1,Pnaphthoquinone thiosemicarbazone, extracted into methyl isobutyl ketone and measured a t 324.8 nm. The sensitivity was 0.6 ng/mL for l % absorption in aqueous solution and the presence of several milligrams of 55 other ions was shown to have negligible effect. Brown et al. (BB)discussed initial studies on the application of high-performance liquid chromatography to the identification of organocopper speciation in soil-pore waters. Reversed-phase chromatography combined with ultraviolet detection for organocopper molecular species and graphitefurnace atomic absorption for inorganic copper provided quantification. Trace copper was determined, using thin-layer chromatography in a method proposed by Kataeva (29B). The method involved the chelation of copper with sodium diethyldithiocarbamate, extraction into chloroform, separation on Silufol, and detection with 0.05% dithizone in chloroform. The linear working range of the method is 0.2-20 pg of copper. Nelson and Mantoura published three papers on the voltammetry of copper species in estuarine waters. Part I (43B) described the electrochemistry of copper species in chloride media. Studies showed that copper electrodeposition in a chloride medium on a hanging mercury drop electrode was controlled by competitive reduction between copper(I1) organic s ecies and copper(1) chloride intermediate. In Part I1 (44Bpestuarine waters were assayed by stripping polarography and results indicated that adsorption mechanisms are significant in the reduction of organocopper in these waters. In addition, voltammetric titrations were conducted to identify the mechanism. In Part I11 (45B) a comparatively non-copper-complexing surfactant, gelatin, was substituted on the hanging mercury drop electrode for natural organic material during differential-pulse anodic strippin voltammetric assay of estuarine waters. The effects of a sorption of natural
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ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
organic material on the electrodeposition and electrooxidation of copper were shown to be diverse and resulted in part through the complexing properties of the organic material. Square-wave polarographic determination of copper in seawater by means by coprecipitation with zirconium hyroxide was discussed by Uzawa and Yoshimura (76B). Thirty milligrams of zirconium was added to l L of seawater and pH adjusted with ammonium hydroxide to copreicipitate copper. The precipitate was dissolved, diluted, and analyzed polarographically at -0.27 V vs. the mercury pool. Copper in seawater at 2.5 pg/L was determined with good precision and 0.1 mg of cadmium, lead, zinc, iron, nickel, cobalt, magnesium, and bismuth did not interfere. Theoretical aspects of the direct titration of natural waters for gainin information on trace metal speciation was outlined by Ruzic &B). Interpretation is based on a graph of the ratio between the free and bound metal concentration vs. the free metal concentration. The application of this technique, which is based on a 1:l complex formation model, is discussed with respect to trace metal speciation. Interpretation of experimental results are proposed for cases where two types of complexes with different conditional stability constants are formed or where the metal is adsorbed on colloidal particles. Advantages and limitations of this approach in comparison to earlier methods are outlined with respect to copper(I1) in seawater. A study was conducted by Terada, Matsumoto, and Kimura (70B) into the sorption and desorption of copper(I1) from 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2,5-dimercapto-1,3,4-thiadizole loaded on silica gel, activated carbon, or poly(trifluorochloroethy1ene) powder. The separations were compared with those based on precipitation or extraction with these reagents. Affinity chromatographic gel was coupled to carboxymethyl(imino)bis(ethylenenitrilo)tetraacetic acid by a carbodiimide reaction and successfully implemented for concentrating copper from seawater in a method described by Culberson et al. (15B).The resulting gel is selective and useful in the range of pH 4 to 9 and is stable and reversible over a 9-month period. Up to 20 pmol copper can be adsorbed and recovered with 99% efficiency with 1g of coated gel. Cervera, Cela, and Perez-Bustamante (11B) implemented solvent sublation for the separation and preconcentration of copper in the form of a dithiazonate. Experimental parameters were studied and optimized and the process was applied to the quantitative separation of trace amounts of copper from seawater. A detailed study was conducted by Tarafdar and Rahman (69B) for the preconcentration of copper from water by plating it out onto zinc dust prior to spectrophotometric determination. They found that 50 ppb copper could efficiency be concentrated from 250 mL of solution with 95% recovery using 100 mg of zinc dust, 90% recovery for 500 mL. Experiments showed that various metal and nonmetal ions generally present in surface water do not interfere. The complexation of copper by aquatic humic matter was investigated by Becher et al. (3B) using reversed-phase liquid chromatography and flameless atomic absorption spectrometry. The major portion of the metal was found as ionic or highly polar complexes; however, significant amounts were also found in fractions containing less polar compounds. Simoes Goncalves and Correia dos Santos (63B)utilized direct current polaragraphy at a dropping mercury electrode and dc voltammetry at a rotating platinum wire electrode to obtain stability constants of copper(1) and copper(I1) chlorocomplexes in seawater. The systems were quasi-reversible and two different calculation methods were used to determine the formation constant of the copper(1) chlorocomplex. In addition, the transfer coefficient and the rate constant were determined. Multimetal. Preliminary evaluation of the use of 4-(2pyridylazo)resorcinolas a precolumn chelating agent for liquid chromatographic simultaneous multielement determinations was discussed by Roston (56B). A conventional reversed-phase chromatography system was used with fixed wavelength ultraviolet absorption and oxidative thin-layer amperometry for chelate detection. Results indicated that the determination of metal ions, such as, copper(II), cobalt(II), nickel(II), and iron(II), at the parts-per-billion level was feasible. Bond and Wallace (6B)developed an automated technique for the determination of nickel and copper by liquid chromatography
WATER ANALYSIS
with electrochemical and s ectrophotometric detection. In situ formation of dithiocar amate complexes, separation of the complexes by high-performance reverse-phase liquid chromatography, and the use of dual detectors were included as integral components in the monitoring system. The versatility associated with the separation and detection system allows the determinations of these analytes at trace levels and within extremely large variations in concentration ratio. Phenylbenzimidazolylazoketoxime and o-phenanthroline were used by Dubinina et al. (I7B) in the formation of mixed-ligand complexes with cobalt, copper, and vanadium. The metal complexes were measured spectrophotometricallyand applied to the analysis of natural waters. The detection limits were 0.001,0.01, and 0.001 p g / d for cobalt, vanadium, and copper, respectively. Motomizu (39B)conducted a fundamental study of the determination of iron and cobalt using 2-nitroso-5dimethylaminophenol as a color reagent in a flow injection system propelled by gas pressure. The sample was injected into the reagent stream and the chromophores of iron(I1) and cobalt(II1) measured at 750 and 530 nm, resyectively. The linear working range for iron(I1) was 2 x 10- to 5 X lo4 M; cobalt(II1) was 5 X lo-' to 6 X lo4 M. Interference studies were conducted with respect to each analyte. Trace iron and chromium were determined in aqueous solutions by laser-intracavity atomic absorption spectrometry by using a dye laser and a tantalum-rhenium alloy furnace atomizer as outlined by Burakov et al. (9B). The detection limits were 1.2 X for iron and 4 X for chromium in 10-pL samples. Reggers and Van Grieken (54B)described a preconcentration method for transition metals from water based on complexation with 2,2'-diaminodiethylamine-modified cellulose. The complexing capacity was 1.5 mequiv/g and recovery was 85%. The method was not affected by humic substances or alkali or alkaline-earth metal ions. 2nd Series. Molybdenum. The catalytic action of molybdenum on the oxidation of iodide by peroxide in acidic medium was combined with flow injection analysis and spectrophotometric detection for the determination of molybdenum by Fang and Xu (19B).The reaction product absorbance was measured at 350 nm and the linear concentration range was 1-1000 pg/L. Replicate determinations of 50 and 13 pg/L molybdenum samples gave relative standard deviations of 0.83 and 19%,respectively. The detection limit for the method was 0.7 pg/L molybdenum using 200-pL injections and a sampling rate of 90 per hour. Ivanova et al. (27B) evaluated an extraction-photometric technique for the determination of molybdenum in drinking water. The method is based on the formation of the thiocyanate-containing complex of molybdenum(V) with crystal violet. The resulting complex is extracted with toluene and measured at 590 nm to give a determination range of 0.02-0.2 mg/L molybdenum. A rapid spectrophotometric method for the determination of molybdenum(V1) in seawater based on extraction with capriquat in benzene and back-extraction with aqueous trichloroacetic acid was described by Shijo, Ide, and Sakai (60B). The absorbance of the analyte chromophore was measured at 460 nm. The relative standard deviation for analyses of seawater containing 11.3pg/L dissolved molybdenum(VI)was 2.1%. The reaction of tetrahalocatecholmolybdic acid complexes, formed in situ, with basic dyes in an acid medium was the basis of a method proposed by Vinarova, Malinka, and Stoyanova (77B). The 1:2:1 complex of molybdenum with tetrabromocatechol and dye was stable for 1 day; however; the complex with tetrachlorocatechol was stable for only 15 min. Molybdenum was selectively adsorbed from natural waters on Sephadex gel, desorbed reversibly with EDTA, and determined by atomic absorption spectrometry or photometrically with bromopyrogallol red as outlined by Yoshimura, Hiraoka, and Tarutani (86B).The detection limit for 250-mL water samples was 1 pg/L and large amounts of sodium chloride had negligible effects on the determination thereby allowing application to seawater analysis. Ternero and Garcia (72B)preconcentrated molybdenum on Chelex 100, complexed the eluted analyte with 174-dihydroxyphthalimidedithiosemicarbazone, and quantified molybdenum using atomic absorption spectrometry. Interferences commonly present in natural waters were eliminated by the addition of ascorbic acid prior to the extraction. The sensitivity of the method is 0.3 pg/L for 1 % absorption.
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Mok and Wai (34B) preconcentrated molybdenum with p rolidinedithiocarbamate and diethyldithiocarbamate into c loroform before neutron activation analysis. A specific extraction pH was selected to eliminate the interference from the 236U(n,f)ggMo. Reaction and interferences in seawater matrices, such as sodium and bromines, were removed during the extraction. Ruthenium. A method for the determination of trace amounts of ruthenium in brines was based on the extraction of its hexamethylenedithiocarbonate complex followed by atomic absorption measurement as discussed by Dornemann and Kleist (16B).Recovery of ruthenium ranged from 98 to loo%, and the limit of detection was 0.05 pg/L ruthenium. Palladium. Palladium-containing wastewaters were analyzed using an extraction-photometric technique developed by Aneva (IB). The method uses 2-nitroso-naphthol at H 1.5-3.5 in the presence of ethylenediaminetetraacetic aci to form a stable complex with palladium. EDTA eliminates interferences from other cations. The detection limit was 0.06 mg/L with a maximum error of 0.1-0.9 mg/L. Terada, Matsumoto, and Taniguchi (71B)preconcentrated palladisilica um(I1) on 2-mercapto-N-2-naphthylacetamide-loaded from aqueous solution before atomic absorption determination. The chelating capacity of the gel was 7.5 pmol/g palladium at pH less than 4, and palladium was quantitatively eluted with 20 mL of 0.2 M thiourea in 0.1 M hydrochloric acid. Silver. Spectrophotometric determination of silver by 4,4'-bis(dimethy1amine)thiobenzophenone was the method of choice for Stryjewska and Rubel (67B). The method permitted the determination of silver(1) in the presence of an excess of copper(II),lead(II), cadmium(II),nickel(II), iron(III), chromium(III), and zinc(I1). Mercury(I1) and anions complexing silver(I), such as thiocyanate, thiosulfate, and the halides, interfered. Bloom and Crecelius (5B) designed a method for the determination of silver in seawater using coprecipitation with cobalt(I1) pyrrolidinedithiocarbamate from 200-mL samples. The resulting precipitate was dissolved and analyzed by Zeeman graphite-furnace atomic absorption spectrometry. The method has a detection limit of 0.1 ng/L and also allows for simultaneous extraction of lead, copper, cadmium, and nickel. The detection limits ranged from 1to 3 pg for the determination of silver using diethylenetriamine, ethylenediamine, and triethylenetetraamine as activators for chemiluminescent analysis as reported by Pilipenko, Karentniova, and Trachevskii (50B). The method was applied in the determination of silver in mineral water preserved with silver and in supernatants from studies of the bactericidal effects of silver. Stryjewska and Rubel (66B)compared voltammetric, spectrophotometric, and atomic absorption techniques in the determination of silver in wastewater. The optimum operating ranges for each method were 0.001-0.5, 0.05-6, and 0.002-0.04 mg/L silver for the subject techniques, respectively. 3rd Series. Osmium. The absorbance and luminescence spectra of osmium(1V)-activated A2BX6crystallophosphors, where A is potassium, rubidium, or cesium, B is tin, and X is halide, were studied in terms of their analytical properties by Karyakin et al. (28B). Phosphors such as potassium stannic hexachloride and cesium stannic hexachloride were used to determine osmium in wastewater with detection limits of 5 x lo4 and 1 X lo-' g per 0.1 g crystallophosphor,respectively. Quantitation employed the method of standard addition and measurement of analytical line intensity at 708 and 966 nm. Gold. A method for the determination of gold in water was presented by Hamilton, Ellis, and Florence (21B). Gold was preconcentrated batchwise from 1L of water at pH 3 to 4 onto 0.1 g of activated charcoal prior to treatment by instrumental neutron activation y-ray spectrometry. Activated charcoal was shown to quantitatively adsorb ionic and colloidal gold from synthetic and surface waters spiked and equilibrated with these forms. Three ion exchange resins and electrodeposition at a carbon fiber electrode were also evaluated for preconcentration effectiveness;ionic gold removal was quantitative, but colloidal gold was incomplete. The detection limit for the charcoal procedure was 0.3 ng of gold.
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Group 12 Metals Zinc. Zinc was spectrophotometrically measured following complex formation with a,P,y,&tetrakis(1-methylpyridiniumANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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3-y1)porphine (HL +) at pH of 10.5 in a method described by Ishii, Koh, a n i datoh (IOC).Copper(I1) was was added to complex excess ligand and the zinc(I1) complex was decomposed by acidifying the solution and the subsequent H4L6+ absorbance of the Soret band measured. The sensitivity for 0.001 absorbance was 0.186 ng/cm2 and the relative standard deviation was 0.48%. The determination of zinc in tap water based on thermally activated delayed fluorometry of zinc complexes with mesotetraphenylporphinetrisulfonic acid is described in a technique authored by Onoue et al. (22C). The chelated compound was adsorbed onto filter paper and the fluorescence recorded at 607 nm after a 25-ms delay. The calibration curve was linear from 1to 162 ppb zinc, and the relative standard deviation for nine replicate analyses at 22 ppb zinc was 1.2%. There was no interference from cadmium, iron, chromium, lead, indium, tin, copper, or nickel. Santiago et al. (25C) designed a method for zinc quantification in seawater using spectrofluorometric measurement. The technique uses a aqueous ethanol medium a t pH 10.5-13.5 and benzyl 2-pyridyl ketone 2-quinolylhydrazoneas the fluorogenic reagent. Seawater samples analyzed by this method were compared to results obtained using atomic absorption spectrometry. Wang and Green (3IC) reported a method using anodic stripping voltametry in a flow system in the determination of zinc in natural waters. A mercury-film disk electrode and exchange of electrolyte solution between the deposition and stripping stages were implemented and the samples did not require deaeration. Cadmium. Cadmium was determined in natural waters and zinc-based alloys by extraction of its 1:2 complex with diantipyrylthiourea from 0.2 M ammonium hydroxide into chloroform, reextraction into an a ueous phase containing Complexon I11 and sulfuric acid, adlition of Chrompyrazole, ascorbic acid, and potassium iodide, and measuring the absorbance of the chromophore in a technique outlined by Degtev, Toropov, and Zhivopistsev (5C). The selectivity of the method was tested. Pruszkowska, Carnrick, and Slavin (23C) determined cadmium directly in coastal seawater by atomic absorption spectrometry with a stabilized temperature platform furnace and Zeeman background correction. The detection limit of 0.013 pg/L in 12-pL samples or about 0.16 pg absolute was attainable and the characteristic integrated amount was 0.35 pg of cadmium per 0.0044 absorbance units. An ammonium hydrogen phosphate and nitric acid matrix modifier was employed and cadmium concentrations calculated directly using a calibration curve. No - interferences were identified. Preconcentration of trace heavy metals in large aqueous samples by coprecipitation-flotation in a flow system was described by Mizuike, Hiraide, and Mizuno (19C). In a sample stream flowing a t 0.5 L/min trace heavy metals are quantitatively coprecipitated with indium hydroxide and floated with sodium oleate and nitrogen gas. Cadmium at nano ramper-liter levels in 20 L of water is concentrated 2000-fol~with recoveries of greater than 93%. Nakashima and Yagi ( 2 I C ) discussed the measurement of cadmium by electrothermal atomic absorption spectrometry following preconcentration and flotation separation. Cadmium was coprecipitated with zirconium oxide at pH 9.1 and floated with the aid of a surfactant and gas stream, collected, and dissolved in dilute hydrochloric acid. The total time required for preconcentration of cadmium from a 1-L sample is 40 min. Kanzaki, Tonoike, and Katsura ( I I C ) implemented the ferrite process to trace cadmium determination. To a 1-L sample solution containing 1 to 10 pg of cadmium, 200 mg of iron sulfate is added and the pH adjusted with sodium hydroxide. As the iron(I1) in solution is partially oxidized by an air stream of 0.1 L/min and 65 OC, the spinel-type ferrite is formed in solution. The completion of the reaction is monitored by the change in the redox potential. The precipitate is separated magnetically, washed with water, and dissolved in concentrated hydrochloric acid. Recoveries for 10 ppb and 1 ppb cadmium were 98 and 90%, respectively. The concentration factor using this technique is 200. Cadmium was complexed with sodium diethyldithiocarbamate,extraced into chloroform, and measured using flame atomic absor tion in a method described by Beaupre, Holland, and Mcaenney (2C). The method was applied in a study of the distribution of cadmium in the Great Lakes and groundwater systems of Ontario, Canada. 52 R
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Mercury. Mercury was determined in water and copper-zinc ores by complexation, extraction, and spectrophotometric detection in a method described by Barbina and Podchainova ( I C ) . Mercury’s 1:2 complex with 1-(1phthalazinyl)-3,5-diphenylformazanat pH 7 is extracted into chloroform and photometrically quantified at 520 nm. The detection limit was 3.4 pg/L mercury. Extensive studies were conducted into method properties and correlations were drawn. Matsibura, Ryabushko, and Pilipenko ( I S C ) studied the reactions of mercury(1) and mercury(I1) with Michler’s thioketone in application to the analysis of wastewater. Ethanol and dimethylformamide solvent systems were investigated. The molar absorptivities of the thioketone complex L/(mol cm) in 40% ethanol and at 560 nm were 1.25 X 1.7 X 10” L/(mol cm) in 20% dimethylformamide and the detection limit in the dimethylformamide/water system was 0.01 pg/mL mercury. A glass reaction vessel was described by Kupchella, Syty, and Mahfood (14C)for use in the cold vapor atomic absorption spectrometric determination of mercury in wastewater. The vessel provides for continuous carrier gas flow, septum-covered injection port, rapid reagent addition, and drain stopcock. Implementation of the apparatus gave a detection limit of 1 ng/mL and a relative standard deviation of 2.9% at 40 ng/mL mercury. Freimann and Schmidt (7C) discussed systematic errors in the determination of trace amounts of mercury in seawater by cold-vapor atomic absorption spectrometry. They pointed out that these types of errors could be avoided by using a Teflon vessel for both the sampling and reaction of the sample with stannous chloride and amalgamation with gold powder. The detection limit for the method is 0.5 ng/L and the relative standard deviation at 1.5 ng/L is 4%. An automated continuous monitoring system for the determination of total or inorganic mercury by cold-vapor atomic absorption spectrometry was developed by Goto et al. (8C). The technique uses continuous flow digestion, reduction, and extraction in small-bore tubes at slow flow rates and is applicable to natural waters and wastewates. The detection limit of 0.1 ppb can be realized by using a condenser circulated with ice-chilled water for condensing the water vapor and an 8-pL flow cell. The amount of reagents required is about one-tenth that required in an AutoAnalyzer method and the response time for total mercury determinations is about 5 min. Robinson and Skelly (24C) reported that a technique based on the use of a quartz-tee atomizer and sample introduction on a carbon disk or by direct injection can be coupled to an atomic absorption spectrometer to give more accurate results as compared to the cold vapor technique. Measurement was made using the 184.9 and 253.7 nm resonance lines and eliminated the need for pretreatment and preconcentration. Ultratrace concentrations of mercury in the North Sea, Baltic Sea, and Arctic Ocean were measured using an integrated single-vessel and atomic absorption spectroscopy as reported by Schmidt and Freimann (26C). Mercury was preconcentrated by amalgamation of mercury vapors on a gold wire in a method outlined by Dmitriev, Granovskii, and Slashchev (6C). The preconcentrated mercury is volatilized at 900 “C and measured using flameless atomic absorption spectrometry. The detection limit was 0.01 ng of mercury, and details of sample preservation and decomposition of biological and environmental samplex were given. Yao, Akino, and Musha (35C) described a technique using immobilized chelating ligands for preconcentrating mercury prior to atomic absorption spectrometric analysis. The preconcentrating system is composed of two minicolumns in series, one packed with iminoacetate coated silica to sequester inorganic mercury and another packed with dithiocarbamate coated silica to sequester organic mercury. The pH adjusted sample is passed through the columns at 10 mL/min followed by 20 mL of 0.1 M hydrochloric acid. The dried columns are then inserted into the furnace of a Zeeman-effect mercury analyzer to strip off the mercury(I1) and organic mercury. The limit of detection was 10 pptr (parts per trillion) when 100 mL of sample is used and the relative standard deviation was less than 4%. Yamamoto, Kaneda, and Hikasa (34C) demonstrated that picogram amounts of methylmercury in seawater can be determined by gold amalgamation and atomic absorption spectroscopy. Methylmercury is extracted into benzene, concentrated by successive extractions, and transferred into a dithizone-chloroform solution before photometric
WATER ANALYSIS
measurement. The detection limit was 0.005 ng of methylmercury when 3.6 L of seawater was treated and the relative standard deviation for 10 ng was about 1%. Total mercury was also determined and the percentage of methylmercury calculated for the seawater sample. Thompson and Coles (30C) enhanced the sensitivity of mercury determination in environmental samples by inductively coupled plasma atomic emission spectrometry by the addition of tin(I1) chloride solution and passing the mixture immediately through nebulizer and into the - a pneumatic plasma source. Bis(diethy1dithiocarbamato)copper in carbon tetrachloride was employed by Smejkal and Tepla (29C) as a complexforming reagent in a sub- and swereauivalent method of isotope-dilution analysis for the dkermhation of active and inactive mercury in the range of 1-30 pg in an acetate buffer a t pH 4.6. This technique is directly applicable to water analysis. Lo et al. (16C) discussed the preconcentration of mercury with lead diethyldithiocarbamate prior to neutron activation analysis. Samples with mercury at the parts-perbillion level could be analyzed and the procedure was successfully used in an environmental mercury pollution control pro ram. A method using dithizone and a low-melting fatty acil, of more than 17 carbon atoms, for extraction preconcentration of mercury was proposed by Lobanov et al. (17C). The method was verified using synthetic mixtures and the standard deviation was 0.5% for determining 56% mercury in diphenylmercury. A nondispersive fluorescence spectrometer was designed by Kimoto et al. (12C) for determining picogram concentrations of mercury in water and air. In water samples mercury liberated from the solution via reduction-aeration is trapped on gold filaments. On heating, mercury is liberated from the filaments and introduced into a flow-type fluorescence cell where the fluorescence is measured. The detection limit was 0.005 ng and the coefficient of variation was 3% for 1ng of mercury. Chiba et al. (3C) showed that alkylmercury in seawater at the nanogram-per-liter level could be determined by gas chromatography-atomospheric pressure helium microwave induced plasma spectroscopy. The detection limits for methylmercuric chloride, ethylmercuric chloride, and dimethylmercury were 0.09,0.12, and 0.40 pg/L, respectively. The method was applied to the determination of alkylmercury in seawater following preconcentration using benzene-cysteine extraction. Cui (4C) applied anodic stripping voltammetry using gold electrodes for the determination of mercury in water. The stripping current was linearly related to mercury concentration in the range 0.01-10 ppb. Recovery of 0.10-4.0 ppb added mercury in natural water ranged from 95 to 107% and the relative standard deviation was 1.8%. Trace mercury in water was preconcentrated with sulfhydryl cotton for ring-furnace determination in a method proposed by Liu (15C). The stated detection limit was 0.004 pg, the concentration working range was 0.01-0.3 pg, and experimental recoveries ranged from 100 to 107%. Zebreva, Matakova, and Zholdybaeva (36C) compared polarographic and stripping voltammetric methods for determing cadmium and zinc in wastewater. Both were found to be effective; however stripping voltammetry using a mercurygraphite electrode was more advantageous in terms of analysis time. Trace uantities of cadmium and zinc in natural waters and other su7Jstances containing significant concentrations of halides were determined by Shcherbakov, Belyaev, and Demkin (27C) using atomic absorption spectroscopy coupled with a special graphite rod that is used to electrochemically preconcentrate the analytes and also serves as the atomizer. Detection limits using the technique were 2.5 x10-5 pg/mL for cadmium and 7.0 X pg/mL for zinc using spectral resonance lines 222.8 nm for cadmium and 213.8 nm for zinc, A study conducted by Morita et al. (20C) indicated mercury absorption by solutions containing oxidants such as dichromate, manganese dioxide, cerous sulfate, and silver nitrate. The rate of mercury vapor absorption into solutions Containing mercury(I1)and/or these oxidants is enhanced with increasing mercury(I1) concentration and with increasing oxidation potential; a mechanism is proposed for this transfer. Wang et al. (32C) studied the absorption of methylmercury(1) and mercury(I1) in aqueous solution by sulfhydryl-cotton using X-ray photoelectron spectroscopy. Results show two distinctive peaks in the spectrum with corresponding binding
energy at about 105 and 101 eV in both cases. In the case of methylmercury(1) one bond between mercury and sulfur is formed, whereas for mercury(II), two bonds between mercury and two sulfur atoms are formed. The necessity for optimal analytical conditions in dynamic studies of mercury concentrations in seawater is described by Simeonov and Andreev (28C) for a particular sampling study. Correlation coefficients suggest that the subsurface layers are important in pollutant dynamics with respect to mercury. Kimura and Arikado (13C) discussed the loss of mercury(I1) from solution as a result of aeration. The rate of mercury loss increased with increasing air velocity and with temperature of the solution. Addition of complexing agents and/or oxidizing agents was effective in eliminating mercury loss. Wrembel(33C) studied the exchange phenomena of mercury and their effects on the determination of ultramicroconcentrations in water. The exchange of mercury between aqueous solution and container walls, due to sorption or dissolution-desorptionprocesses from the container walls or to pasage through container walls from ambient air, was investigated using low-pressurering discharge atomic emission spectroscopy. Changes in mercury concentration from lo4 to g/L depended on the container material and were highest during long-term storage of the samples in sodium glass and polyethylene containers. Humic acid was shown to prevent significant loss of trace mercury(I1) from aqueous solutions in polyolefin containers by Heiden and Aikens (9C). At a level of 90 mg/L, humic acid reduced losses from solutions containing 1mg/mL mercury(I1) over 15 days to less than 10%. Humic acid suppresses mercury loss better than preservatives based on nitric acid and other oxidants. Group 13 Elements
Aluminum. Campbell et al. (20) described a procedure for the speciation of aluminum in acidic freshwaters. After filtration through polycarbonate membrane filters, filtrates were differentiated on the basis of their kinetic and thermodynamic properties with a fractionally loaded Chelex 100 ion exchange column (75% hydrogen form). Monomeric hydroxoand fluoroaluminum complexes exchanged readily, as did low molecular weight polynuclear species. Forms of aluminum assoeiated with fulvic and humic acids of natural origin exchanged more slowly. Wyganowski, Motomizu, and Toei (70) reported on a flow injection spectrophotometric system for the determination of aluminum in river water. The reaction reagents consisted of bromopyrogallol red, n-tetradecyltrimethylammoniumbromide, and hexamine in 60% ethanol solution, and the carrier solution was 1,lO-phenanthroline, hydroxylammonium chloride, and an acetate buffer. Samples acidified by sulfuric acid are injected and the peak absorbance at 623 nm was measured, yielding a detection limit of 0.001 ppm. Experiments on the formation of ternary complexes of aluminum with Eriochrome Cyanine R, Chrome Azurol S, and Pyrocatchol Violet in the presence of zephiramine, CTAB, or cetylpyridinium chloride were performed by Marczenko and Jarosz ( 5 0 ) . They recommended a spectrophotometric method based on the aluminum-Eriochrome Cyanine R-zephiramine complex for the determination of aluminum in river water. Comparison studies of continuous-flow and flow-injection techniques for the photometric determination of aluminum in water samples were performed by Zoeltzer and Schwedt (90).An absorbing complex was formed between aluminum and Chromazurol S. Interferences by iron(II1) were eliminated with ascorbic acid. The flow-injection determination showed more peak symmetry, higher sampling frequencies, and better reproducibility than the continuous-flow system. Detection limits are 10 ng/mL. Wyganowski, Motomizu, and Toei (80)reported the spectrophotometric determination of aluminum with bromopyrogallol red and a quaternary ammonium salt. They stated that aluminum in river water at the 100 Mg/L level was determined by reacting the bromopyrogallol in the presence of n-tetradecyltrimethylammoniumbromide to form a ternary complex with an absorption maximum at 623 nm. Interference from iron was masked with hvdroxvlammonium chloride and 1,lO-phenanthroline. ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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A procedure was developed by Nemodruk et al. (6D)for the photometric determination of aluminum in natural waters with Chromazurol S in the presence of Sintanol DS 10 as nonionic surfactant. The procedure determined aluminum at 0.1 to 10 pg/L with a relative standard deviation of 0.03-0.12. Interferences from copper, iron, and other elements were eliminated by masking with thioglycolic acid. The direct determination of aluminum in natural waters by stepwise laser photoionization was described by Bekov et al. (ID). This new, highly sensitive technique was based on single atom detection and involves thermal ionization of the sample in vacuum and the detection of the element atoms through their stepwise excitation to a Rydberg state and ionization in electric field pulse. Isozaki, Kawakami, and Tusumi ( 4 0 ) described a technique for the determination of aluminum in water based on electrothermal-atomic absorption spectrometry. Aluminum was atomized directly from a chelating resin suspended in the graphite tube without weighing the resin or elution of the aluminum. A batch exchange process was used prior to the filtration of the loaded resin from the sample solution. A 10-pL suspension of the resin was directly injected into the graphite tube. The calibration curve was linear up to 4 ppb with a relative standard deviation of 4.1% at 2 ppb. Thallium. Hoeflich, Gale, and Good ( 3 0 )used differential pulse polarography and differential-pulse anodic stripping voltammetry for the determination of trace levels of thallium. The simultaneous determination of thallium and dimethylthallium by both techniques was described for various buffered matrices. Detection limits were 130 and 250 ppb, respectively, for conventional differential-pulse polarography. Corresponding values were 3.2 and 3.4 ppb for differential-pulse anodic stripping voltammetry. Ethylenediaminetetraceticacid was added to prevent interference from other metal ions. Group 14 Elements
Lead. De Jonghe, Van Mol, and Adams (6E)described a simple extraction procedure for the sensitive determination of trialkyllead compounds in water. After enrichment by vacuum distillation and saturation of the residue with sodium chloride, the analyte was extracted into chloroform. The extract was acidified with sulfuric acid and back extracted into the aqueous phase. The analysis was completed by graphite furnace atomic absorption spectrometry, achieving a detection limit of 0.02 pg/L. Rowley, Law, and Husband (16E) described the use of a polystyrene supported poly(maleic anhydride) resin for the preconcentration of lead from tap water. After elution with dilute nitric acid, the lead was determined by flame atomic absorption spectrometry to a detection limit of 50 ng mL. A technique for the concentration of lead from fres and saline waters prior to analysis by atomic absorption spectrometry was described by Matthews (12E). The lead was absorbed quantitatively on manganese dioxide supported on glass fiber filters at 75 mg of lead/g of manganese dioxide. Alonso et al. (2E)described a technique for the separation of lead prior to atomic absorption by complexing it with salicyclohydrazones of di-Ppyridyl ketone and 2-benzoylpyridine followed by solvent extraction into methyl isobutyl ketone as the perchlorate ion pair. The advantages of this technique include (a) high sensitivity, (b) wide pH range for extraction (4-ll), and (c) the use of a solvent medium that forms nontoxic products in the flame. Shrivastava and Tandon (17E) reported a coprecipitation procedure for the preconcentration of lead from natural, polluted, and synthetic water by atomic absorption spectrometry. They used zirconium hydroxide as the precipitation carrier. De Mora and Harrison (7E) reported on experiments to determine the efficiency of the preconcentration of lead from tap water by the use of chelating resins. They found that the use of Chelex 100 in the calcium form was unsuitable for totallead, however, polystyrene-supported poly(ma1eic anhydride) resin completely removed lead in a batch mode but not when used in a column. Lead was determined by a continuous-flow, hydride-generation atomic absorption procedure by Jin and Taga (11E).Three chemical approaches for the generation of plumbane were investigated. Sensitivities (0.0044 absorbance) and plumbane generation efficiencies were 3.2, 1.7, and 1.1 ng/L and 33,47, and ?Os%, respectively for maleic acid/potassium dichromate, nitric acidlhydrogen peroxide, and nitric acid/ peroxydisulfate all reduced with sodium borohydride.
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They recommend a dithizone extraction followed by a backextraction to eliminate interferences from silver, gold, copper, and cadmium. Fukushi and Hiro (1023) used an electrolytic deposition technique to separate and preconcentrate lead from seawater prior to analysis by graphite-furnace atomic absorption. Lead was deposited on a cylindrical platinum electrode at 2 V for 2 h. Results compared favorably with those determined by diethyldithiocarbamate-methyl isobutyl ketone solvent extraction. Fletcher (9E)measured lead concentrations in 30 different well and surface water samples by using direct, standard addition, and lanthanum matrix modification procedures with electrothermal-atomization atomic absorption spectrometery. He reported a suppressive interference in most samples by the direct procedure. This interference was eliminated by the addition of nitric acid and lanthanum chloride or lanthanum nitrate. Estes, Uden, and Barnes (8E)have described a procedure for the determination of n-butylated trialkyllead compounds by gas chromatography with microwave plasma emission detection. Analytes were extracted into benzene from an aqueous solution saturated with sodium chloride. They were then quantitatively converted into the n-butyltrialkylead derivatives with a n-butyl Grignard reagent. Chau, Wong, and Kramar (5E) reported that dialkyllead, trialkyllead, and lead(I1) ions are quantitatively extracted into benzene after chelation with sodium diethyldithiocarbamate. The lead species were butylated by a Grignard reagent to tetrabutyllead. This species was quantified to a detection limit of 0.1 pg/L by a gas chromatographic-atomic absorption technique. Lead was determined in tropical seawater by anodic stripping voltammmetry in the differential-pulse and linear-sweep modes by Acebal and De Luca Rebello (123). They discussed the two techniques as well as the relative efficiencies of the hanging mercury drop and mercury thin-fiim electrodes. Tao, Liu, and Xu ( B E ) published a method for the determination of lead in surface water by a catalytic polarographic procedure. The technique utilized hydrochloric acid, vanadyl ion, potassium iodide, and ascorbic acid to induce a measurable adsorption current along with a parallel dynamic current. A catalytic current linearly related to lead concentration up to 0.4 pg/mL was measured at a peak potential of -0.46 V. Nishikawa et al. (14E)has reported that Calcein reacts with lead(I1) at pH 4 to form a 1:2 complex. This complex emits intense phosphorescence with an excitation maximum at 490 nm and a emission maximum at 620 nm with a lifetime of 4.5 ms at room temperature. They stated that a calibration curve was linear from 0.1 to 20 ng. Iron(III), nickel(II), and copper(I1) interfered with this determination but could be eliminated by using zinc sulfide paper to selectively separate the lead(I1). The recovery of this separation was greater than 93%. Tin. Andreae and Byrd (3E) described a hydride generation procedure for the determination of tin and organotin compounds in water. Graphite-furnace atomic absorption, quartz-cuvette atomic absorption, and flame emission spectrometry were all used for detection with limits of 50,50, and 20 pg, respectively. Camail et al. (4E)also determined traces of tin in freshwater and seawater by a hydride-generation atomic absorption procedure. Tin was quantitatively reduced to tin hydride in an acid medium in the presence of potassium permanganate using sodium borohydride. The hydride is transported by a nitrogen carrier to a heated quartz cell in a air-acetylene flame, atomized and measured at 224.6 nm. The detection limit was reported to be 1.2 wg/L. Tin in wastewater was determined by Zou, Yu, and Lian (19E)using a tungsten-coated graphite furnace atomic absorption procedure. The tungsten coating enhanced the tin absorption signal by more than 6-fold and improved its stability. The presence of phosphoric or nitric acids caused serious interference. Mueller (13E) developed a sensitive and specific method for the determination of tributyltin species in water and sediments. The procedure was based on the methylation of the tributyltin to tributylmethyltin which is separated by gas chromatography and detected by either flame photometry or mass spectrometry. The detection limits in water and sediment were 1 pptr and 0.5 ppb, respectively. Omar and Bowen (15E)determined tin spectrophotometrically after absorption and preconcentrationby polyurethane foam soaked in toluene-3,4-dithiol and complex formation with catechol
WATER ANALYSIS
violet and CTAB. Interfering substances were removed by converting the tin tetraiodide and extracting with toluene. Group 15 Elements
Bismuth, Lee (IF) described a method for determining picogram quantities of bismuth in environmental samples. Bismuth is reduced in solution to bismuth hydride with sodium borohydride, stripped with helium, and collected in a modified carbon rod atomizer for subsequent atomic absorption spectrometric analysis. The absolute detection limit was reported as 3 pg with a precision of 6.7% for 25 pg. Shimizu et al. (2F) determined bismuth in seawater by graphite-furnace atomic absorption after evaporative preconcentration and solvent extraction. Tartaric acid and ethylenediamminetetraacetic acid were added to the solution, and the pH was adjusted to 9.3. Sodium diethyldithiocarbamate was added and the resulting complex was extracted into carbon tetrachloride. The organic phase was placed on a rotary evaporator and reduced to near dryness. The residue was dissolved in nitric acid for transfer to the graphite furnace. A preconcentrtion factor of 1000 fold was achieved and a detection limit of 0.004 ng/L was realized. Metalloids
Boron. The association of boric acid and 3,5-di-tert-butylcatechol to form a complex anion that can be extracted into toluene as an ion pair with ethyl violet for subsequent spectrophotometric measurement was described by Oshima, Motomizu, and Toei (16G). The absorbance of the ion pair was monitored at 610 nm to give a linear calibration curve in the concentration range from the detection limit to 0.45 pg of boron and a molar absorptivity of 1 X lo6L/(mol cm). The method compared well with other methods in its application to the analysis of seawater. Several a-hydroxy acids were examined by Sat0 (22G) as complexing agents for the extraction-photometric determination of boron. Mandelic acid was found to be best for forming the boron complex. The complex is extracted with malachite green into benzene and boron is determined directly by measuring the absorbance at 633 nm. The linear working concentration range was 7.5 X lo-' to 1.5 X M boron and the method was applied to the determination of boron in natural waters. The reaction of boron with 2-hydroxy-2-methylbutyric acid in a weakly acidic medium to form a complex anion that forms an ion associated with malachite green was used by Sat0 and Uchikawa (23G) for the determination of boron in natural waters. The chromo hore absorbance was measured at 629 nm and the method h a f a linear concentration range of 7.5 x lo-' to 2.0 X M boron. The apparent molar absorptivity was 6.5 X lo4 L/(mol cm). The same authors (24G) used naphthalene2,3-diol to form a complex anion with boron that was extracted into benzene with crystal violet and photometrically measured at 610 nm. The linear working range in natural waters was 9X to 8 X lo4 M; the apparent molar absorptivity was 9 X lo4 L/(mol cm). The reaction of boric acid with 2,6-dihydroxybenzoic acid in a weakly acidic solution to form a 1:2 complex anion was implemented in the determination of boron by Oshima, Motomizu, and Toei (I7G). The anion complex is extracted into chlorobenzene as an ion associated with malachite green. The absorbance of this species is measured at 628 nm to give a linear working range up to 0.6 pg of boron and an apparent molar absorptivity of 9.5 x lo4L/(mol cm). Interferences from coexisting cations were eliminated by adding ethylenediaminetetraaceticacid. The advantages of the method are reaction occurs in a weakly acid medium, short reaction time, high sensitivity,and no significant interferences. The reaction of boron and hydrobenzoin in a weak alkaline medium was used by Sat0 and Uchikawa (25G) for the determination of boron in seawater. The resulting anion complex was extracted into benzene with crystal violet and photometrically quantified at 600 nm. The concentration range was 2.5 X lo4 to 2.5 X M boron. Experimental parameters such as pH, reagent concentrations, shaking time, complex stability, and solvent types were examined as were sources of interferences. Nazarenko, Flyantikova, and Chekirda (15G) studied the formation of 1:l:l compounds of boron with H-Resorcinol and various dyes, such as fluorescein, eosine, or erythrocine, in the presence and absence of diphenyl-
guanidine as a basis for the determination of boron in solution via spectrophotometric measurement. Beer's law was obeyed in the concentration range of 0.02-1.0 pg/mL boron when the fluorescein-H-Resorcinol boron complex is monitored at 510 nm. Motomizu et al. (IIG) determined boron by ion-pair liquid chromatography with 1,8-dihydroxynaphthalene-3,6disulfonic acid. The method used the reaction of boric acid with chromotropic acid and tetrabutylammonium bromide in an acetate buffer in the presence of ethylenediaminetetracetic acid prior to separation by reversed-phase liquid chromatography and ultraviolet detection at 350 nm. The peak area calibration was linear for 1-1000 ppb boron. Studies were conducted for the identification of interfering constituents. Boron in water was determined fluorometrically with dibenzoylmethane following extraction of boron into methyl isobutyl ketone with 2-methylpentane-2,4-diol as described by Aznarez, Bonilla, and Vidal(3G). The experimental conditions and the influence of potential interferents were researched. Fluorometric measurement of boron with chromotropic acid using flow injection analysis was examined by Motomizu, Oshima, and Toei (12G). Sample solution was injected into a carrier stream flowing at a rate of 0.85 mL/min and mixed, The absorbance maximum for the boronchromotropic acid complex was 313 nm. The linear working range for the system described was 0.5-5000 ppb with a detection limit of 0.2 ppb and a 160-pL injection volume. Experimental parameters such as pH, reagent concentrations, length of mixing coil, and flow rates as well as possible interferences were studied. Tsaikov, Boichinova, and Brynzova (32G)developed a coulometric procedure for the determination of boron in seawater with H-metric end point detection. Trujillo et al. (31G ) evaluatef different analytical methods for measuring boron in geothermal and natural waters. The authors showed that three colorimetrictechniques, two plasma emission spectroscopy methods, and thermal neutron-capture y spectroscopywere comparable and acceptable; however each had distinct advantages and disadvantages. Silicon. Flow injection analysis was used to automate the determination of silicate in natural waters by the molybdenum blue method as presented by Thomsen, Johnson, and Petty (30G). The method was specifically applied to the analysis of seawater and could achieve 80 determinations per hour on a continuous stream basis or 30 discrete samples per hour in duplicate. The relative precision was better than 1%for silicate concentrations greater than 10 pM and the detection limit was 0.5 pM silicon. The refractive index interference was eliminated and effects from salt and phosphate were discussed. Wang and Wang (35G) found that heteropolymolybdosilicic acid complex produces five well developed differential-pulse voltammetric peaks at a glassy-carbon electrode in citrate buffer containing 2-butanone that can be used to quantify silicon. The peak current at each peak potential was proportional to the silicon concentration. The linear concentration range of the most sensitive peak was to M silicon; the lower limit fixed by blank conditions. Germanium. Inorganic and methylgermanium species were determined in an aqueous matrix at the parts-per-trillion level through the combination of hydride generation, graphite-furnace atomization, and atomic absorption spectrometry as described by Hambrick et al. (8G). The germanium species are reduced by sodium borohydride to the corresponding gaseous germanes and methylgermanium hydrides, stripped from solution by a helium gas stream, and collected in a cold trap. The trap is then rapidly heated to release the germanes which are subsequently swept into the furnace. The absorption peak is recorded and electronically integrated to give detection limits of 155 pg for inorganic Ge, 120 pg of germanium as methylgermanium(III), 175 pg for germanium as dimethylgermanium(II), and 75 pg of germanium as trimethylgermanium(1). The precision of the determination ranges from 6% for trimethylgermanium(1) to 16% for methylgermanium(111). Arsenic. The usual pyridine or chloroform solution of silver diethyldithiocarbamate was replaced by iodine solution in a method based on the reduction of all forms of arsenic to volatile hydrides by metallic zinc in the presence of potassium iodide and stannous chloride as modified by Udal'tsova and Soldatova (34G). The arsine hydride is adsorbed into the iodine solution which is subsequently used to quantitate arANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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senic as arsenic-molybdenum blue at 750 nm. Tsuji et al. (33G)developed a sequential spectrophotometric method for the determination of inorganic arsenic(II1) and arsenic(V) species in groundwaters by coprecipitation with zirconium hydroxide. The photometric determination used silver diethyldithiocarbamate. Recovery experiments showed accurate and precise results could be obtained. Dodoo and Vrchlabsky (6G) optimized the silver diethyldithiocarbamate spectrophotometric method for the determination of arsenic in water. The optimal conditions were obtained through factorial design and simplex procedures. The reproducibility of the determination was less than or equal to 2.9% for arsenic concentrations in tap water from 2 to 50 pg/L. Arsenic in water was converted to a hydride and quantified as molybdoarsenic acid-Rhodamine-B spectrophotometrically in a method presented by Ye and Liu (38G). Recovery efficiency ranged from 92 to 104% and the relative standard deviations for ten determinations of 0.2 and 0.5 pg arsenic were 3-7% Zhou and Wang (39G)proposed a new procedure for the determination of trace amounts of arsenic in water. The method is based on the reaction of arsenic with silver acetate in the presence of Tween-80 to form a yellow solution that has an absorption maximum at 420 nm. Beer’s law is satisfied in the concentration range of 0.015-0.25 pg/mL arsenic and the molar absorptivity was 4.8 x lo4 L/(mol cm). Puttemans and Massart (19G)found that arsenic(II1) could be extracted quantitatively from an acidic medium with ammonium pyrrolidinedithiocarbamate and with diethyldithiophosphoric acid prior to analysis by electrothermal atomic absorption spectrometry. Arsenic(V) could be differentiated from arsenic(II1) by performing the determinations after the addition of a reducing agent. Arsenic was measured in seawater through the determination of dimethylarsinic acid in the sub-part-per-billionconcentration range by electrothermal atomic absorption spectrometry following preconcentration on an ion-exchange column as outlined by Persson and Irgum (18G). Elution parameters were optimized to enable the separation of dimethylarsinic acid from other sample constituents, such as group 11 and 12 metal cations, that may cause interference. The technique’s detection limit is 0.02 ng/mL arsenic. The fractional determination of arsenite, arsenate, monomethylarsonic acid, and dimethylarsinic acid in natural waters by hydride generation with atomic absorption spectrometry coupled to a cold-trap concentrator was described by Tanaka et al. (27G). The analytes were reduced with sodium borohydride to arsine, methylarsine, and dimethylarsine, respectively, and collected in the cold trap. Separation was brought about by sequential vaporization based on their boiling point differences. Detection limits were 4 pptr for arsenate and arsenite, 14 pptr for monomethylarsonic acid, and 26 pptr for dimethylarsinic acid. The relative standard deivations were 4.3% at 5 ng, 5.1% at 5 ng, 4.9% at 20 ng, and 3.7% at 30 ng, respectively. Maher (IOG) used a zinc-column arsine generator for the determination of methylated arsenic species. Monomethylarsenic (I) and dimethylarsenic (11) are reduced to arsine and subsequently decomposed in a carbon-tube furnace and measured by atomic absorption. The detection limits, based on 4 times the standard deviation of the blank analyses, were 0.006 pg/mL for I and 0.001 pg/mL for 11. The relative standard deviation at the 0.05 pg/mL level was 3.2% for I and 2.1% for 11. Arsenic in wastewater containing 500 mg L copper and iron and 100 mg/L nickel was determined by ydride generation and atomic absorption spectrometry at concentrations greater than 0.001 mg/L in a study described by Welz and Melcher (36G). Recovery experimental data and the identification and elimination of interferences were discussed. Arsine species obtained through hydride generation were separated by high-performance liquid chromatography and detected by inductively coupled plasma atomic emission in a method proposed by Bushee et al. (4G). The method was optimized with regard to detection limit, response linearity, and interferences for various arsenic species. The ability to speciate arsenic in drinking water was demonstrated. The preferential extraction of arsenite from water by 5 mL of a 0.01 M CBHI4solution of sec-dibutylthiophosphate for subsequent determination using graphite-furance atomic absorption was described by Charkraborti, Irgolic, and Adams (5G). The calibration range was linear to 1500 ng of arsenic, and 100 ng of arsenic could be confidently determined.
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Relative standard deviations of analyses of natural and synthetic river water spiked with arsenite ranged from 4.8 to 8.0%. The formation of volatile arsenic species during electrothermal atomic absorption spectrometric determination of arsenic was suppressed through the addition of nickel(I1) as described by Puttemans and Massart (2OG). Also many oxidizing agents, including nitric acid, substantially enhance the arsenic signal. Therefore, simplex optimization was used to optimize the concentrations of these reagents. These optimum values were 2000 ppm nickel(I1) in 2% nitric acid. Hudnik and Gomiscek (9G)described a procedure for the determination of arsenic and selenium in mineral waters based on electrothermal atomic absorption spectrometry. Both analytes were separated from macrocomponents by coprecipitation in hydrated ferric oxide, and the precipitate was dissolved in 0.2 M sulfuric acid prior to injection. The detection limits were 0.2 pg/L arsenic and 0.5 pg/L selenium. A two-stage anion exchange procedure was developed by Aggett and Kadwani (1G)for the speciation of inorganic arsenic(V) and arsenic(III), monomethylarsonic acid, and dimethylarsinic acid. Arsenic(II1) and dimethylarsinicacid were eluted in succession with a carbonate buffer and monomethylarsonic acid and arsenic(V) eluted with carbon dioxide-sodium chloride solution. The method was applied to the analysis in interstitial waters of sediment. Sadana (21G)proposed a method for the determination of arsenic in the presence of copper by differential-pulse cathodic stripping voltammetry at a hanging mercury drop electrode. Drinking water contaminated with copper(I1) was acidified and arsenic was preconcentrated in the mercury drop, followed by cathodic stripping. The resulting peak current was proportional to the arsenic in solution. The detection limit was calculated to be 1ng/mL and 10 replicate analyses of a natural water sample containing 10 ng/mL arsenic(II1) gave a relative standard deviation of 6.4%. A variant of the standard additions calibration procedure for the determination of arsenic in seawater by anodic stripping voltammetry was developed by Whang et al. (37G). The new technique uses two deposition times and two standard additions in the determination; the advantage being an accurate assessment of the background under the current peak is not required, assuming a constant background. A quantitative method for concentrating arsenic and antimony from salt water and freshwaters was described by Elson, Milley, and Chatt (7G). The method was based on the addition of selenium(1V)to an acidified sample followed by the precipitation of selenium by stannous chloride and the coprecipitation of arsenic and antimony. The precipitate was dissolved, dried, irradiated, and analyzed by neutron-activation y spectrometry. Detection limits were 9 ng of arsenic and 12 ng of antimony in 500 g of water and data were tabulated on the method performance for eight reference standards. Terada, Matsumoto, and Inaba (29G) employed 2mercapto-N-2-naphthylacetamideon silica gel for differential preconcentration of pg/L levels of arsenic(II1) and arsenic(V) from aqueous solution. Batch experiments quantitatively retained arsenic(II1) at pH 6.5-8.5; arsenic(II1) and organoarsenic compounds were not retained. Chelating capacity of the gel was 5.6 pmol of arsenic(III)/g at pH 7.0. Arsenic was determined by subsequent analysis of the silver diethyldithiocarbamate by atomic absorption spectrometry. Arsenic(V) was determined following reduction to arsenic(II1). Antimony, Nagaosa and Sana (13G)proposed a procedure for the determination of ng/mL to sub-ng/mL level concentrations of antimony(II1,V) in the presence of 5000-fold copper(I1) and 100-fold iron(II1) by differential-pulse anodic stripping voltammetry following extraction into acetonitrile. Deposition was carried out for 3 min at -0.35 V vs. silver/silver chloride. After 30 s, the stripping curves were recorded at a scan rate of 0.5 mV/s and a pulse amplitude of 10 mV. The peak current produced gave a linear calibration curve in the range of 0.2-20 ng/mL. The lower limit of determination was 0.1 ng/mL at a deposition time of 10 min. The coefficient of variation was 10% for 10 replicate determinations of 1.0 ng/mL antimony(II1 or V). Molecular photoluminescence detection was employed by Tao et al. (28G) for the determination of antimony and arsenic in river water and seawater. Hydrides of antimony and arsenic were generated and irradiated with ultraviolet light. The broad continuous emission bands were measured in the ranges of 240-750 nm and
WATER ANALYSIS
220-720 nm, and the detection limits were 0.6 ng for antimony and 9.0 ng for arsenic. Data and explanations from an interference study were also included. Tellurium. The combination of flotation and extraction in the determination of tellurium in wastewater by a conventional photometric technique employingbutylrhodamine-C was presented by Skripchuk et al. (26G).The working range of the method was 0.002-0.1 pg L and the total analysis time was 1-1.5 h. Interference stu ies showed that a suite of 13 metals had ne li ible effect on the determination. Nakashima and Yagi (14G7&scribed a coprecipitation-flotation procedure used for the determination of tellurium in water and seawater. Tellurium(IV) is coprecipitated with hydrated iron(II1) oxide at pH 8-9 and floated with the aid of a surfactant and a stream of nitrogen. On collection, the precipitate is dissolved and the resulting solution analyzed by atomic absorption spectrometry. Recovery of spiked tellurium, 0.4 and 0.8 pg/L, was approximately 88%. Total preconcentration time was 30 min. A selective method for the determination of tellurium in natural waters based on the concentration of tellurium on sulfhydryl cotton fiber and tellurium/rhenium catalytic polarographic measurement was discussed by An and Zhang (2G). Application of the method to seawater analysis gave tellurium concentrations ranging from 4 x to 8 x g/L.
d.
Nonmetals
Carbon. Ogren, Charlson, and Groblicki (17H)developed a three-step procedure for the determination of elemental carbon in rainwater. Samples were passed through a fine nylon mesh to remove macroparticles followed by filtration throu h a quartz-fiber filter. Biogenic carbon on the filter is oxiiized with basic peroxide and any remaining nonelemental carbon is volatilized in an inert atmosphere at 900 O C . Elemental carbon was then determined by oxidation to carbon dioxide, which was measured by a nondispersive infrared analyzer. They reported that the method was capable of measuring 10 mg of carbon to an accuracy of 50%. Nitrogen and Phosphorus. Sawatari et al. (20H)reported the determination of total nitrogen in wastewaters having high carbon content. They used a thermal cracking technique with hydrogen over a highly active nickel-aluminum oxide catalyst at 700 "C followed by a coulometric measurement of the resulting nitrate and nitrite. Relative standard deviations were approximately 2 % for samples containing 100 ppm nitrogen. Bazilevich and Predtechenskaya (IH) used a coupled unit for the Kjeldahl determination of total nitrogen in water samples. They described the operation and performance characteristics of the apparatus. Total nitrogen and phosphorus were determined in river water and wastewater by Takami et al. (23H). They described a method based on the determination of total nitrogen and phosphorus by measuring the nitrate and phosphate concentrations by ion chromatography after digestion with potassium persulfate in an alkaline medium. Calcium, magnesium, and heavy metal interferences were removed by a Chelex 100 column. The detection limits for nitrogen and phosphorus were 0.007 and 0.017 mg/L, respectively. Ebina, Tsutsui, and Shirai (6H)reported a simultaneous procedure for the determination of total nitrogen and total phosphorus by oxidation with alkaline persulfate for the former and acid persulfate for the latter in the same autoclave. The resulting nitrate and phosphate were measured colorimetricallywith an automated analyzer. Randtke (18H) discussed the implications of using a micro-Kjeldahl method for the determination of total nitrogen and total phosphous in surface and wastewaters. Bowman and Delfino (2H)determined total nitrogen and total phosphorus in waters using a single modified Kjeldahl digestion approach followed by the simultaneous automated determination of nitrogen and phos horus from the same digestate. The recovery and stanfard deviation of nitrogen from nicotinic acid and glutamic acid were 95, 102% and 3.6, 9.2%, respectively. For phosphorus, the recovery and standard deviation was 101 and 2.8%, respectively. Phosphorus was determined in natural waters by long-capillary-cell absorption spectrometry by Wei, Fu'iwara, and Fuwa (27H). With a minimum volume of 1-3 mi!,, 5 pg/mL of phosphorus was detectable using the molybdenum-blue procedure. The advantages of long-capillary-cell absorption
spectrometry were reported to be low cost, simple manipulation of sample, and high signal stability. Fujiwara et al. (7H) determined parts-per-trillion levels of phosphorus by laserinduced thermal lensing colorimetry. An argon-laser pumped rhodamine 101 laser was used as the heat and probe source. A detection limit of 5 pg/mL was achieved using the molybdenum-blue absorption method. Ichinose et al. (9H)reported that the determination of dissolved total phosphorus in anoxic brackish waters spectrophotometrically by the heteropoly molybdenum blue method after oxidation with potassium persulfate resulted in the negative organic phosphorus content obtained by the difference between total phosphorus and inorganic phosphorus. A major cause was reported to be the coprecipitation of phosphate ion with the colloidal hydrated iron(II1) oxide. The problem was avoided by the addition of nitric and perchloric acids. An indirect determination of sub-ng/mL levels of phosphorus in waters by the diisobutyl ketone extraction of reduced molybdoantimonylphosphorus acid and inductively coupled plasma emission spectrometry was done by Miyazaki, Kimura, and Umezaki (14H). Spectrometry measurements were made of the molybdenum 202.03 nm or antimony 206.83 nm emission lines. Arsenic(III),silicon, germanium, iron(III), and most anions did not cause serious interference, but arsenic(V) must be absent. The detection limits are 5.2 and 45 pg/mL phosphorus, respectively, for the molybdenum and antimony measurement. A technique for the determination of phos horus using the fluorescence quenching of rhodamine 6 8 with molybdophosphate was described by Motomizu et al. (15H). A flow-injection system was used to measure the decrease in fluorescence. Hiiro et al. (8H)described a new method for the spectrophotometric determination of phosphorus in seawater based on the color intensity of membrane filters colored by the filtration of molybdenum-bluesolution. The technique was very sensitive for the determination of trace amounts of phosphorus (aproximately 0.001 ppm). The relative standard deviation for the eight measurements at 0.1 ppm was 2.5%. Ichinose et al. (IOH) also reported the determination of dissolved or anic phosphorus in anoxic natural waters based on a preoxifation with nitric and perchloric acids, followed by a colorimetric measurement by the ascorbic acid method. A high-speed liquid chromatographic procedure for the determination of phosphorus in anoxic waters was described by Ichinose et al. ( I I H ) . The technique is based on the extraction of molybdoheteropoly yellow with methyl propionate. Microamounts (0.015 ppm) of phosphorus in the anoxic waters were determined rapidly and with a coefficient of variation of 4.4%. Sakurai, Kadohata, and Ichinose (19H)also described the use of liquid chromatography using solvent extraction for the determination of the molybdoheteropoly yellow complex of phosphorus. Nuernberg (16H)discussed the iron and hydrogen sulfide interferences in the analysis of soluble reactive phosphorus in anoxic waters. Cabrera et al. (3H)modified the hydrogen peroxide method for determining total phosphorus in natural waters. They added extra quantities of sulfuric acid to avoid the loss of phosphorus by adsorption on hydrous iron and aluminum oxides formed during neutralization prior to filtration. Finally, Stauffer (22") performed chemical studies to optimize reduced molybdenum blue for arsenic and phosphorus determinations in groundwater. He found that phosphate ion strongly catalyzed the development of the arsenic(V) molybdate complex; decreasing pH or increasing the hydrogen ion-molybdenum ratio retarded complexation, but the effect was greatest for the potentially interfering silicomolybdate complex. Selenium. Cutter (5H)reported a technique for the elimination of the interference of nitrite on the determination of selenium by hydride-generation atomic absorption spectrometry. He suggested the addition of sulfanilamide to react with the nitrite to form a diazonium compound, eliminating the interference. Takayanagi and Wong (2423)determined selenium(1V) and total selenium in natural waters by a fluorometric procedure. Selenium(1V) was preconcentrated by extracting its complex with ammonium 1-pyrrolidinedithiocarbamate into chloroform, followed by a back extraction into nitric acid. It was then complexed with 2,3-diaminonaphthalene to form 4,5-benzopiazselenol which was measured fluorometrically. Selenium was also determined fluorometrically in marine materials by Maher (1323.He decomposed the sample with nitric, perchloric, and hydrofluoric acids prior ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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to isolation from potential interferents by coprecipitation with lanthanum hydroxide. The piazselenol was then formed at pH 1.0 and extracted into cyclohexane. The selenium was determined in the extract fluorometrically to a detection limit of 3.2 ng. Chakraborti et al. (4H)used a Zeeman background-corrected graphite-furnace atomic absorption spectrometer as a selenium-specific detector for ion chromatography. They reported the separation and determination of both selenate and selenite ions to a detection limit of 20 ng. Tao et al. (26") reported the determination of trace selenium in water by catalytic polarography. They were able to determine selenium at 1-2 ppb in a s stem containing ammonium hydroxide, ammonium chlori e, ethylenediaminetetraacetic acid, ammonium thiosulfate, chlorite ion, gelatin, and potassium iodate. Shibata, Morita, and Fuwa (21H) determined selenium by liquid chromatography with spectrofluorometric detection. Naphtho[2,3-C.,1,2,5]selenadiazolewas formed from selenious acid and 2,3-diaminonaphthalene. The detection limit was reported to be 130 fg of selenium; however, the sample blank limited the reporting limit in water samples to 3 pg/L. Sulfur. Takeuchi and Ibusuki (25H) described the continuous measurement of dissolved sulfur dioxide in water by a flow chemiluminescence method. The chemiluminescence was based on the reaction between sulfur dioxide and potassium permanganate. The intensity of the radiation was proportional to the bisulfite concentration over the range of 0.8-100 ng mL. No interferences were reported by the presence o sulfate, carbon dioxide, phosphate, sodium, potassium, ammonium ion, magnesium, and acetaldehyde; however, nitrite, peroxide, and formaldehyde decreased the light yield. Kijowski and Steudler (12H)reported a procedure for the determination of total reduced sulfur in natural waters. It was based on the alkaline digestion of samples using Raney nickel as a reductant. Hydrochloric acid was used to liberate hydrogen sulfide, which was trapped in zinc acetate solution and measured spectrophotometrically.
B
i
Radionuclides
Radium. Radium was determined in environmental water by Higuchi et al. (54 using a liquid scintillation counting technique. The radium was collected on a cation exchange resin by a batch procedure. The entire process required 2 h and a detection limit of 0.03 pCi of radium-226 L was reported. Elsinger, King, and Moore (24 measure radio-224 in natural waters by y-ray spectrometry using a lithium-drifted germanium detector. The radium-224 was preconcentrated onto manganese dioxide impregnated acrylic fibers. The fibers were leached, the radium coprecipated with barium sulfate, and the y-ray activity counted so that the activity ratio of radium-224, radium-226,and radium-228 could be calculated. Concentrations were determined by measuring the radium-226 on a small separate sample. Noyce, Hutchinson, and Kolb (9J)used liquid scintillation counting and y-ray spectrometry to determine radium-228. Radium-228 was separated by liquid-liquid extraction followed by ion exchange purification prior to measurement by @-particlecounting of the actinium-228 daughter product. Results were confirmed by yspectrometry of the radium-228 in equilibrium with its thorium-232 precursor which had been measured avimetrically. The application of an CY-ycoincidence metho for measuring radium-226 concentrations in water was investigated by Lowe et al. ( 7 4 . For a counting period of 12 h, the lower limit of detection was 2-5 pCi/L. Joshi and Padmanabhan ( 6 4 reported a rapid radiochemical separation technique for radium in environmental samples using ion exchanger Zeokarb-225. The radium was preconcentrated by precipitation as the carbonate along with other alkaline-earth elements. Subsequently, most of the alkaline-earth elements were complexed with ethylenediamminetetraacetic acid at pH 7.5 and the solution was passed through a column of Zeokarb-225. The sorbed radium was eluted with 2 N nitric acid and finally coprecipitated with barium sulfate. The CY particles from the radium-226 were counted in a silicon surface barrier detector and the @ particles from the radium-228 were counted in an end-window Geiger-Mueller counter. Thorium. Both uranium and thorium were determined in deep sea sediments by Thomson (134. He used a total dissolution of the sample by fusion with sodium and potassium
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ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
pyrosulfate and potassium fluoride followed by anion exchange for purification. The uranium and thorium activities were measured by CY spectrometry and electroplating. Isotopic tracers were added at the beginning of the process. Burk, De Jong, and Wiles (14 performed studies to characterize the coprecipitation of thorium-230 and thorium-234 with barium sulfate. It was observed that the presence of monovalent ions, especially potassium, promoted the formation of crystals while the presence of polyvalent ions tended to prevent it. Wang et al. (144 reported a manganese dioxide coprecipitation procedure for the separation of thorium, uranium and cerium from freshwater samples. They determined that the average recovery from 20-L samples was greater than 95% for thorium-234 and cerium-144 tracers. Hashimoto et al. ( 4 4 determined natural radioactive nuclides of thorium, radium, bismuth, actinium, and lead by y and CY spectrometry. Recoveries were determined by using thorium-234 as a tracer. Other Radionuclides. Riley and Siddiqui (114 determined technetium-99 in seawater and marine algae by preconcentrating the pertechnetate ion on Duolite A1010. After elution with nitric acid, it was separated from other radionuclides by scavenging with hydrous iron(II1) oxide followed by extraction from alkaline media into methyl ethyl ether. After evaporation of the organic solvent, technetium was then electroplated from an oxalic acid solution onto a bronze disk. The sample was then counted on a low-background @ counter. Overall recovery was better than 90% with a precision of 0.02 pCi/L at a concentration level of 1pCi/L. Palagyi and Larsen ( 1 0 4 reported a method for the determination of cadmium113 by the addition of a known amount of cadmium carrier to the sample followed by the coprecipitation with ferric hydroxide. The separated cadmium was purified by anion exchange procedures and finally coprecipitated with copper sulfide. The activity of the cadmium-113was measured with a low-backgroundgas-flow proportional @ counter. For a 24-h counting period, the lower limit of detection was approximately 50 pB/L. Studies were performed by Sasaki, Kondo, and Kimura (124 on the recoveries of cobalt-60 by coprecipitation from natural waters spiked with amino acids. Coprecipitation with sodium nickelhexacyanoferrate was effective for fresh seawater directly, aged samples required a prior digestion with potassium persulfate. Recoveries of greater than 99% were achieved. Lead-210 and polonium-210 were determined in snow samples by Hashimoto et al. (34. Both nuclides were coprecipitated with aluminum phosphate. Polonium was extracted with tributylphosphate-isopropyl ether followed by electrodeposition on nickel. CY Spectrometry was used to measure the activity of the specimen. Lead was estimated from a second measurement of polonium-210newly grown in the remaining lead fraction during the storage period of less than 3 months. Watari et al. (154 reported that a macroreticular resin, Amberlite XAD-7 selectively adsorbed iron-59 from seawater in the presence of a large excess of lithium chloride. The pH of the seawater was less than 2. Cosmogenic phosphorus-32 was determined in seawater by Merkushov, Sapozhnikov, and Nesmeyanov (84. Oxymagnesium reagent was used to precipitate phosphate followed by reprecipitation as ammonium phosphomolybdate. The @ activity was measured with a low-background counter. Actinide Elements
Nguyen, Kalvoda, and Kopanica ( 1 1 K ) reported a voltammetric method for the determination of uranium in natural waters. The method is based on the adsorptive accumulation of uranium(V1)-pyrocatechol complex on a hanging mercury drop electrode followed by its reduction. A concentration of 0.2 mg L was determined. Izutsu et al. (7K, 8K) have describe a method for the preconcentration of uranium from seawater on a tri-n-octylphosphine oxide coated glassy-carbon electrode followed by the measurement of the reduction current of the voltage scanned wave. A detection limit of 2 x M of uranyl ion was reported. Lubert, Schnurrbusch, and Thomas ( I O K ) have also reported the preconcentration and determination of uranyl ions on a tri-n-octylphosphine oxide coated electrode. They used cyclic voltammetry as the electrochemical procedure with an indication that oxidizing agents interfered. Berthoud et al. (3K) used a laser-induced thermal lensing effect to measure the concentration of low levels of uranium-
d
WATER ANALYSIS
(VI) in water. They employed a pulsed tunable dye laser as a heating beam and a helium-neon laser as a probe. The limit of detection was reported to be 4 X lo* M. A rapid spectrophotometric determination of uranium(V1) in seawater was described by Shijo and Sakai (12K). They performed an extraction with apriquant followed by a back extraction with Arsenazo 111,oxalic acid, and hydrazine dihydrochloride. The absorbance of the resulting solution was measured at 655 nm. The value of uranium(V1) in seawater was reported to be 0.6 MIL. Spevackova, John, and Prazska (13K) determined uranium in natural waters by an X-ray fluorescence procedure after preconcentrating with several precipitants including, a-nitroso-@naphthol, methylene blue, ammonium thiocyanate, and tannin with urotropine. They used the cadmium-109 radioactive isotope as the excitation source of the L-series X-ray lines of uranium. Uranium was determined in seawater by passing a sample through clinoptilolitesorbents, followed by neutron activation analysis by Ivanenko and Metelev ( S K ) . Irradiation with a californium-neutron source stimulated y-ray emission which was measured with a semiconductor detector. A detection limit of 24 pg was achieved. Alimarin, Golovina, and Runov (1K)reported an experimental design study to optimize the determination of uranium(V1) by extraction-spectrophotometry of 8-hydroxyquinoline and butarhodamine complexes. They reported the method was more selective than other techniques and allowed a detection limit of 0.03 pg/mL. Gladney, Peters, and Perrin (5K) discussed a procedure for the determination of the uranium-235/uranium-238 ratio in natural waters by Chelex 100 ion exchange and neutron activation analysis. Impurities were removed by hexone extraction and ion exchange on Dowex AG-1 resin. The isotope ratio was determined by thermal neutron activation using a single irradiation. Burba, Cebulc, and Broekaert (4K) reviewed several methods for the determination of uranium in natural waters. The techniques included inductively coupled plasma emission spectrometry, X-ray fluorescence, and spectrophotometry. Liu, Yan, and Chen (9K) described a method for the determination of plutonium-238 in water by precipitation as the hydroxide with calcium chloride, magnesium chloride, and sodium hydroxide. Electrodeposition and a counting was used for the final measurement. AsWurov and Zemlyanukhina (2K) determined plutonium in environmental samples with an extraction and chromatographic separation on ftoroplast 4 coated with methyltriacetylammonium nitrate. Multlelement Technlques
Electrochemistry. Brihaye and Duyckaerts (7L) and Brihaye, Gillain, and Duyckaerts (8L) used a rotating glassy-carbonring-disk electrode to determine cadmium, lead, copper, antimony, and bismuth in seawater by both linear sweep and differential-pulse anodic stripping voltammetry. Concentrations were determined in the ng/L range. Andruzzi, Trazza, and Marrosu (2L)compared the performance of the sessile-drop mercury electrode to the conventional hanging mercury drop electrode in the direct determination of trace metals by differential-pulse anodic stripping voltammetry. Their studies showed that in seawater, the sessile-drop electrode offered better stability, reproducibility and detection limits (50 ng/L) than other electrodes. Zinc, cadmium, lead, and copper were determined in surface waters using differential-pulse anodic stripping voltammetry by Golimowski and Sikorska (26L). They acidified the samples with hydrochloric acid to pH 2 followed by digestion with peroxide and ultraviolet irradiation. Deposition was carried out at a potential of -1.2 V. Schlieckmann and Umland (72L) determined zinc, cadmium, lead, thallium, and copper in natural watewrs in the presence of humic acids using direct stripping voltammetry. The sup orting electrolyte used was a combination of potassium hylroxide, carbonate, and citric acid. Valenta et al. (84L) described an automatic voltammetric analyzer for the simultaneous determination of toxic trace metals in water. They used a differential-pulse polarograph, a microprocessor, and an automated hanging drop mercury electrode. Cui (17L) reported the simultaneous determination of copper and bismuth a t a gold electrode by anodic stripping voltammetry. Analyses were performed in a sulfuric acid media containing
a trace of iodide. Zebreva, Matakova, and Zholdybaeva (92L) determined copper, zinc, manganese, and iron in wastewaters by stri ping voltammetry at a mercury-plated graphite electrog. Brainina, Gruzkova, and Roitman (6L)developed a method for the continuous determination of heavy metals in natural waters. Mercury-graphite electrodes were periodically regenerated by dissolution of the mercury film in nitric acid followed by replating for 5 min at 0.5 V. Anodic stripping voltammetry was used by Chen and Zhang (13L)to study the adsor tive properties of lead and cadmium on the surface of vessei. They concluded that on polyethylene or glass and in an acid media (pH 1.9-2.0) the adsorption was negligible; in a slightly acid media (pH 4-5), it was insignificant; and in a neutral media (pH 7) it was evident. They also concluded that the amount of lead absorbed was always greater than cadmium. An intercomparison study of zinc, cadmium, lead, copper, nickel, and cobalt in Baltic seawater by differential-pulse anodic stripping voltammetry and atomic absorption spectrometry was reported by Gustavsson and Hansson (2915). Both the hanging mercury drop electrode and the mercury thin-film electrode were used in the study. Electrothermal atomization atomic absorption was used for cadmium, lead, copper, nickel, and cobalt, while flame atomization was employed for zinc. Coetzee, Hussam, and Patrick (15L)extended the scope of potentiometric stripping analysis to include electropositive elements by solvent optimization. Alkali and alkaline-earth metals were investigated using thin-iilm mercury electrodes and a variety of organic solvents and their mixtures with water. They found that the most effective solvents were aprotic; however, being a good hydrogen bond acceptor was an equally important factor. The sum of sodium and potassium ions was determined in seawater after the addition of dimethyl sulfoxide. Hu, Dessy, and Graneli (35L) described a potentiometric stripping analysis procedure for the determination of heavy metals in groundwater. Flow injection techniques provided a convenient automated method for the determination of copper, cadmium, and lead. Drabaek, Madsen, and Soerensen (19L) described the analysis of seawater by potentiometric stripping analysis. They determined lead, cadmium, and zinc with a precision of 5-16% relative standard deviation, depending upon the concentration level. The accuracy of the methd was evaluated by comparison with other techniques. Cadmium and lead were determined in biological wastewater treatment by respiration measurements with gas-sensitive electrodes as reported by Sztraka, Haug, and Nouri (78L). Respiratory activity was measured with both carbon dioxide sensitive electrodes and dissolved oxygen sensors. Gutsol and Golubev (30L)reported good selectivity for metal ions at pH greater than 4 using nonaqueous solution of salts of monoisooctyl methylphosphonate for extraction from water to determine total water hardness with a liquid ion-exchange membrane electrode. Ashkinazi et al. (3L)determined metals in wastewater by chronopotentiometry. They reported that the detection limit for the determination of lead in a hydrochloric acid medium was 0.002 mg/L for an accumulation period of 200 s. Spectrophotometry. Motomizu, Wakimoto, and Toei (54L)reported the solvent extraction of heteropoly acid with ethyl violet and the spectrophotometric determination of phosphorus, arsenic(V), and arsenic(II1). The ion associates of ethyl violet with molybdophosphate and molybdoarsenate were extracted into mixed cyclohexane/4-methyl-2-pentanone. Absorbance of the organic phase at 602 nm was linear for 0-1 pg of phosphorus and 0-2 pg of arsenic(V). In the presence of sodium thiosulfate, only phosphorus existing as orthophosphate was extracted; in the presence of potassium dichromate, orthophosphate, arsenic(III), and arsenic(V) were extracted. In the absence of any of these reagents, orthophosphate and arsenic(V) were extracted. Therefore, each of the species was determined by the differences of the appropriate combination of conditions. Tang (80L) reported on a method for the simultaneousdetermination of microamounts of zinc and nickel in water by spectrophotometry. Complexes with 1-(2-pyridylaz0)-2-naphtholin the presence of Triton-X 100 absorbed at 567 nm and 552 nm, for nickel and zinc, respectively. Trace arsenic and low-valent sulfur were simultaneously determined in water by Xie and Xie (88L). The sulfur was determined as hydrogen sulfide and arsenic as the hydride in separate absorption tubes. The tubes for sulfur ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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and arsenic contained ammonium molybdate and diethyldithiocarbamate, respectively. Andreena, Lebedeva, and Kavelina (1L)determined small amounts of molybdenum and tungsten as complexes with bromopyrogallol red. The influence of surfactants on complex formation was studied. The reaction was used for the determination of molybdenum(1V) and tungsten (IV) in seawater. Atomic Absorption Spectrometry, Lo et al. (49L) described a method utilizing a solvent extraction of dithiocarbamate complexes into chloroform followed by back extraction with a dilute mercury(I1) solution. Several elements were simultaneously preconcentrated from seawater by this technique, including cadmium, cobalt, copper, iron, manganese, nickel, lead, and zinc. Graphite-furnace atomic absorption spectrometry was used to make the final analysis. Lead and cadmium were determined in organic- and silica-rich sediments by Hsu and Locke (34L). They used both an open beaker and bomb procedure to digest the samples with nitric, perchloric, and hydrofluoric acids. Flame atomic absorption spectrometry was used to measure the concentrations in the digestates. Lamathe, Magurno, and Equel (44.5) tested a selective extraction method using Chelex 100 resin followed by electrothermal atomization atomic absorption spectrometry. The results from three laboratories roved the validity of the method for cadmium and copper, !ut the dispersion of results observed for lead was related to the poor precision of eleotrothermal atomization. Manning and Slavin (52L) determined a number of trace metals in natural waters using the stabilized temperature platform furnace with atomic absorption spectrometry. Aluminum, arsenic, beryllium, cadmium, cobalt, chromium, copper, manganese, lead, selenium, and vanadium were determined with suitable matrix modifiers. Detection limits were reported to be 0.1-1 pg/L for most of the elements, with a precision of 10-15%. Sugaya, Kuga, and Hayashi (76L) used a sequential determination of arsenic and mercury by a reduction-aeration atomic absorption technique. The sample solution was made basic with sodium hydroxide and 4% sodium borohydride was added to reduce the analytes. Mercury vapor was trapped on gold-coated nichrome wire and subsequently thermally atomized into the absorption cell. Next, copper sulfate and stannous chloride solutions were added to the same sample. Mercury vapor evolved by the reduction of organic mercury was trapped and determined as before. Finally, an acid mixture (sulfuric-hydrochloric) was added to the sample to generate arsine, which was trapped in a liquid nitrogen cold trap. The trap was warmed and the atomic absorption was measured in the heated quartz cell. Detection limits were 0.002 and 0.02 pg for mercury and arsenic, respectively. A universal flame atomic absorption method was reported by Schinkel(71L) for the determination of 14 elements. Lanthanum and cesium were added to suppress interferences. Sperling and Bahr (75L) reported the determination of heavy metals in seawater and marine organisnis by atomic absorption spectrometry. They used electrothermal atomization and reported poor precision and accuracy due to variations in graphite quality. This imprecision was minimized by the addition of an acid matrix modifier to the final analysis digest. Mandic and Mesaric (51L) made atomic absorption determinations of chromium, manganese, iron, cobalt, nickel, copper, and zinc after extraction of the monooctyl ester of cu-(2-carboxyanilino)benzylphosphonic acid complexes into isobutyl methyl ether. Lieser, Sondermeyer, and Kliemchen (48L) reported the precision and accuracy of the determination of cadmium, chromium, copper, iron, manganese, and zinc by electrothermal atomization atomic absorption spectrometry. Burba and Willmer ( l l L , 12L) used natural cellulose and cellulose-Hyphan to preconcentrate trace metals from water prior to atomic absor tion analysis. Detection limits of 0.1-1 pg/L were reported. Flotation preconcentration prior to the atomic absorption determination of lead and cadmium was described by Nemets, Turkin, and Zueva (62L). The technique used coprecipitation with ferric and alumiunum hydroxides followed by flotation separation after the addition of sodium salts of C12-h)fatty acids. Detection limits were found to be 1.5 and 10 pg/L for cadmium and lead, respectively. Sukhareva, Zolotareva, and Ryzhak (77.L) determined calcium, magnesium, and iron in natural water and wastewater with an airacetylene flame atomic absorption procedure. Methanol was added to the samples to enhance sensitivity. Detection limits 80R
ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
were determined to be 1, 0.05, and 0.2 pg/L for calcium, magnesium, and iron, respectively. Lead and zinc in seawater were effectively extracted into carbon tetrachloride with added octanoic acid. A detection limit of 0.1 pg/L was achieved by this method. Willie, Sturgeon, and Berman (87L) compared 8-quinolinol-bondedsupports for the preconcentration of trace metals in seawater. Cross-linked poly(vinylpyrrolidinone), a macroreticular styrene-divinylbenzene, or methylated polystyrene substrates coated with immobilized 8-quinolinol were used for the preconcentration of cadmium, zinc, lead, copper, iron, manganese, nickel, cobalt, and chromium from seawater. Final measurements were made by electrothermal atomization atomic absorption spectrometry. Danielsson et al. (18L)extracted dithiocarbonate complexes into Freon-TF followed by back extraction into dilute nitric acid. Graphite-furnace atomic absorption was used for final metal measurement. Osipov, Charikov, and Panichev (66L)stated that 1-octanoic acid in carbon tetrachloride extracted lead and zinc from seawater for atomic absorption analysis. A detection limit of 0.1 bg/L was achieved. Atomic Emission Spectrometry, Ng and Caruso (63L) determined trace metals in synthetic ocean water by inductively coupled plasma atomic emission spectrometry with electrothermal carbon cup vaporization. No memory effects were observed on consecutive 5-pL samples. The precision for 0.1 ppm solutions was typically 6%. Detection limits in the parts-per-billion range were achieved for arsenic, gold, cadmium, lithium, tin, and zinc. Goulden and Anthony (27L) reported the determination of trace metals in freshwaters by inductively coupled argon plasma atomic emission spectrometry with a heated spray chamber. The modified heated spray chamber produced a stable aerosol. Using a 10-fold preconcentration in the digestion step, detection limits were $0.6, and 0.3 pg/L for aluminum, lead, and manganese, respectively. Tao et al. (8115)used xylene extractions of ammonium tetramethyldithiocarbamate and hexamethyleneammonium hexamethylenedithiocarbamate complexes of heavy metals with inductively coupled plasma emission spectrometry. They determined cadmium, copper, cobalt, chromium, iron, manganese, molybdenum, nickel, lead, vanadium, and zinc in river water and seawater. The elements were concentrated 100-fold by the solvent extraction. The limits of detection for the method range from 0.017 ng/L for cadmium to 0.5 ng/L for lead. Miyazaki et al. (53L) extracted several metals into diisobutylketoneprior to simultaneous analysis by inductively coupled plasma emission spectrometry. Dichloro-8-quinolinol, hexamethyleneammonium hexamethylenedithiocarbamate, and ammonium pyrrolidinedithiocarbamate were used as complexing agents. The latter was preferred because it formed complexes with cadmium, lead, zinc, iron, copper, nickel, molybdenum, and vanadium at pH 2.4. The nonaqueous extracts were aspirated directly into the plasma. Large batches of 10-mL river water samples were preconcentrated by evaporation and rapidly analyzed simultaneously for 16 elements by inductively coupled plasma spectrometry by Thompson, Ramsey, and Pahlavanpour (82L). The effects of background interference and its on-peak correction on realistic detection limits of 30 elements were studied on solutions with high levels of calcium and magnesium. Nygaard, Chase, andd Leighty (65L) discussed the requirements associated with determinations near the detection limit with a sequential scanbing inductively coupled plasma spectrometer. Interstitial water, extracted from field-most soils by immiscible displacement with a dense fluorocarbon liquid, was analyzed using inductively coupled plasma emission spectrometry by Kinniburgh and Miles (43L). Samples were separated using a high-speed centrifuge. Zhti (93L)used inductively coupled plasma emission to simultaneously determine 15 elements in oil refinery industrial water. The relative standard deviation was 1.3% at a concentration level 100 times the detection limit. Kempf and Sonneborn (42L) used a combination of flame atomic absorption and plasma emission spectrometry to serially determine several elements in water including phosphorus and sulfur. A comparative study of the determinations of cadmium, copper, and lead by atomic absorption and inductively coupled plasma emission spectrometry was performed by Rubio, Huguet, and Rauret (68L). The comparison included accuracy, precision, and detection limits as well as rapidity of determinations. Their conclusions showed that both methods exhibited similar detection limits and analogous
WATER ANALYSIS
accuracy by the standard addition procedure. Jaeger (40L) related some practical experiences in using inductively coupled plasma emission in the routine study of wastewater. He compared the results for the determinations of boron, calcium, cadmium, chromium, and phosphorus to those obtained by atomic absorption spectrometry. Himeno et al. (31L) determined heavy hetals in wastewater by inductively coupled plasma atomic emission spectrometry after coprecipitation with lanthanum hydroxide. Copper, lead, zinc, cadmium, nickel, chromium, manganese, antimony, arsenic, and iron were determined simultaneously. After coprecipitation with lanthanum hydroxide, the precipitate was filtered on a 1.2 pm membrane filter. The precipitate was dissolved with dilute hydrochloric acid prior to analysis. Blakemore, Casey, and Collie (5L) described an electrothermal carbon atomizer for the simultaneous determination of 10 elements in wastewater by inductively coupled plasma atomic emission spectrometry. Minor elements in concentrated brines were determined by Buchanan and Hannaker (IOL)using inductively coupled plasma spectrometry. Magnesium present in the brine solutions was used as a carrier by adjusting the pH of the sample to 8.0-9.0 with sodium hydroxide. The resulting precipitate was redissolved and analyzed for 14 cation and 3 anion species. Urasa (83L) determined arsenic, boron, carbon, phosphorus, selenium, and silicon in natural waters by a direct-current plasma atomic emisson technique. He evaluated the method in terms of the detection limits, sensitivity, linear dynamic range, precision, interference effects, matrix effects, and element selectivity. He found that in most cases the detection limits and SenSitiVitieB were equal to or better than those achieved with other techniques. Novikov, Anismimova, and Tsyplakova (64L) described an emission spectrographic technique for the determination of trace elements in natural waters. Spectra were photographically recorded and a total error of determination was reported to be about 15%. Pavlenko, Safronova, and Karyakin (67L) reported a thin-layer method for the direct-current arc emission spectrochemical determination of manganese, iron, lead, cobalt, nickel, copper, zinc, molybdenum, chromium, tin, vanadium, and titanium in natural waters. They used a magnetic field applied to the discharge to achieve detection limits in the range from to lop4pg/mL. Mass Spectrometry. Foss, Svec, and Conzemius (24L) determined trace elements in an aqueous medium without preconcentration using a cryogenic hollow cathode ion source on a mass spectrometer. A glow discharge in a hollow cathode containing 20-50 pL of aqueous sample held at liquid nitrogen temperatures was used as a source of ions in a double-focusihg mass spectrometer. Fluorine, phosphorus, sulfur, selenium, manganese, nickel, and tantalum could not be determined because of interferences. All other elements were determined at detection limits ranging from sub-ng/mL to pg mL levels. Shelpakova et al. (73L) reported a method for t e analysis of high purity water. It consisted of the preconcentration of impurities by evaporation on a thin-layer silicon substrate, followed by ionization by a high-frequency spark. The ions are then measured with a mass spectrometer. The detection limits for 60 elements were reported to range from to 10-l2% with a relative standard deviation of 0.17 to 0.36. X-ray Fluorescence Spectrometry. Clechet and Eschalier (14L) re orted determining traces of mercury and barium in water y selective retention on ion-exchange paper and X-ray fluorescence spectrometry. Mercury collected from hydrochloric acid acidified samples was collected on anionexchange paper disks and barium was collected on cationexchange paper disks after coprecipitation with lead chromate and dissolution of the precipitate Ih 1,2-diaminocyclohexanetetraacetic acid. The disks were then subjected to X-ray fluorescencespectrometry. E h et al. (21L,22L) studied seven methods for the preconcentration of chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, selenium, silver, cadmium, antimony, mercury, thallium, and lead from water prior to energy- or wavelength-dispersion X-ray fluorescence spectrometry. The final step of each preconcentration required the formation of a solid residue which could be introduced directly into the spectrometer. Yamada and Sat0 (89L) described a method for the routine determination of managanese, iron, nickel, copper, zinc, lead, and chromium in wastewater by energy-dispersive X-ray fluorescence spectrometry. For the determination of total
h
E
metals, after the di estion with nitric acid, diethyldithiocarbamate was addef to the sample at pH 7. The precipitate was collected by filtration through 0.45-pm membrane. For the determination of chromium(VI),reduction was performed with ethanol and hydrochloric acid with boiling prior to coprecipitation with iron(II1) and ethylenediaminetetraacetic acid. For the determination of iron and manganese, nickel and 1-(2-pyridylazo)-2-naphthol-methano~ were added to the digested sample and the pH was adjusted to 10. Sodium lauryl sulfate was added prior to filtration on the membrane. Detection limits were reported to range from l to 10 ppb. Adsorption of copper, zinc, lead, and iron as the L-ascorbic acid complexes onto activated carbon for X-ray fluorescence analysis was investigated by Saito and Ui (69L).The four trace metals were determined in seawater with detection limits of 2.3, 1.9, 8.4, and 2.3 pg for,copper, zinc, lead, and iron, respectively. Holynska and Markowicz (32L) reported the application of X-ray fluorescence to the analysis of environmental samples using two low-power X-ray tubes. Iron, nickel, zinc, manganese, and lead were preconcentrated by precipitation with sodium diethyldithiocarbamate and subsequent filtration on a membrane filter, followed by direct excitation in the spectrometer. Selenium in organic matter was reduced to the elemental form with stannous chloride and hydroxylamine hydrochloride using tellurium as a carrier. The detection limit was reported to be 1-2 ppb. Filter paper impregnated with 1-(2-pyridinylazo)-2-naphtholand sodium diethyldithiocarbamate was used by Gao, Hu, and Hu (25L) to enrich metal ions from aqueous solutions (pH 10.2) for X-ray fluorescence determinations. The detection limits for arsenic, lead, and bismuth were 0.02 ppm and for cobalt, iron, and magnesium, 0.04 ppm. The detection limit for chromium was 0.01 ppm. Losev (50L)reported the quantitative X-ray spectrometric analysis of water using ternary fluorescence spectra. Elements from chlorine to lead were excited with a low-power X-ray tube and measured with a semiconductor detector. Brueggerhoff et al. (915)described a method for the preparation of trace concentrate targets for analysis by proton-induced X-ray fluorescence. The preconcentration was based on the coprecipitation of trace elements with molybdenum diethyldithiocarbamate. The precipitate was separated by filtration. Landsberger et al. (45L) characterized trace elemental pollutants in urban snow using proton-induced X-ray fluorescence and neutron activation analysis. Samples were filtered through 0.4-pm pore filters to discriminate between soluble and insoluble particulate fractions. Saleh (7OL) used proton-induced X-ray fluorescence analysis to determine trace metals in drinking water in Jordan. Samples were preconcentrated by evaporation to dryness prior to multielement analysis. Jervis et al. (41L)compared the use of proton-induced X-ray fluorescence, neutron activation, and graphite furnace atomic absorption for the analysis of wet atmospheric deposition. The analysis of urban snow was evaluated by these techniques. Murata, Omatsu, and Mushimoto (55L) simultaneously determined heavy metals in the parts-per-billionconcentrations range by a combination of solvent extraction and X-ray fluorescence spectrometry, Complexes of sodium diethyldithiocarbamate were extracted into diisobutyl ketone followed by evaporation of the solvent onto filter paper. Detection limits for manganese, iron, cobalt, nickel, copper, zinc, and lead were 15,16,8,8, 13, 13, and 40 ppb, respectively. Neutron Activation Analysis. Imai et al. (39L)reported the use of dithiocarboxypiperazinylcelluloseammonium salt to preconcentrated trace elements prior to neutron activation analysis. Ten liters of water was passed through a column packed with the cellulose salt at a given pH. The packing was then ashed in a low-temperature plasma asher, and the resulting ash was encapsulated in polyethylene and subjected to neutron irradiation. y Spectrometry was then performed to determine 19 elements. Procedures were described by Greenberg and Kihgston (28L) to preconcentrate trace elements with a chelation resin and subsequent analysis by neutron activation analysis. This technique essentially removes all alkali, alkaline-earth metals, and halogens from the sample. Arsenic, molybdenum, uranium, and vanadium were determined in seawater usin colloid flotation and neutron activation by Murthy, Shreedfara, and Ryan (56L).Hydrous ferric hydroxide was used to separate the analytes by flotation in the presence of sodium dodecyl sulfate at a pH of 5.7. ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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WATER ANALYSIS
Selenium(1V) and tungsten(VI) could also be recovered by this procedure, but their concentration levels in seawater were below the detection limits for 1-L sample volumes. Nakata et al. (59L)also determined metals in seawater by neutron activation analysis. They used electrolysis on a carbon-fiber column for the preconcentration and separation of gold, cadmium, molybdenum, uranium, and zinc. After preconcentration, the carbon-fiber electrode is removed and irradiated in a nuclear reactor and analyzed by y spectrometry. Ndiokwere and Guinn (60L) determined toxic trace metals in Nigerian river and harbour water samples by neutron activation analysis. Arsenic, cadmium, chromium, mercury, manganese, molybdenum, nickel, antimony, and selenium were preconcentrated by freeze evaporation under reduced pressure. Postirradiation chemical separation of sodium using hydrated antimony pentoxide in 6 M hydrochloric acid, and of bromine by oxidation with potassium permanganate and subsequent removal by chloroform solvent extraction, was used to eliminate interferences. Ndiokwere (61L) also determined trace elements in rainwater by neutron activation analysis. After acidification to pH 5, the samples were freeze-evaporated to approximate 10-mL volume. They were irradiated with neutrons and counted on a coaxial lithium-drifted germanium detector. Bem and Ryan (4L)used neutron activation analysis to determine uranium in seawater after selective preconcentration with 1-(2-pyridylazo)-2-naphthol.Coprecipitation was most effective at a pH of 4.5-6.5. The method was highly selective for uranium by using 1,2-cyclohexylenedinitrilotetraacetic acid as a masking agent. After neutron irradiation, the uranium was determined via the uranium-239 isotope with a detection limit of 3-4 ng/L. Yu, Lo, and Wai (91L)extracted gold and mercury from seawater with bismuth diethyldithiocarbamate prior to neutron activation-y spectrometry. Chloroform was used as the solvent for the extraction to remove the sample matrix effects. The detection limits for gold and mercury were 0.001 and 0.01 pg/L, respectively. Preconcentration and Separation. Aluminum, lead, and vanadium were determined in North Atlantic seawater by coprecipitation with ferric hyroxide by Weisel, Duce, and Fasching (85L). They suggested that this technique would be suitable for a variety of analytical procedures. Cox et al. (16L) performed metal speciation by Donnan analysis. Aqueous samples were separated from receiver electrolytes by an ion exchange membrane. They demonstrated that the dialysis of metals into salt solutions occurred in proportion to the sum of the concentrations of the free metal and the metal held in the form of labile complexes. With strongly acidic or chelating receivers, the dialysis was proportional to the total soluble metal. The method was demonstrated for lead, zinc, copper, and cadmium complexes of glycine, humic acids, and nitrilotriacetic acid was applied to lake water samples. Murthy and Ryan (57L) reported the use of a dithiocarbamatocellulosederivative for the preconcentration of copper, cadmium, mercury and lead from seawater and tap water. Ethylenediamine, 2,2’-diaminodiethylamine,and triethylenetetraamine were introduced onto microcrystalline cellulose after tosylation. Dithiocarbamate groups were added by reaction with carbon disulfide. Welte, Bles, and Montiel (86L)studied speciation of heavy metals in sediments. Two schemes were investigated, method A, which utilized acidified ammonium acetate, hydroxylamine hydrochloride, and aqua regia, was preferred to method B, which utilized nitric acid, sodium dithionite, sodium citrate, and aqua regia. Flotation of submicrogram amounts of antimony, bismuth, and tin in water using coprecipitation with zirconium hyroxide was reported by Nakashima and Yagi (58L). Zirconium hydroxide, sodium oleate, and air at pH 9.1 was used for the flotation of the precipitate. Iron, nickel, copper, zinc, and uranium were quantitatively separated by Lieser and Gleitsmann (47L)from seawater in a fluidized bed by Hyphan-bead cellulose reaction product. Loading curves of the individual elements were calculated in the range where loading was proportional to concentration. The Hyphan-bead cellulose exchanger gave good separation of uranium from seawater. Shvoeva et al. ( 7 4 )preconcentrated and separated elements on chelating sorbents. Conditions were optimized for the preconcentration of copper and silver from salt solutions using a fibrous sorbent. These techniques were applied to the analysis of natural waters. 62R
ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
Yamamoto et al. (90L) used ion chromatography with ethylenediaminetetraaceticacid as an eluent to simultaneously determine inorganic anions and cations. Magnesium, calcium, chloride, nitrate, and sulfate were all detected using a conductivity detector and an IC-Anion-SW (porous silica gel) column. Calcium and magnesium are determined as the EDTA anion complexes. Legrand, De Angelis, and Delmas (4615)determined common ions at ultratrace (ppb) levels in Antarctic ice and snow by ion chromatography. Calibration data for ammonium, sodium, potassium, chloride, nitrate, and sulfate ions were presented. Selenium, arsenic, molybdenum, tungsten, and chromium as their oxyanions were separated and determined by ion chromatography by Zolotov, Shpigun, and Bubchikova (94L). The oxyanions were formed by treatment in an alkaline medium with hydrogen peroxide. Sodium carbonate eluent was used to achieve separation of all of the ions. They reported the detection limits as 1-50 ppb with a conventional column and 0.01-0.5 ppb with a concentrating column. They employed the method for the analysis of natural and wastewaters. Ficklin (23L)reported the separation of tungstate and molybdate by ion chromatography and application to the analysis of natural waters. He used a standard anion separator column and sodium carbonate solution as the eluent. The tungstate and molybdate were preconcentrated on a chelating resin prior to introduction into the chromatograph. Hoover and Yager (33L) reported that selenate, selenite, and arsenate ions were separated from the major anions in water on a multidimensional ion chromatograph. Detection limits of 0.02-1.2 pg of trace element, depending on the major components, were achieved. High-performancereversed-phase liquid chromatography was used to separate copper from zinc as reported by Igarashi et al. (38L). The sample was treated with ethanol, pH 8-8.5 buffer, and cu,&G,y-tetrakis(4-hydroxyphenyl)porphine.After refluxing for 10 min, a 100-pL aliquot was injected into 75% ethanol mobile phase and the separated chelates determined by adsorption at 420 nm. Ten-fold excesses of rhenium(II), nickel(II), cobalt(II), and lead(I1) did not interfere with the determination of copper, but manganese(I1)and cadmium did interfere with the zinc measurement. Ichinoki and Yamazaki (36L)simultaneously determined heavy metals in water by high-performance liquid chromatography following solvent extraction as pyrrolidinedithiocarbamate chelates into chloroform. Nickel, lead, cobalt, copper, mercury, and bismuth were determined at partsper-billion levels using acetonitrile-water-ammonium pyrrlidinedithiocarbamate as an eluent. Chelates were detected by absorption at 254 nm. Edward-Inatimi (20L) used highperformance liquid chromatography after solvent extraction for the complete separation of trace amounts of dithizone and diethyldithiocarbamate complexes of trace metals prior to their nonspecific ultraviolet detection. The absorption mode of high-performance liquid chromatography was used because of the high solubility of metal chelates in nonpolar solvents such as chloroform. The high distribution ratio of the complexes in such solvents made possible the use of small volumes for extraction and, hence, obviated the need for evaporation to preconcentrate prior to direct injection. Ichinoki, Morita, and Yamazaki (37L)used solvent extraction of metal hexamethylenedithiocarbamate chelates followed by high-performance liquid chromatography for the analysis of water. Cadmium, nickel, cobalt, copper, bismuth, and mercury were determined at parts-per-billion levels, with detection limits in the 45-600 pg range. Tanaka, Ishihara, and Kakajima (79L) reported the determination of alkali and alkaline-earth elements by ion chromatograph fitted with a coulometric detector. Results of the determination of inorganic ions (lithium, sodium, potassium, rubidium, cesium, ammonium, magnesium, calcium, strontium, and barium) were compared using the conductometric and coulometric detectors. Anlons
Multiple Anions. An automated suppressed-ion chromatographic method for the determination of inorganic anions in a variety of industrial water matrices is described by Mosko (64M). Chromatographic conditions, sample pretreatment protocol, and interference identification and handling are discussed. Accuracy and precision data are also provided. Schwabe et al. (89M) used ion chromatography to determine
WATER ANALYSIS
a suite of inorganic anions and organic acids in surface, rain, and drinking waters. Results from rainwater studies exhibited marked seasonal variations for individual constituents. Anions in rainwater were also separated and quantified using ion chromatography in a report published by Oikawa and Saito (76M). A sodium carbonate and sodium hydroxide eluent was em loyed to separate fluoride, bromide, nitrate, sulfite, sulfate, and3 phosphate. Reproducibility of the determinations in terms of variation coefficient ranged from 2 to 4%. Using similar analytical procedures nitrite was determined with precisions less than 10%. Mueller (68M) increased the sensitivity of anion determinations using ion chromatography by reducing the dead volume of the column, thermostating the conductivity detector, suppressing pump pulsations, and optimizing the eluent concentration. These modifications gave the needed sensitivity for the determination of anions in atmospheric deposition. The inorganic anion concentrations in snow samples were determined by both suppressed and nonsuppressed ion chromatography by Jenke, Mitchell and Pagenkopf (44M). Results obtained for chloride, nitrate, and sulfate using both techniques were equivalent within the experimental precision. Nonsuppressed ion chromatography has experienced a marked increase in applications over the past few years. Bucholz, Verplough, and Smith (16M) analyzed rainwater for chloride, nitrate, and sulfate using this technique. Detection limits were 0.1 mg/L for chloride and nitrate and 0.25 mg L for sulfate. Single-column ion chromato raphy was used y Jupille, Burge, and Togami (48M) to letermine chloride, nitrate, and sulfate in a total time of 6 min. The column consisted of a 200 mm by 4.6 mm liquid chromatography column packed with a low-capacity ion exchange chemically bonded silica. The lower limit of determination was 100 ppb. Data from a study conducted by Okada and Kuwamoto (77M) showed that the determination of anions in lake water using nonsuppressed ion chromatography correlated closely with other analytical techniques employing ion specific electrodes or spectroscopy. The correlation coefficients for chloride and nitrate were 0.998 and 0.977, respectively, and the related standard deviation for 8 mg/L chloride was 0.17% and for 670 pg/L nitrate was 3.5%. An ion chromatographic analyzer was designed by Wang, Bunday, and Tarter ( I O I M ) implementing two different types of detectors. By use of both electrochemical and conductometric detectors, fluoride, chloride, bromide, iodide, sulfate and thiosulfate were determined sequentially using a single injection in a suppressed eluent system. The complete analysis required 37 min and all the above mentioned analytes could be determined at concentrations less than 1 mg/L with good precision. Rokushika, Qiu, and Hatano (83M) combined a hollow-fiber suppressor and a microcolumn to form a microcolumn ion chromatograph. The column comprised a newly developed low-capacity anion exchange resin packed into a fused silica capillary (190 pm inside diameter, i.d.). The micro suppressor column was constructed from sulfonated hollow fiber tubing (10 by 0.2 mm i.d.1. The authors reported excellent separations for inorganic anions as well as carboxylic acids with this system. Optimal operating conditions for the determination of chloride, nitrate, sulfate, nitrite, fluoride, and phosphate in river water by column-coupling ca illary isotachophoresis were outlined by Zelensky et al. ( 1 0 7 d The analysis time was 25 min and no sample pretreatment was required. Detection limits for the analytes ranged from 30 to 60 pmol. The decomposition of nitrite was observed and the mechanism of the reaction proposed. Lash and Hill (57M) evaluated ion chromatographyfor the determination of anions, fluoride, chloride, bromide, and sulfate, and cations, lithium, sodium, potassium, and ammonium, in geothermal water through the use of data obtained in a round-robin test. A comparative study of methods for the determination of inorganic anions was conducted by Schwedt and Reinaecker (90M).Comparisons were drawn between rapid commercially produced analysis kits and standard methods for determining chloride, nitrate, sulfate, and phosphate in natural and wastewater. Analysis kit chloride results were in good agreement with standard methods, as was phosphate, although there was a potential silica interference. Rapid determinations of nitrate varied substantially from standard methods. A titrimetric method based on 2-aminoperimidine bromide compared favorably for sulfate, while a turbidimetric method
i
gave higher results. Gebauer et al. (3IM) used capillary free-zone electrophoresisas a technique for the determination of nitrate, chloride, and sulfate in drinking water. The method used an isotachophoretic device composed of a capillary with an on-line potential gradient detector. The analyte anions could be measured in the concentration range from 0.1 to 0.7 mmol. An ion selective electrode interfaced with a computer was used by Kiselev, Mezhburd, and Nikonov (50M) in an automated multiconstituent analysis system. The sample throughput was on the order of 30 per hour for determinations of chloride, nitrate, fluoride, sodium, ammonium, and calcium. Sulfur Anions. Sulfate was extracted from natural waters with a nonionic surfactant and determined spectrophotometrically using crystal violet as the chromophore in a method published by Sat0 (87M). The sulfate anion is extracted into toluene with sorbitan monolaurate. The calibration curve is linear over concentrations between 2.5 X 10" and 2.5 X lo4 M sulfate when measured at 600 nm. Utsumi, Tanaka, and Isozaki (96M) outlined a method for measuring sulfate by implementing a barium chromate acid suspension and photometric detection. The suspension was enhanced by adding a uniform mixture of barium chromate, acetic acid, and hydrochloric acid to the sample followed by aqueous ammonia containin calcium and ethanol. After centrifugation diphenylcar azide reagent and hydrochloric acid is added to the supernatant and the chromophore quantified at 545 nm. This method is applicable for sulfate concentrations between 0.3 and 10 mg/L. The reaction between slightly hydrolyzed zirconyl chloride and xylenol orange to form a 1:l zirconiumxylenol orange complex is catalyzed by sulfate, phosphate, or fluoride. This reaction was used by Sakuragawa and Okutani (85M) for the spectrophotometric determination of sulfate. The absorbance s ectrum was enhanced and shifted to a longer wavelength \y adding cetyltrimethylammonium chloride to the reaction mixture. Sulfate concentrations in the range from 0.5 to 10 mg/L were measured at 605 nm and fluoride and phosphate interferences were eliminated by masking with aluminum(II1) and coprecipitation with zirconium hydroxide. Flow injection analysis is being used to automate spectrophotometric determination of sulfate. Nakashima et al. (72M) employed dimethylsulfonazo-I11and flow injection analysis in their method. At sulfate concentrations of 6 to 10 mg/L the standard deviation was 0.94-1.2%. The detection limit of the technique was approximately 0.2 mg/L and the concentration calibration was linear to 14 mg/L. Extensive studies focusing on interferences were also discussed. Interfering effects of suspended solids, organic substances, and color are automatically eliminated by using an active carbon filter incorporated into a flow injection analysis system in a technique described by Van Staden (98M). The method is highly reproducible and the accuracy is comparable with that of a standard automated segmented flow system and manual filtration. Turbidimetric measurement of sulfate in natural waters using flow injection analysis with alternating streams was described by Krug et al. (55M). Samples are injected into an inert carrier stream that is mixed with barium chloride to form a barium sulfate suspension. The method is extended to low concentrations by continuously adding sulfate to the sample carrier stream. All operations are controlled by an electrically operated proportional injector-commutator. The proposed method is capable of analyzing 120 samples per hour with a relative deviation less than 1% for concentrations of 1-30 mg/L. Inductively coupled plasma atomic emission spectroscopy was used by Miles and Cook (6IM) to determine sulfate directly and simultaneouslywith other constituents. Measuring the emission at the 180.73-nm sulfur line and o erating under compromise operating conditions gave a 3a etection limit of 0.08 mg/L and a relative standard deviation of 0.8% at 200 mg/L was obtained. Spectral interferences were alleviated through software corrections. Schnitzler, Sander, and Sontheimer (88M) proposed a method for the determination of sulfate through thermal decomposition and subsequent microcoulometric sulfur dioxide analysis with a chlorate-silver titration cell. Sulfate is decomposed on tungsten trioxide in an argon atmosphere. The sulfur dioxide formed reduces chlorate to chloride which is determined microcoulometrically. The relative standard deviation for sulfate concentrations less than 500 mg/L in various waters was 1.5%.
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A colorimetric method for the determination of sulfite in water and wastewater based on the formation of tris(1,lOphenanthro1ine)ferrous complex was presented by Haskins, Kendall, and Baird (36M). The absorbance of this complex was measured at 510 nm and the detection limit was 0.01 mg/L. Sulfide was determined in a method outlined by Roman Ceba, Vinagre Jara, and Munoz Leyva (84M) based on the decoloration of carbon tetrachloride solutions of 8quinolinolate-copper(I1) as a result of mixing with samples containing sulfide and subsequent spectrophotometric measurement. The effects of pH, mixing time, volume ratio, and iodine concentration were investigated. The apparent molar absorptivityat 410 nm is 2.4 X 104L/(mol cm)and the method was tested in the presence of five other anions without difficulty. Bhat et al. (15M) described a spectrophotometric method for the quantification of sulfide and sulfite. Bis(2,9-dimethyl-l,l0-phenanthroline)copper(II) ion is reduced a t pH 10 by sulfide in the presence of formaldehyde and by sulfide and sulfite in its absence. The resultant copper(1) complex is extracted for subsequent measurement. With sample volumes between 1and 100 mL, the detection limits are 0.1 pg for sulfide and 0.25 pg for sulfite. Interference effects due to iron(I1) and nitrite are also discussed. Total dissolved sulfide could be measured in the pH range of 7.5-11.5 using an ion selective electrode as described in a publication authored by Guterman, Ben-Yaakov, and Abeliovich (34M). A total dissolved sulfide meter was designed and tested over the range of lod to 10-1M concentration. The new instrument uses a sulfide ion activity electrode and a pH glass electrode whose potentials are measured against a double-junction reference electrode. Sugino (91M) reported results of the determination of sulfide species, such as hydrogen sulfide, bisulfide, and sulfide in water based on a vaporization-absorption method. A sample solution is placed in a closed reaction vessel consisting of an inner tube and an outer flask. Hydrogen sulfide released through acidification of sample is collected in the inner tube containing zinc acetate. The resulting zinc sulfide precipitate is then determined by iodometric titration. A semiquantitative field testing procedure was developed by Garoff (29M) for measuring sulfide in water. The procedure uses strips of paper impregnated with lead acetate with one end inserted into the water sample. As the sulfide soaks into the paper it forms a precipitate pillar with the lead in the paper. The height of the pillar corresponds to the sulfide concentration. A suite of analytical methods for determining organic sulfur, carbon-bonded and ester sulfate, and inorganic sulfur, sulfate, and sulfide was described by Landers, David, and Mitchell (56M). Methods of sample preparation and a modification of the Johnson-Nishita digestion-distillation approach are given. The methods use a hydrochloric acid digestion, zinchydrochloric acid reduction, hydrogen iodide reduction, sulfate extraction, wet oxidation, and dry oxidation. Results are given that demonstrate the method's usefulness in the analysis of water, sediment, soil, and sludge. Nitrogen Anions. Three different photometric methods for the determination of nitrate were used by Vonderheid et al. (99M) to illustrate statistical approaches for standardization. A procedure for photometric determination of nitrate was modified by Nakamura (70M) to enhance the sensitivity and reduce the use of toxic reagents. The method is based on the reduction of nitrate to nitrite by the catalytic action of chloride in sulfuric acid followed by extraction with 4,5dihydroxycoumarin dissolved in benzene. The study emphasized the effects of different solvents with respect to sensitivity enhancement. Fakhri, Rahim, and Bashir (23M) developed a sensitive and selective spectrophotometricmethod for determining nitrate in aqueous solution based on the reduction of nitrate to nitrite by chloride in a strongly acidic medium. The resulting nitrite reacts with indole to form a stable water-soluble compound that is a strong absorber at 395 nm and which follows Beer's law for nitrate concentrations between 0.4 and 2 mg/L with molar absorptivity of 1.6 X lo4 L/(mol cm). The cadmium reduction method was modified by Gaugush and Heath (30M) to provide for a rapid manual nitrate determination on small volumes. Nitrate levels of between 2 and 100 pg of nitrate, as nitrogen, per liter in water samples as small as 5 mL were determined without any loss of sensitivity. Thirty samples can be batch-analyzed in 1 h 64R
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and reaction tubes can be used 5-10 times before the reactivation of the cadmium is necessary. An alternative to column cadmium reduction in nitrate determinations was proposed by Jones (46M). Small volumes of buffered sample are shaken for about 90 min with spongy cadmium to reduce nitrate to nitrite; the quantification of nitrite used standard colorimetric methods. The advantage of this modification is that more consistent contact time can be achieved. Wakida et al. (1OOM) employed a combination hydrogen-form cation exchange resin and sulfate-form anion exchanger in series coupled with an ultraviolet spectrophotometer for the determination of nitrate in water. The nitrate was eluted from the anion column with 0.05 M sodium sulfate solution and detected at 210 nm. The detection limit of nitrate as nitrogen was 1 pg/L using an analysis time of approximately 10 min. Ion chromatography was utilized by Darimont, Schulze,and Sonneborn (20M) for nitrate determinations in drinking water. The concentration range was 1 to 100 mg L and gave a standard deviation of 0.5-2% at 10-100 mg/ and 2-12% at 1-10 mg/L. In a unique a plication Heumann and Unger (38M) developed a new caligration method for the determination of nitrate in water. The definitive method is based on isotope dilution and mass spectrometric detection of the formation of nitrite-thermal ions on a hot metal surface. Nitrate in river water was determined as a pentafluorobenzyl derivative using electron capture gas chromatography in a method discussed by Wu et al. (102M). A stainless steel column packed with 10% OV-210 on Chromosorb W HP with nitrogen carrier as was employed. Interferences of several anions were s t u i e d and the detection limit was 4.6 ng/mL nitrite. An automated technique for the determination of nitrate in waters with a microcomputer-based stopped-flow mixing system was reported by Koupparis, Walczak, and Malmstadt (52M). Nitrate is reduced to nitrite with copperized cadmium-silver d o y or a cadmium tube column fitted to the flow system. Nitrite is determined using fast kinetic, multipoint or single-point procedures using N-(1-naphthy1)ethylenediamine dihydrochloride as the color reagent. Analysis parameters are optimized to allow analyses in the concentration range from 0.025 to 3 mg/L nitrate, as nitrogen, a throughput of approximately 100 samples per hour, and a detection limit of 0.013 mg L. Desirable features of both flow injection analysis an segmented flow systems were achieved by Gardner and Malczyk (28M) by introducing samples into a segmented flow system by loop injection. Sample loop sizes of 0.2-0.3 mL produced the best peak height-width ratio in nitrate and phosphate analyses. Peak heights produced by these injections were 80% as high as the steady-state signals produced by a much larger sample size, yet the advantages of long reaction time and minimum sample dispersion were maintained. This technique was used to measure nitrate and phosphate in 0.2 mL of water at concentrations down to 1 ng/mL as nitrogen or phosphorus. Relative standard deviations varied from less than 1 to 4%, depending on the concentration. Hilton and Rigg (39M) adapted the hydrazinecopper reduction method for determination of nitrate in water for use on a discrete analyzer. Performance statistics and a critical comparison of results with a segmented flow system were outlined. An inexpensive and very reliable technique for the determination of nitrate and nitrite in seawater was based on the conventional method of reducing nitrate to nitrite and colorimetric determination of nitrite by Johnson and Petty (45M).Modifications permitted flow injection analysis and automated sample processing. Sample throughput was approximately 75 per hour; discrete samples could be analyzed at about 30 per hour. The detection limit was 0.1 pM and analysis precision greater than 1% at concentrations greater than 10 p M . Zhou and Xie (108M)developed an improved rapid extraction-photometric procedure for the determination of trace amounts of nitrate and nitrite in aqueous solutions. Nitrate is rapidly reduced to nitrite at pH 3.0 in 5 min with freshly prepared cadmium sponge produced in situ by action of zinc powder in a dilute solution of cadmium chloride in the presence of ammonium chloride. At pH 2.0, nitrous acid diazotizes p-aminoacetophenone, which is then coupled with N-(1-naphthy1)ethylenediamineto form an azo dye. This is extracted into 1-butanol in the presence of P-naphthylsulfonic acid and aluminum nitrate. The absorbance is measured at
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WATER ANALYSIS
550 nm and the molar absorptivity is about 5 X lo4 L/(mol cm). The other ions normally present in water do not interfere when sodium metaphosphate is added as a masking agent. A simple and specific high-performance liquid chromatographic amperometric method was used by Alawi (3M) to measure nitrate and nitrite in water. The method is based on the nitration of an excess of phenol using the nitrate ions and (or) the oxidized nitrite ions in solution, extraction of the o-nitrophenol formed, high-performance liquid chromatographic separation on a reversed-phase column, and amperometric detection of o-nitrophenol in the reduction mode. Recoveries were 83 f 2.4% for nitrate and 77 f 1.9% for nitrite in the 0.01-1 pg mL concentration range. Kok, Buckle, and Wootton (51M) etermined nitrate and nitrite in water using high-performance liquid chromatography with a detection limit of 0.1 mg/L. At a flow rate of 3.0 mL min, each analysis was completed in 6 min. Ion exclusion c romatography was employed by Tanaka (92M) for the simultaneous determination of nitrate, nitrite, and ammonium in wastewater during the nitrification-denitrification process. The method consists of a cation exchange resin in the hydrogen ion form with an ultraviolet detector for determining nitrate and nitrite and an anion exchange resin in the hydroxide form with coulometric detection for ammonium ion. A spectrophotometric procedure for the determination of nitrite in water was described by Bashir, Flamerz, and Ibrahim (12M). Nitrite reacts with acidified orthanilic acid solution to form a diazonium ion that is subsequently coupled with resorcinol, in an alkali medium, to form an intensely yellow, stable, water soluble azo dye having maximum absorption at 426 nm. The absorbance-concentration calibration is linear for 1-12 pg of nitrite in a final volume of 10 mL, with a molar absorptivity of 3.9 X lo4 L/(mol cm), a sensitivity index of 0.0012 pg/cm2, a relative error of 0.5-0.2%, and a relative standard deviation of 0.34-3.5%. Optimization of conditions affecting the color reaction and interferences were studied and outlined. Chaube, Baveja, and Gupta (17M) diazotized p nitroaniline in hydrochloric acid using nitrite and coupled it with 8-quinolinol in alkaline medium to produce a purple chromophore having maximum absorption at 550 nm and a molar absorptivity of 3.9 X 104 L/(mol cm). Extraction of the dye into 3-methyl-1-butanol shifted the absorption maximum to 570 nm and improved the apparent molar absorptivity to 5.8 X lo4 L/(mol cm). Beer’s law was followed for concentrations of 0.01-0.06 mg L of nitrite and the Sandell sensitivity was 0.00078 pg/cm2. pectrophotometric determination of nitrite in wastewaters was based on the extraction of nitrite with 4,5-dihydroxycoumarin in ethyl acetate in a method described by Nakamura and Mazuka (71M). Beer’s law was obeyed to 0.75 mg/L nitrite, as nitrogen, and results correlated with those obtained by the diazotizing-coupling method. A method for continuous flotation of trace amounts of nitrite from water is reported by Aoyama, Hobo, and Suzuki (6M). In this method the sample is continuously fed at flow rates of 2-3 L/h into a separation tube. The nitrite in the concentration range between 3 and 40 pg/L is continuously converted to an azo dye for photometric measurement at 1Bmin intervals. Nitrite was measured in water and wastewater using diazotization of p-rosaniline followed by coupling of the diazonium ion with N-(1-naphthyl)ethylenediamine, and the absorption at 565 nm as outlined by Baveja and Gupta (13M). The linear working range was 0.08-0.72 pg/mL nitrite and the molar absorptivity was 5.8 X lo4L/(mol cm). Studies showed that interferences could be masked using tartrate or ethylenediaminetetraaceticacid. Xin (104M)reported using a method for determining nitrous acid based on or-naphthylamine hydrochloride colorimetry. A stabilizing agent containing the same volume of 12.4 M hydrochloric and 95% ethanol was added to the samples after color development. As a result, the azo dye formed in the solution remains stable for 18 h without coagulation, and the detectable upper limit is increased by a factor of 3. Flow injection analysis was used by Nakashima et al. (73M) to automate the spectrophotometric determination of nitrite. The method employed p-aminoacetophenone, which was diazotized by nitrite and coupled with m-phenylenediamine to form an azo dye. The limit of detection was 0.2 pg/L for sample injections of 650 pL. A sampling rate of 30 per hour could be achieved and the precision of the analyses was approximately 1.3%. An automated kinetic method for the
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determination of nitrite in waters with a stopped-flow analyzer was implemented by Koupparis, Walczak, and Malmstadt (53M). The technique was based on the diazotization of sulfanilamide and coupling of the product with N-(1naphthy1)ethylenediaminedihydrochloride to form a highly colored azo dye that is measured at 540 nm. A single-point kinetic procedure used a delay time of 10 s and one measurement of 0.7 s. A multipoint reaction rate method used a delay time of 0.8 s and a measurement time of 1.5 s. The sample throughput for routine analyses is approximately 360 samples per hour in the concentration range of 0.025 to 2.0 mg/L of nitrite, as nitrogen. A technique for measuring concentrations less than 1 pg/mL of nitrite in water by gas chromatographic determination of the benzotriazole product of the reaction of nitrite with aryl-1,2-diamines was outlined by Dilli and Patsalides (22M). The synthesis, chromatographic behavior, retention data, and detection limits for flame ionization detection, alkali-flame ionization detection, and electron capture detection are reported for 13 benzotriazole derivatives. The strong interaction of the derivatives with the column were minimized by suitable selection of deactivated support, stationary phase, and reagent. Belyavskaya and Ryabinin (14M)used rapid anodic voltammetry to measure nitrite in salt solutions. With a graphite electrode the concentration range was 0.2-10 mg/L and the detection limit was 0.25 mg/L. Voltammetric curves were presented from 0.40 to 1.20 V, vs. saturated silver chloride electrode, and the half-wave potentials for nitrite in sodium chloride and calcium chloride solutions were 0.83 and 0.90 V, respectively. The method was used for determining nitrite in contaminated Black Sea water samples. An electrolytic sensor based on the oxidation of nitrite at a platinum electrode modified with chemisorbed iodine and coated with a thin layer of quaternized poly(4-vinylpyridine)(qPVP) was designed by Cox and Kulesza (18M). The sealed sensor uses an anionexchange membrane to separate a thin layer electrolysis cell from aqueous samples. A steady state is established between Donnan transport of nitrite across the membrane and controlled potential electrolysis at the platinum/iodine/qPVP indicator electrode. Linear response of the system is 4 X lo* to 2 X M and the detection limit is 2 X lo4 M nitrite. Anions that are electroactive at 0.7 V vs. silver/silver chloride will interfere. Total ammoniacal nitrogen in water was determined using flow in’ection analysis and a gas diffusion membrane in a method reported by Van Son, Schothorst, and Den Boef (97M). Both ammonia and ammonium ion can be measured spectrophotometrically as ammonia diffuses through a gaspermeable membrane, causing an absorbance change of a bromothymol blue indicator solution. The detection limit is lo4 M, the response is linear for concentrations from lo4 to M, the standard deviation at M is about 3%, and the sample throughput is 100 per hour. Krug et al. (54M)used zone trapping in flow injection analysis and photometry to determine low levels of ammonium ion in natural waters. In zone trapping a selected portion of a processed sample is removed, held for a predetermined period, and reinjected into the same carrier stream. Photometric measurement was based on a modified Berthelot reaction. Zone trapping retained the main portion of the reacting sample zone at 38’ so that an 80% reaction completion is achieved without limiting the sampling rate. This method is suitable for 90-100 measurements per hour with a relative standard deviation of 0.5% for 0.15 mg/L. Beer’s law is followed up to 1 mg/L and the detection limit is 5 pg/L. Interferences from metal cations are eliminated through masking with ethylenediaminetetraacetic acid. A method using continuous flow fluorometricdetermination of ammonia in water was published by Aoki, Uemura, and Munemori (5M). Sample solution is mixed with 1N sodium hydroxide in an outer tube of concentrically arranged lengths of Teflon tubing. The liberated ammonia permeates through the tubular microporous Teflon membrane and reacts with an o-phthalaldehyde reagent stream in an inner tube to produce a highly fluorescent isoindole fluorophore. The intensities at the excitation wavelength, 370 nm, and the fluorescence wavelength, 486 nm, were proportional to the ammonia concentration in the range from 2.0 X lo-’ to 2.0 X M. The detection limit at 3u for ammonia was 1.8 X lo-’ M with an analysis time of 6 min. Mizobuchi et al. (62M) ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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determined ammonium ion in water using high-performance liquid chromatographyfollowing a reaction of the analyk with fluorescamine. Less than 1 mL of water sample is needed to produce ammonium fluorophor and 5 to 20 pL was injected into the chromatograph. The proposed method was compared to the phenate method on over 100 river waters, 20 effluents, and 16 rainwaters with good agreement. Recoveries for these types of waters ranged from 95.8 to 99.8%. A modification in the preparation of pyridine-pyrazolone and pyridine-barbituric acid reagent for spectrophotometric determination of cyanide was reported by Nagashima (69M). The new preparation procedure was found to be easier and the colors develo ed faded less rapidly than those with reagents prepare in the usual manner. A sensitive color reaction of copper with Cadion 2B in the presence of Triton-X 100 and its application to the spectrophotometric determination of cyanide in wastewater was described by Fu-Sheng, Bai, and Nai-Kui (26M). Total cyanide was measured in wastewaters using a method described by Csikai and Barnard (19M). At low pH, thiocyanate reacts with nitrate or other oxidants to produce free cyanide. Therefore for thiocyanate containing wastewaters a total cyanide procedure was designed to use ethylenediaminetetraacetic acid at pH 4.0, acetate buffered, to disrupt the complexes of cadmium, chromium, copper, iron, nickel, and zinc. Nitrite interference is obviated by adding sulfamic acid to the sample. Sulfides are removed from the sample by pretreatment with cadmium carbonate and, if necessary, from distillates with cadmium nitrate. Selectivity coefficients of a cyanide ion electrode were determined by Tuhtar (95M) in the presence of several additional anions. The study emphasized the effects of 28 different anions on the quantitation of cyanide at approximately 0.020 mg/L, a concentration that paralleled naturally occurring levels in surface water. A com arison was drawn between determined coefficients and puglished values. Akiyama et al. (2M) devised a simple method for the determination of cyanide in wastewater, based on acidification with sulfuric acid and hydrogen cyanide adsorption by 0.15 M sodium hydroxide in a microdiffusion apparatus, using an acetate film and cyanide specific electrode detection. This method produced higher values than the official method and sulfite and thiosulfate interfered slightly. Hefter and Longmore (37M) presented a method for the determination of cyanide in seawater using a cyanide selective electrode. Although chloride interferes at low cyanide concentrations, its effect can be eliminated by appropriate selectivity corrections. The method allows determinations of cyanide of less than 20 pg/L. A sensitive and specific method was established by Wu et al. (103M) for the determination of cyanide as pentafluorobenzyl cyanide, based on the derivatization of cyanide in an alkaline medium with pentafluorobenzyl bromide. The derivative is injected directly into a gas chromatograph equipped with an electron-capture detector. The detection limit was 2 ng/mL cyanide in an aqueous sample. The optimization of reagents and reaction parameters was established. Interferences due to other anions were minimal except for thiocyanate. Results from this method agreed well with those obtained using the pyridine-pyrazolone photometric method. Gao et al. (27M) determined cyanide in water by converting it to cyanogen chloride followed by gas chromatographic headspace analysis. The calibration curve was linear for cyanide concentrations of 0.005-0.30 m /L. Recovery at concentrations of 0.05-0.1 pg/mL cyanite was 100.8% and the relative standard deviation for seven determinations was 5.6%. The derivatization reaction of cyanide and an aldehyde at pH less than 3 to form a cyanohydrin was implemented by Nota et al. (75M) for the determination of cyanide. A glass column packed with Porapak Q-S, nitrogen carrier gas, and a nitrogen-phosphorous detector were employed in the analysis. The interference by metal cations was eliminated by ultraviolet irradiation; thiocyanate and proteins did not interfere. Gas chromatographic separation and flame thermionic detection were used by Funazo et al. (24M) to measure trace levels of cyanide in wastewater as benzonitrile. Yoshida, Tamaura, and Katsura (105M) developed a new procedure for total and latent cyanide in metal-containing wastewater using gas chromato raphic measurement of cyanogen bromide extracted from flrominated aqueous samples with ethyl ether. Alternate use of excess metaarsenite and permanganate permits measurement of total and latent
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cyanide values apparently free of interferences common to other standard methods. Concentrations of both cyanide and thiocyanate in turbid metallurgical wastewaters were determined by titration with silver nitrate using an automated potentiometric titrator coupled with a silver electrode and reference electrode. The method by Atkinson, Byerley, and Mitchell (BM) required minimum pretreatment for sharp end points and good reproducibility in the concentration ranges of 1 to 100 and 1 to 1500 mg/L and cyanide to thiocyanate ratios of 1:lOOO. A method proposed by Matsueda (58M) for the determination of cyanide in water was based on ion-pair extraction and atomic absorption spectroscopy. To a neutral solution containing less than 25 pg of cyanide, an acetate buffer solution, 0.075 M copper sulfate solution, and 0.3 M thiourea solution were added. The ion pair formed was extracted with 5 mL of methyl isobutyl ketone and the organic phase as irated into the flame to measure the absorbance of copper. d e calibration curve was linear in the range of 0.04-1 pg/mL cyanide and the variation was 1.7% at 0.2 pg/mL cyanide. Cyanide must be distilled at pH 2 with phosphoric acid in the presence of ethylenediaminetetraacetic acid to prevent interference by metal cations, nitrite, perchlorate, thiocyanate halides, and alkylbenzenesulfonate ions. Phosphorus Anions. The chromophore formed with molybdate and malachite green in aqueous solution with trace amounts of orthophosphate was the basis of a method proposed by Motomizu, Wakimoto, and Toei (66M). The molar absorptivity was 7.8 X lo4 L/(mol cm) a t 650 nm. The absorbance of the reagent blank was about 0.02, and its relative standard deviation was less than 10%. The concentration range was 0.1-5 pg of phosphorus, and the limit of detection was 0.1 pg of phosphorus. The chromophore was stabilized by adding poly(viny1 alcohol). The method was applied to the determination of pg/L amounts of phosphorus in river and tap water; the relative standard deviation was about 4% and recoveries ranged from 95 to 101%. Motomizu, Wakimoto, and Toei (65M) established a very sensitive spectrophotometric method for phosphate. Of the several cationic dyes and extraction solvents examined, ethyl violet and a mixture of cyclohexane and methyl isobutyl ketone (1:3 volumetric ratio) were found to be most satisfactory. When the absorbance of ethyl violet is measured in the organic phase a t 602 nm, the concentration calibration is linear for 0-0.6 pg/L phosphorus; the molar absorptivity is 2.7 X lo5L/(mol cm). The method was applied to the determination of phosphate and condensed phosphate in natural waters. The standard deviation and relative standard deviation for the determination of several pg/L of phosphorus in tap water were 0.11 and 1.3%,respectively. A flotation-spectrophotometric method is described for the determination of soluble inorganic phosphate in freshwaters by Aoyama, Hobo, and Suzuki (7M). Orthophosphate in the range of 5 to 150 pg L in 1-L samples is coprecipitated with aluminum hydroxi e at pH 8.5. The precipitate is floated with the aid of sodium oleate and nitrogen gas and was dissolved in l M sulfuric acid. The analyte is then determined by the conventional molybdenum blue method with recoveries greater than 95% and standard deviations of l %, Imasaka et al. (42M) reported that the stability of the output power of a solid-state emitter, at 814 nm, is so great when operated from two 1.5-V batteries that an absorption photometer equipped with such a device can be used to measure absorbances of 1.5 X lo6 L/(mol cm). A detection limit of 15 ng/L was obtained for the determination of phosphorus by the molybdenum blue method. Factorial design and simplex optimization were employed by Janse, Van der Wiel, and Kateman (43M) to optimize a flow injection analysis scheme for the determination of phosphate in water. Criteria on the performance of a particular analysis method were formulated in terms of signal height, peak width, base line noise, and calibration linearity. Flow rates of the carrier stream and reagent streams, the injection volume, and the length of the coils were the parameters studied in the optimization procedure. A method was described by Goto et al. (32M) using semidifferential electroanalysis for the determination of trace orthophosphate by the formation of molybdophosphatein the presence of excess paramolybdate in 1 M sulfuric acid and adsorption on a rotating glassy-carbon electrode. The semiderivative of the reduction current of the adsorbed analyte is recorded vs. the electrode potential after exchange of the
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WATER ANALYSIS
natural water spiked with acidic paramolybdate solution. The detection limit for phosphate was M with standard deviations of 0.64 and 2.0% a t 0.1 and 1.0 pM, respectively. Interferences from metasilicate, arsenite, and arsenate were negligible in 2000, 200, and 20 times excess, respectively. Halides. The reaction between slightly hydrolyzed zirconium and xylenol orange is catalyzed by trace concentrations of fluoride. This reaction was implemented for the determination of fluoride in a method proposed by Sakuragawa et al. (86M). The addition of cetyltrimethylammonium chloride shifts the absorption maximum to 605 nm and enhances the absorbance thereby increasing the sensitivity of the measurement. Reaction conditions were optimized and the absorbance reading taken 40 min after the addition of h drolyzed zirconium solution. Okutani et al. (78M) modifieithe preceding method by replacing the slightly hydrolyzed zirconium oxychloride with zirconium oxide to improve both the sensitivity of the method and the stability of the reagent. A sample containing 10 gg of fluoride was mixed with 1mL of 3 M nitric acid, 1mL of 5 X lo4 M iodide solution, and 1mL of 3 M cetyltrimethylammonium chloride. This mixture was then spiked with 1 mL of a solution containing 5 X lo-" M zirconium(IV), 0.2 M peroxide, and 0.3 M nitric acid. The absorbance was measured at 605 nm and fluoride could be measured in the range of 1-10 Fg; however sulfate, phosphate, aluminum, and ferric ion interfere. Trace concentrations of fluoride were measured in wastewaters using a kinetic method involving the potential produced by an ion selective electrode as a function of the oxidation of bromide by chloramine-B catalyzed by fluoride as reported by Barkauskas and Ramanauskas (IOM). The electrode was fabricated by coating platinum from a solution of 0.05 g poly(viny1 chloride) and 0.2 g of the precipitate obtained by reacting methyl green with chloroamine-B. The relative error was less than 25% in the determination of 2 X loa to 2 X pg fluoride. Also simplex optimization was used to evaluate experimental conditions. Tanaka (93M) outlined a method for the determination of fluoride in wastewater using ion exclusion chromatography with a cation exchange resin, in the hydrogen ion form, and methanol/water eluent. The fluoride eluted was monitored with conductivity and flow-coulometric detectors. The concentration calibration obtained using the conductivity detector was nonlinear; however a good linear response was obtained in the concentration range of 5 to 100 mg/L fluoride with the flow-coulometric detector. An automated chloride procedure em loying flow injection analysis and turbidimetry was describe{ by Zaitzu, Maehara, and Toei (106M). The carrier solution, 0.2 M nitric acid, and reagent solution composed of 500 mL of 0.01 M silver nitrate, 75 mL of 1.6 M nitric acid, and 25 mL of 1 g poly(viny1 alcohol)/L, were pumped using a double-plunger pump at a rate of 1.2 mL/min. A 500-mL aliquot of sample solution was injected into the carrier stream and mixed in a 2-m Teflon tubing coil before being passed into a flow cell where the tubidity was measured at 440 nm. Peak height to concentration graph gave a linear relationship a t concentrations between the detection limit and 14 ppm. Silicate and carbonate at 0.001 M concentration interfered with the determination of chloride. The mercury(II)-2,4,6-tri-2-pyridyl1,3,5-triazine-iron(II) system was used by Roessner and Schwedt (82M) for the spectrophotometric determination of 10 pg/L to 10 mg/L chloride. Manual, continuous flow, and flow injection analysis techniques were compared as applied to the determination of chloride in natural waters, air, bitumen, and calcium nitrate. Trojanowicz and Matuszewski (94M) used potentiometric detection with a silver/silver chloride electrode and flow injection analysis for the determination of chloride. Low electrode response, where the usual logarithmic relationship holds, showed a direct proportionality between the electrode potential and the concentration. In the Nernstian region, the dispersion in the flow system influences the lower limit of the linear detection, whereas in the subNernstian region it influences the slope of the electrode characteristics. Monastyrenko, Sukhorukova, and Dolya (63M)automatically measured chloride using a potentiometric system composed of a conventional chloride specific electrode, a standard auxiliary silver chloride electrode, and support instruments. The electrode potential monitored in relation to the auxiliary electrode, changes as a function of the chloride in solution. The analytical concentration range is 200 to 800
.
mg/L and the absolute determination error is 3-7 % The pretreatment method used in the determination of chloride with an ion selective electrode was examined by Hori et al. ( 4 0 in an attempt to eliminate interferences from sulfide, cyanide, and iodide. Potassium permanganate was added to the sample at pH 4 in order to oxidize sulfide and eliminate interference from iodide; nickel azide and was also added at pH 11. Tolerable concentrationsof sulfide, cyanide, and iodide were W3,5 x and 3 X M, respectively. Midgley published two papers on reference electrodes for use in the potentiometric determination of chloride. Part I (59M)assessed the performance of mercury-mercurous sulfate reference electrodes over several weeks of continuous use in the potentiometric determination of chloride in boiler feed water. Electrodes with ceramic-frit junctions were found more suitable for use in continuous monitoring applications than those with ground-glass sleeve junctions. Part I1 (60M) presented results of a reference electrode consisting of platinum or gold electrodes immersed in solutions of constant pH saturated with quinhydrone as applied to the potentiometric determination of chloride in feed water. The potentials of the new electrode were similar to that obtained with a composite mercury-mercurous sulfate electrode. Microgram amounts of chloride and hypochlorite were measured successively with a chloride-selective electrode in a method reported by Hori and Kabayashi (41M). After pH adjustment of the sample solution, the chloride and hypochlorite containing solution is analyzed for chloride using the electrode. The solution is then treated with peroxide to convert all the hypochlorite to chloride and again analyzed for chloride. Hypochlorite was determined by difference. The method was applied to natural waters and wastewater. Chlorite was determined in drinking water a t levels greater mg L in a method presented by Hartung than or equal to and Quentin (35M). A ter chlorine dioxide was removed by stripping or extraction, the chlorite is oxidized with sodium peroxydisulfide to chlorine dioxide and analyzed photometrically. Aieta, Roberts, and Hernandez (1M)published a method for the determination of chlorine dioxide, chlorine, chlorite, and chlorate ions in water based on the oxidation of iodide and the amperometric or potentiometric titration of iodine with sodium thiosulfate or phenylarsine. Sample pretreatment and pH adjustment differentiated the chlorine species. The phenol red method for the determination of bromide in water was automated by Basel, Defreeze, and Whittemore (11M) using a segmented-flow system. Samples could be analyzed at a rate of 20 per hour with a detection limit at 3a of 10 pg/L. Samples analyzed included oil-field brines, halite brines, contaminated groundwater, and fresh groundwater. Chloride and carbonate cause significant positive bias at levels as low as 100 mg/L and 50 mg/L, respectively. An ionic strength buffer was used to suppress a positive ionic strength interference, correction curves were used to suppress a positive ionic strength interference, correction curves were used to compensate for chloride interference, and the carbonate interference is minimized by acidification. Pilipenko, Zui, and Terletskaya @OM) utilized the chemiluminescent reaction of bromine with luminol. The reaction was studied in aqueous solution and in 1:l benzene/ethanol mixture by photoelectric and photographic methods. Bromide was oxidized to bromine, solvent extracted, and measured with a detection limit as bromine at 1ng/mL in aqueous solution and 0.02 Fg/mL in benzene/ethanol. An automated ion chromatograph, including a program controller, an automatic sampler, an integrator, and an amperometric detector, was used by Pyen and Erdmann (81M) for developing a procedure for the determination of bromide in rainwater and groundwater. Chromatography takes approximately 10 min and provides a detection limit for bromide of 0.01 mg/L and a relative standard deviation less than 5% a t concentrations between 0.05 and 0.5 mg/L. Chloride interferes if the chloride/bromide ratio is greater than 100O:l for the range of 0.01 to 0.1 mg/L; similarly, chloride interferes in the 0.1-1.0 mg/L range if the ratio is greater than 5000:l. Recoveries of known concentrations of bromide ranged from 97 to 110%. Solvent extraction followed by ion chromatographic separation was used by Katoh (49M) in the determination of bromine in seawater. After the sample was mixed with carbon
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WATER ANALYSIS
tetrachloride, potassium nitrate, nitric acid, and sodium hypochlorite, the mixture is shaken for 1min and the bromine extracted into the carbon tetrachloride. The bromine is then reduced using peroxide and acidified with acetic acid prior to analysis using ion chromatography. Ando and Sayato (4M) designed a method for the microdetermination of bromide in water using head space gas chromatography. In the method microgram quantities of bromide are reacted with citric acid and potassium permanganate to form pentabromoacetone which degrades to bromoform and is subsequently determined using a gas chromatograph. Ion exchange chromatography is used to separate the analyte from interfering substances such as chloride, humic acid, and phenols. The detection limit for bromide is 10 ppb and the calibration curves are linear up to 1.5 ppm. A sensitive, rapid, and simple method for the determination of iodide was outlined by Deguchi et al. (21M),based on the catalytic reduction of sulfatocerium(1V) ion by arsenic oxide in sulfuric acid conducted in a flow injection system. A sample is injected into a distilled water stream, previously premixed with reagents, and heated to 60° to help promote the reaction and cooled prior to being passed into the flow cell. The detection is based on measuring the discoloration of the trisulfatocerium(IV)complex at 312 nm. Optimization of reagent concentrations and flow rates is presented. A linear relationship was obtained between peak height and concentration for iodide in the range from the detection limit to 50 ppb. The detection limit was 1ppb with a sampling rate of 30 samples per hour. Interference from thiocyanate was documented and the method was applied to the determination of iodide in rainwater. Iodine and iodate-iodine were determined in natural freshwaters using a method described by Jones, Spencer, and Truesdale (47M)that is based on the catalytic effect of iodide on the reaction between ceric ammonium sulfate and arsenic trioxide. Replicate analyses showed precision of 0.1 pg/L with 95% confidence. Optmization studies are outlined for the extraction procedure and totaliodine could be determined at a rate of approximately 50 samples per hour. Nomura (74M) employed catalytic oxidation of l-amino-2naphthol-4-sulfonic acid by microgram quantities of iodide while in the presence of sodium chlorate at pH 1.3-2.0. The oxidation product, the direct result of the iodide concentration, shows a sensitive tensammetric wave at potential of about +0.03 V vs. standard calomel electrode therefore providing a means of determining trace quantities of iodide. The optimized method has a working range of 0.4-6.5 ng/mL with a relative error of approximately 3%. Interferences in the determination of total iodide in river water and seawaters are described. Methods for the determination of total inorganic iodide and free iodide, based on the catalytic effect of iodide on the destruction of thiocyanate by nitrite, were developed and automated by Moxon (67M). A throughput of 20 samples/h was achieved using a Technicon analyzer. The coefficient of variation of total iodine in drinking water was 3% the detection limit was 0.2 pg/L, and spike recoveries ranged from 89 to 109%. Pesavento and Biesuz (79M)described a method for the photometric titration of total iodine in concentrated chloride solutions based on the reduction of total iodine to iodide with sulfite at low pH. Excess sulfur dioxide is removed by a nitrogen gas stream, and the resulting solution titrated spectrophotometrically with a standard solution of iodate. The method was applied to the determination of total iodine in seawater. A gas chromatographic method for the determination of chloride, bromide, and iodide in water based on derivatization using 7-oxabicyclo[4.1.0]heptanewas published by Baechmann and Matusca (9M). Bromide and iodide in water at concentrations of 50 and 5 pg/L without preconcentration, and 0.5 and 0.2 pg/L with preconcentration, respectively, were determined using gas chromatography as described by Grandet, Weil, and Quentin (33M). The analytes are transformed into 2-bromohydrine and 2-iodohydrine which are extracted with ethyl acetate and measured individually using an electron capture detector. Simultaneous determination of trace concentrations of bromide and iodide by methylation with dimethyl sulfate and electron capture gas chromatography was outlined by Funazo et al. (25M). The detection limits are 0.1 pg/mL for bromide and 0.5 ng mL for iodide. Interference and recovery studies were conI lucted and the method could be used for determining total bromide and iodide. 68R
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Gases
Ammonia. Hirose et al. (1lN)determined ammonia in water by using a Stark microwave cavity resonator and a dialyzer in which ammonia is liberated from the sample with sodium hydroxide. The system was based on a continuous flow process. The calibration plot was linear for 1-20 mg/L. Alcohols, amines, and amino acids did not interfere. Otsuki and Sekiguchi (16N)reported a method for the automated determination of ammonia in natural freshwaters using the salicylate/hexacyanoferrate/dichloroisocyanuratesystem. They suggested that this technique has comparable sensitivity to the manual phenol method. Chlorine. Aoki and Munemori ( I N )described a technique for the continuous flow determination of free chlorine in water. They used a double-tube system made from Teflon. The sample is mixed with hydrochloric acid in the outer tube. Molecular chlorine permeates the microporus tube and dissolves in sodium hydroxide solution in the inner tube. The resulting hypochlorite ion flows into an ultraviolet detector, and the absorption is measured at 290 nm. They reported that the absorbance is pro ortional to the free chlorine concentration from to 10-PM, with a lower limit of detection of 2 X lo4 M. They also reported that the free chlorine could be measured in the presence of permanganate, chromate, and heavy metals. Barbolani, Piccardi, and Pantani (2N) studied the use of potentiometric titrations for the identification of break-point curves for chlorine in water chlorination. In ammonia/chlorine mixtures, ammonia was determined before and after the addition of sulfite as a dechlorination agent, and results were compared with potentiometric titrations of combined chlorine. Cooper et al. (7N) reported that the free available chlorine test with syringaldazine was equivalent to both the N,N-diethyl-p-phenylenediamine test and to amperometric titration. Hatch and Yang (9N) stated that the starch/iodine end point indicator in the titrimetric determination of residual chlorine in water is temperature dependent. They also proposed a mechanism for the decolorization of the starch/iodine complex. Cooper et al. (8N) compared several instrumental methods for determining chlorine residuals in drinking water. They used two-membrane electrodes, a potentiometric electrode, and a continuous total chlorine analyzer. Their results showed that the analyzer was operator dependent and the other techniques gave variable results. Toei et al. (19N)determined residual chlorine in city water by absorption spectrophotometry using 4,4'bis(dimethy1amino)thiobenzophenone. Absorbance measurements were made at 650 nm and they showed that the technique was suitable for flow injection analysis. Carlson and Weberg (SN)showed that iodate and bromide were detected by chromatography after the addition of hypochlorite to a solution of bromide and iodide under the conditions of the iodometric titration of residual chlorine in seawater. Bromate was not observed. The effect of iodate could be minimized by rapid titration at pH 4 or by the use of a correction curve. Wong (21N)studied the factors affecting the amperometric determination of trace quantities of total residual chlorine in seawater. He found that the interference from iodate originated from the reaction between iodide and hypobromite and from naturally occurring iodate in seawater to yield variable blank and underestimated results. A titration at pH 2 resulted in the true concentration of total residual chlorine after the contribution from naturally occurring iodate is corrected. A flow injection analysis of residual chlorine using the spectrophotometric absorption of N,N-diethyl-pphenylenediamine in a phosphate buffer was described by Legget, Chen, and Mahadevappa (15N).They achieved an analysis rate of 252 samples per hour with a detection limit of 0.3 ppm. Smart and Freese (18N)determined chlorine dioxide in water with a rotating voltammetric membrane electrode. The electrode was constructed with a silicone/ rubber/polycarbonate composite membrane. Ozone. Chrostowski (6N)described the interference of organic solutes in the indigo test for ozone in waters. Because of this interference, timing of the analysis was critical when ozone measurements were made. The addition of phenolic antioxidants inhibited the interferences. Tomiyasu and Gordon (20N)used a colorimetric method for the determination of ozone in water based on the reaction with bis(terpyridine)iron(III) in a dilute hydrochlaric acid solution. The
WATER ANALYSIS
ozone concentration was proportional to the change in absorbance a t concentrations down to 0.05 mg/L. Oxygen. Kulin, Schuk, and Kugelman (14N)studied the field measurement of dissolved oxygen using several different commercially available meters. A protocol was proposed for a detailed field test. Hertkorn-Obst, Printer, and Schmitz (ION) reported that there was no significant difference in the 30-day oxygen depletions of fresh river water samples and frozen samples stored for 14 days at -20 "C. A procedure for the continuous determination of soluble oxygen in water based upon the quenching of the afterglow hydrophobic adsorbates submerged in the water stream was reported by Zakharov and Grishaeva (22N). The appearance of a thin gas shell around the absorbate granules isolated the luminescent activator molecules from direct contact with the water, improving sensitivity and selectivity of the method. Barcelona and Garske (3N) described a nitric oxide interference in the determination of dissolved oxygen by the azide-modifiedWinkler method. In the range of 2-30 mg/L, nitric oxide contributed from 0.1 to 0.6 mg/L oxygen to the analysis result. Increased amounts of azide minimized the effect. Carbon Dioxide. Kikuchi and Furusaki (13N)determined carbon dioxide in water by gas chromatography. The procedure consisted of contacting the aqueous sample in a vessel with carbon dioxide free air. After vigorous shaking, the carbon dioxide partitioned into the air, where it was determined by gas chromatographic separation from the air components. The separation was performed on a Porapak Q column at room temperature. Rudenko (17N) determined carbon dioxide in seawater gas chromatographically. Barrenstein, Eckrich, and Obermann ( 4 N ) determined several gases in groundwater by a gas chromatographic method. Carbon dioxide, oxygen, hydrogen, nitrogen, methane, and nitrous oxide were a l l measured by stripping the sample with a helium carrier gas. Horner and Smith (12N)described a method for the determination of total carbon dioxide in seawater based on the addition of a trace quantity of NaHI4CO3. After acidification of the labeled seawater, a fraction of the gaseous 14C02/12C02 mixture is trapped with a substoichiometric quantity of a quaternary amine. Miscellaneous
Alkalinity-Acidity. Hillbom, Liden, and Pettersson (3P) developed a probe for the in situ measurement of alkalinity and pH in natural waters. It worked on the inverse buret principle, where the buret was used simultaneously as a titration vessel and to incrementally introduce sample and reagents through solenoid valves. The potentiometric pH measurements were made with a combination pH electrode mounted through the buret piston. A complete titration cycle took less than 5 min. Willis and Mullins (12P)modified an automated method for the determination of alkalinity at concentrations of 10 to 500 mg L of calcium carbonate. McQuaker, Kluckner, and San berg (6P)discussed and quantified the residual streaming potential and the residual junction potential on the accuracy of pH and acidity measurements. They used a Gran's titration method to assess acidity. The pH measurements had an accuracy of 0.01 pH unit. Mean relative standard deviations of 1.4 and 3.4% were obtained for strong and total acidity in the intervals 24-97 and 34-110 mequiv/L hydrogen ion, respectively. Molvaersmyr and Lund (8P)reported that the acidification of samples to pH 3.6 and a Gran's titration to pH 10.3, were necessary to give accurate determinations of strong and weak acids in synthetic solutions containing weak bases, buffers, and natural waters. pH. Covington, Whalley, and Davison (2P)used a flow cell with a renewable free-diffusion liquid junction for obtaining high quality pH measurements in low ionic strength water. Midgley and Torrance (7P)measured pH in boiler feedwater with special experimental glass electrodes which provided overall temperature compensation in the range of 15-35 OC. The chemistry was arranged so that the cell potential only responded to changes in pH brought about by changes in alkalinity. The glass electrode used N-glycylglycine as its internal reference solution and a silver-silver chloride or calomel reference electrode.
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Hardness. Bellomo, De Robertis, and D'Arrigo (1P)used semiautomatic end point detection in the determination of total hardness in water by the Erichrome black T-ethylenediaminetetraacetic acid titration. Yamane and Kamijo (13P) used flow injection spectrophotometry to determine water hardness. The method was based on the liberation of magnesium ion by the reaction of calcium ion with magnesium ethylendiaminetetraaceticacid, and the formation of a colored blue chelate between magnesium ion and hydroxynaphthol blue at pH 10. Absorbance a t 645 nm was linear at concentrations of 25 and 41.2 mg/L, for magnesium and calcium, respectively. Iron(III), aluminum(III), zinc(II), and copper (11) showed a positive interference. Sampling. Schmidt (1OP)described techniques for the sampling of seawater for the ultratrace analysis of heavy metals. Scheuermann and Hartkarnp (9P) reported that in the determination of heavy metals in water, errors due to adsorption on the sample container walls were prevented by pretreatment with aluminum(II1) ions or by shock freezing the sample with liquid nitrogen. Subramanian et al. (11P) described an on-site, pump-integrated, water sampler preconcentrating device. Chelex 100 was used to sorb cadmium, capper, lead, and zinc from drinking water samples. Maas and Dressing (5P) described a technique for the purification of nitric acid for use in trace metals analysis. Approximately 500 mL per day could be distilled from the Pyrex apparatus to a polyethylene collection bottle. Kinsella and Willix (4P)have reported that new polyethylene and Teflon bottles that have been acid washed by standing with 19 nitric and hydrochloric acids for 14 days still contained detectable amounts of cadmium, lead, and copper. These were removed with relative ease with an ultrasonic technique; they recommend this as a routine clean-up technique.
ORGANIC ANALYSIS Gas Chromatography
A gas-liquid chromatographic method has been described by Chmil (7Q)for the determination of chlorophenoxyalkylcarboxylic acids and chlorophenols in water as their 2,2,2-trichloroethyland pentafluorobenzyl esters. Continuous steam distillation continuous liquid-liquid extraction was used by Janda an Krijt (16Q)for isolation of phenols from water. Extracts were analyzed by capillary gas chromatography over a concentration range of 0.1-30 mg/L following acidification, salting, and 1.5 h distillation/extraction time. The detection limit is approximately 10 mg/L. A direct determination of trace amounts of chlorophenols in freshwater, wastewater, and seawater is reported by Abrahamsson and Xie (18).Chlorophenols are acetylated and analyzed by glass capillary gas chromatography with electron capture detection. A 100-mL sample is sufficient for n /L sensitivity. Sugawara et al. (38Q)have described a procefure for the determination of phenol and its derivatives in wastewater by gas chromatography. Samples are brominated, treated with sodium sulfite, and extracted with hexane. Results are comparable to the 4-aminoantipyrinemethod. Hrivnak and Steklac (14Q) have evaluated pentane, chloroform,methylene chloride, arid diethyl ether for the extraction of monohydric alkylphenols from water at Ng/L concentrations prior to glass capillary gas chromatographic analysis. Highest recoveries, which were compared to n-octadecane, were obtained with diethyl ether. A thin-layer chromatographic method for the separation and identification of dihydroxybenzenes in the presence of trihydroxybenzenes has been reported by Thielemann and Grahneis (406).This approach was based upon treatment of thin-layer films with silver nitrate which oxidizes the ortho and para but not the meta isomers. Chlorobenzenes in wastewater are determined by gas chromatography with electron capture detection according to Bao and Zhao (39). All 12 chlorobenzene isomers were completely separated and determined by this procedure. Trace concentrations of nitrobenzenes and chlorohydrocarbons in water at trace concentrations are simultaneously determined by capillary gas chromatography with electron capture detection according to Li and He (27Q). Samples are prepared by resin adsorption and elution with benzene. Sensitivity is at the ng/L level with greater than 80% recovery. Wang and Zhou (43Q) have developed a gas chromatographic method for determination of volatile phenols in wastewaters from pulp and paper mills. ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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WATER ANALYSIS
Resin concentration furnishes 500-fold concentration factors leading to a detection limit of 4 pg/L. Three volatile fatty acids C2-Cs in highly polluted refuse seepage water have been determined by gas chromatography on specially prepared columns by Kittlemann, Hartun , and Krueger (22Q). No "ghosting" was observed on these cofumns a t 10 to 20 mg/L detection limit. Lahl et al. (26Q) have demonstrated by gas chromatographic analysis of drinking, surface, and swimming pool water, that trichloroacetic acid is generated by the reaction of ligninsulfonic acid and humic acids and hypochlorite ion. Tribromoaceticacid was generated in the presence of high bromide ion concentrations. Capillary gas chromatography has been applied to the determination of volatile organic acids in rain and fog samples by Kawamura and Kaplan (18Q). Analytes are converted to their p bromophenacyl ester derivatives. Sensitivity is approximately 10 pmol. A method for the determination of trace amounts of benzene, toluene, and C aromatics in aqueous effluents is presented by O'Brien and McTaggart (31Q). Analytes are preconcentrated using purge-and-trap techniques and separated by gas chromatography. Limit of detection is 10 pg/L. Sampling, transportation, and storage of the effluent are also discussed. Binder and Weis (4Q) have discussed the determination of diesel fuel as a pollutant in water. Their gas chromatogra hic method follows dispersion of the oil with methanol anfTween 80 in a high-speed mixer and separation of hydrocarbons on extraction cartridges. The method is applicable in the 40 ng/L to 20 mg/L range. Analysis of process waters generated from the retorting of oil shale for volatile organic acids, bases, and neutral compounds by steam distillation, solvent extraction and ion exchange procedures is the subject of a report by Richard and Junk (32Q). The relative advantages of each approach to isolation are discussed. The method for determination of 2,3,6-trichlorotoluene and 2,3,6-trichloro-p-tert-butyltoluene in water was presented by Kozlova and Kocherovskaya (25Q). These compounds are extracted into chloroform, solvent transferred into carbon tetrachloride, and analyzed by gas chromatography with flame ionization detection. An approach to the determination of volatile contaminants at the ng/L level in water by capillary column gas chromatography with electron capture detection is presented by Comba and Kaiser (88). The head-space method is applicable to drinking, surface, and groundwaters for measurement of haloforms, halomethanes, and haloethanes. It is also wellsuited to cryogenic applications. Gruber (12Q)has also used head-space analysis based upon time-delayed injection together with a calibration standard for halogenated hydrocarbons in water at a detection range of 0.1-1.0 pg/L. Volatile halocarbons in drinking water have been determined by Schulz (34Q) using quartz capillary column gas chromatography with electron capture detection. This technique employs a duck-bill type on-column injector. Graydon et al. (11Q) have described a method for the determination of highly volatile organic contaminants in water by the closed-loop gaseous strippin technique followed by thermal desorption from an activates carbon filter. The solvent-free thermal desorption approach permits the determination of compounds that normally would elute under gas chromatographic solvent peaks. Good qualitative agreement was achieved on determination of volatiles from a secondary sewage effluent when compared with results furnished by two other established methods. Kirshen and Wood (21Q) have reported on the analysis of volatile saturated and unsaturated halocarbons and aromatic compounds in water at 20 pg/L usin gas chromatography in combination with photoionization an electrolytic conductivity detection. Volatile halocarbons have been determined in canal water, groundwater, and estuarine river water by the purgeclosed loop gas chromatographic method of Wang and Lenahan (42Q) which combines pas stripping and head-space chromatography. A modified liquid-liquid extraction method for the determination of lower halogenated hydrocarbons in drinking water was developed by Inoko, Tsuchiya, and Matsuno (15Q). Samples are extracted with xylene and analyzed by gas chromatography with electron capture detection on a column consisting of tricresyl phosphate, squalene, and DC-200. Automatic determination of chlorinated hydrocarbons in water by gas chromatography has been demonstrated by Grandi, Basei, and Magelli (1OQ). The instrument is equipped with dual columns with flame ionization
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detectors, a specially modified seven-port sampling valve, and a low-temperature evaporation system. Water is retained in the first column, where it is urged countercurrently, and organic analytes are separateaon the second column. This system has been used for continuous determination of chlorinated hydrocarbons in cooling, process, and brackish waters. Blanchard and Hardy (5Q) have developed a permeation sampler device for volatile Priority Pollutants. Samples are collected by permeation through a silicone polycarbonate membrane and sorbed onto activated charcoal. This approach offers the advantage of providing time-weighted average concentration values. Gas chromatography-atmospheric pressure helium microwave-induced plasma emission spectrometry was applied to the determination of halogenated organic compounds in tap, pond, river water, and seawater by Chiba and Haraguchi (6Q). Analytes are collected on a Tenax GC column by purge-and-trap techniques. Results of the analysis of photolysis products of trichlorofluoromethane and dichlorodifluoromethane in coastal water are presented by Tomita et al. (41Q). Volatile chlorinated hydrocarbons in water-unsaturated soil matrices have been measured by Stoedtgen (37Q). This approach permits estimation of concentrations of trichloroethylene, tetrachloroethylene, and l,l,l-trichloroethane in soil water as it relates to concentration in soil air. Benzene, toluene, styrene, and xylenes have been analyzed in tire industry wastewaters by Sirotkina, Minina, and Klimak (35Q). The gas chromatographic method has a sensitivity between 5 and 15 Mg/L. Coupled columns for capillary gas chromatographic separation of organic pollutants in water have been demonstrated by Mehran, Cooper, and Jennings (29Q). Two fused silica columns joined through zero dead volume fittings were used to separate 18 volatile organohalogen pollutants. A thermally modulated electron capture detection system and a two-dimensional host-detection peak recycling gas chromatograph was employed by Keith, Hall, and Hanisch (19Q) for trihalomethane and haloacetonitrile determinations in drinking water. Applications of this approach to complex mixtures of pesticides, polychlorinated biphenyls, and dioxins are given. Gas chromatography with flame ionuation detection furnished good separation of volatile petroleum products in urban runoff water accordin to Kononyuk and Kol'nenkov (23Q). Summer rain containef much lower concentrations than snowmelt. Ryzhova et al. (33Q) has described the analysis of lake brines for 21 polycyclic aromatic hydrocarbons using packed columns. Dimethyl sebacqte in natural water and wastewater derived from sebacic acid manufacture is discussed by Gosteva and Fedonina (98). Samples are acidified with hydrochloric acid, extracted with diethyl ether, and analyzed by gas chromatography. Selective determination of volatile carbonyl compounds in polluted water and winery effluents is the subject of a report by Korol and Dovbush (24Q). Carbonyl compounds are isolated as the 2,4-dinitrophenylhydrazones. Gas chromatography has been used by Kaiga, Iyasu, and Kashihara (I7 8 )to characterize foul odors in raw water samples. Diosmin and 2-methylisoborneol were determined directly. Hattori, Kuge, and Nakamoto (13Q) have determined tripropyltin chloride in environmental waters by hexane extraction, microcolumn cleanup on phosphoric acid treated alumina, and gas chromatographic analysis with electron capture detection. Sensitivity for this compound is 0.3 pg/L. During a study of the kinetics of conversion of diethylamine into nitrosodiethylamine in model water systems, Maksimovich and Stankevich (28Q) developed a gas chromatographic method with a sensitivity of 0.5 mg/L using equilibrium vapor phases. Murayama et al. (30Q) has determined cyclohexylamine at trace concentrations in environmental water by gas chromatography with flame thermionic detection following both acid and base extraction with hexane and acetylation. At a concentration of 0.5 ng/L in river water, recovery of cyclohexylamine exceeded 90%. Similarly, diphenylamine, 4-aminodiphenylamine, and diaphene fp have been determined in antioxidant manufacturing wastewaters by Svechnikova (39Q). Phenol, cyclohexanol, cyclohexanone, isopropylamine, and diisopropylamine do not interfere in this gas chromatographic method. Simultaneous determination of 17 phosphoric acid triesters together with 11 organophosphate pesticides in environmental water by gas chromatography is the subject of a report by Kenmochi et al. (20Q). A discussion of gas chromatography and associated methods
WATER ANALYSIS
for characterization of oils, fats, waxes, and tars in water is presented by Armson et ai. (2Q). Both low- and high-resolution gas chromatographic approaches are included. Stephens (36Q) has developed a new procedure for both trace and percent level determination of 1-methyl-2-pyrrolidone in refinery waters by gas chromatography. Analyses are performed quickly on a gas chromatograph equipped with flame ionization or nitrogen-phosphorus detectors. Gas Chromatography/Mass Spectrometry
Analytical hazards resulting from artifacts inherent in the determination of trace organic contaminants in water by gas chromatography/mass spectrometry are discussed by Scott, Sutherland, and Vincent (35R). Burchill et al. (4R) have presented a general method for the determination of the organic composition profile of water resources using computerized gas chromatography/mass spectrometric analysis. A Mass Spectral Information System has been developed for the evaluation of data from the gas chromatography/mass spectrometry determination of organic contaminants in water by Martinsen, Tobin, and Song (23R). Determination of Priority Pollutants by gas chromatography/mass spectrometry in wastewater obtained from a aseous diffusion plant is presented by McMahon (25R). 8oncentrations of analytes from the volatile fraction ranged from 10 Ng/L to 2 mg/L. A method for the determination of volatile organic contaminants in well water near a chemical waste recycling plant is described by Siefker and Sapuan (39R). Chloroform extracts of water samples are subjected to acylation of the phenolic components and esterification of the carboxylic acid components prior to computerized gas chromatography/mass spectrometric analysis according to Sun and Long (40R). This technique is promoted as a general approach for acidic organic pollutants in water. The gas chromatography/mass spectrometric analysis of organic contaminants in a water extract of a soil sample exposed to hazardous waste is described by Shafer et al. (38R). The utility of capillary gas chromatography/Fourier transform infrared spectroscopy to gas chromatography/mass spectrometry as an ancillary technique is demonstrated. Fortythree compounds were completely identified by using a combination of the two techniques. Heitke (13R) has evaluated purge-and-trap methods and a commercial purge-and-trap sampler for identification of volatile compounds in water by gas chromatography mass spectrometric techniques. The device proved to be a equate for removal of purgeable Priority Pollutants in water at the 4 ng/mL level. Optimization of purging efficiency and quantitative determination of organic contaminants in water using a closed-loopstripping apparatus and computerized gas chromatography/mass spectrometry is presented by Coleman et al. (6R). Studies were conducted on both drinking water and groundwater. A comparison of packed column and fused silica capillary column gas chromatography/mass spectrometry in terms of precision and accuracy in the determination of organic contaminants in water is discussed by Eichelberger et al. ( I I R ) . Recovery results are presented for more than 80 compounds in water at low ng/L concentrations. Murata et al. (26R)have applied gas chromatography mass spectrometric techniques to the analysis of organic su stances present in tap water. Analytes are isolated and concentrated on XAD-2 resins prior to instrumental analysis. Gas chromatography/mass spectrometry in the selected ion monitoring mode has been used by Suzuki (41R) to investigate the determination of hexachlorocyclohexane isomers in aquatic environments. Manahan (22R)has used gas chromatography/mass spectrometry in the development of a simplified scheme for the determination of organic contaminants in groundwater and leachates. This approach has been demonstrated for a variety of analytes obtained as byproducts of underground coal gasification. Gas chromatography/mass spectrometric characterization of toxic organic compounds present in municipal wastewaters from 25 treatment plants is the subject of a report by Hannah and Fhsman (12R).Development of analytical methods and results in the survey are discussed. Gas chromatography/mass spectrometry was employed by Dietrich, Millington, and Christman (IOR) to establish a trace organic pollutant profile of the Haw River in North Carolina. During a 15-month study time, 52 organic pollutants were detected at concentrations in the low pg/L
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range. Dickson, Karasek, and Clement (9R)have described new computer programs which significantly increase the storage capabilities of a low-cost calculator system for gas chromatography/mass spectrometry. They convert raw selected ion monitoring data to a more compact form and permit storage of 14 60-min gas chromatography/mass spectrometric chromatograms on disks which were premously limited to four runs. The software was used in the gas chromatography/mass spectrometric determination of organic compounds extracted from a groundwater leachate taken at a municipal dumpsite. Pulse positive ion/negative ion chemical ionization mass spectrometry has been evaluated for environmental and hazardous waste analysis by Betowski, Webb, and Sauter (3R). This approach can aid in confirmation of structural assignments made by electron impact gas chromatography/mass spectrometry or electron capture gas chromatography. Shackelford et al. (37R)have completed a computerized survey of gas chromatography/mass spectrometric data acquired in Environmental Protection Agency’s Priority Pollutant screening program in wastewater samples. A system of computer programs was assembled which automatically extracts the pure spectrum from the stored chromatograms and matches against library reference materials. Negative ion chemical ionization gas chromatography mass spectrometry has been applied to the determination o trihalomethanes in drinking water by Daishima, Iida, and Kajiki (8R). Using a tetrachloroethane internal standard, detection ranges between 1 and 100 ng/L are obtained. Two new methods for compliance monitoring of purgeable organics in drinking water are described in a report by Alford-Stevens (1R).The new techniques focus on the four regulated trihalomethanes. Photodegradation products in seawater of trichlorofluoromethane and dichlorodifluoromethane have been studied by Tomita, Saitou, and Kanamori (42R). Bromochlorodifluoromethane and butadiene were identified as major products by gas chromatography/mass spectrometry. A method for determination of tributyltin chloride and dibutyltin dichloride in water has been developed by Ochi, Shinozaki, and Hayashi (28R). The approach is based upon pentylation followed by gas chromatography/mass spectrometric analysis to yield a detection limit of 1 pg/L. Waldock (43R) has described a method for determination of phthalate esters in marine environment samples using gas chromatography/mass spectrometry. The method gave satisfactory sensitivity for phthalate levels above the commonly found blank concentrations of 1-20 ng/L. Evaluation of suitable procedures for the determination of aniline and selected derivatives in wastewater and sludge by chromatographic approaches is the subject of a report by Riggin et al. (34R). This method is recommended for determination of aniline and 18 other halogen- and nitro-substituted derivatives in industrial wastewater a t low pg/L concentrations. Ogino, Saito, and Tanimoto (29R) have used gas chromatography mass fragmentography for the determination of ethylene c lorohydrin in environmental water with good precision. Water samples are extracted with hexane or ethyl acetate, concentrated with an inert gas, and analyzed directly. Zelinka (47R)has designed a gas-extraction device and described its application to water analysis for organic contaminants sorbed onto activated carbon. Analytes are desorbed with carrier gas and determined by gas chromatography/mass spectrometry. Analysis of a National Bureau of Standards sediment sample of a sludge protocol has been reported by Lopez-Avila et al. (21R).The technique involves methylene chloride extraction at dual pH, followed by gel permeation chromatography, and gas chromatography/mass spectrometric analysis. Method precision and accuracy are discussed. Kenmotsu et al. (17R)have presented a gas chromatography/mass spectrometric technique for determination of organic phosphates in water matrices exposed to heavy contamination from household sewage. Thin-layer chromatography together with mass spectrometry have been applied to identification of benz [a]acridine and benz[c]acridine in groundwater by Lei et al. (20R). Quantitative fluorometry at 384 nm yields a detection range between 0.01 and 0.40 ng/L with 65% recovery. Sampling and analysis of benthic polynuclear aromatic hydrocarbons in industrialized urban watersheds by selected ion mass spectrometry is the subject of a report by Settine and Burchfield (36R). Gas chromatography/mass spectrometry is used to quantitatively characterize areas of high concentration of specific benthic
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compounds. Recent contributions of high-resolution chromatography to the analysis of environmentally important hydrocarbons is discussed by Bayona et al. (2R). Plotting of mass chromatograms from data compiled by computer-controlled gas chromatography/mass spectrometry remains the most appropriate method for conclusive identification of these materials. Polycyclic aromatic hydrocarbons in bottom sediments are determined by capillary column gas chromatography/mass spectrometry by Ozaki, Tominaga, and Kurosaki (32R). Gas chromatography/mass spectrometry together with secondary ion mass spectrometry using phenanthrene-d,, internal standard permitted determination of 11 compounds. However, results are not reproducible for compounds with retention times greater than 1,2-benzofluorene. Negative ion chemical ionization and electron impact mass spectrometry were used by Koida et al. (18R) for determination of organobromine compounds in water. Brominated derivatives of the trihalomethanes were analyzed at concentrations of 1 pg/L. Wong et al. (46R) have developed a technique for determination of 2,3,7,8-tetrachlorodibenzo-pdioxin in industrial and municipal wastewaters by high-resolution gas chromatography/low-resolutionmass spectrometry. Recoveries from wastewater matrices are greater than 70% with a nominal detection limit of 3 ng/L at a signalto-noise ratio of 51. Peters, Nestrick, and Lamparski (33R) have described an approach to 2,3,7,8-tetrachlorodibenzo-pdioxin determination at ng L levels in wastewater which is based upon extraction and c eanup on both silica and alumina columns. Collard and Irwin (7R) applied gas chromatography/mass spectrometry to the determination of incidental polychlorinated biphenyls in complex chlorinated hydrocarbon process and waste streams. Selected-ion monitoring mode mass spectrometry is used to distinguish between various polychlorinated biphenyl formulations. The method has been used on more than 1000 samples representing about 30 different matrix types. Determination of polychlorinated biphenyls in process streams by time-programmed limited mass scan gas chromatography/mass spectrometry is reported by Westerberg, Alibrando, and Van Lenten (44R). This approach provides an optimal compromise between sensitivity and selectivity for polychlorinated biphenyl analysis in both electron impact and negative-ion chemical ionization mass spectrometry. Reduction of interferences permits less rigorous sample pretreatment and concentration as well as increased confidence in peak assignments. A simple procedure has been developed by Carlucci, Airoldi, and Fanelli (5R) for the determination of tetrahydrothiophene in water by headspace gas chromatography/mass spectrometry in the selected-ion monitoring mode. It is suitable for detecting contamination of water by tetrahydrothiophene at concentrations as low as 10 ng/mL. Isophorone and phorone in benzene or methylene chloride extracts of environmental water have been determined at the 0.1 ng/mL level by Okamot0 and Shirane (30R) using gas chromatography/mass spectrometry. Hosokawa, Kamishima, and Fukuoka (14R) have applied gas chromatography/mass spectrometry techniques to the identification of organic compounds in pulp wastewaters. Model compounds were evaluated chromatographically as their trimethylsilyl derivatives. A wastewater sample analysis produced no positive matches but several peaks were presumed to be pentose and hexose lactone derivatives. Chlorhexidine in medical wastewater is determined by selected-ion monitoring gas chromatography/mass s ec trometry according to Matsushima and Sakaurai (24R). "his disinfectant is extracted with ethyl acetate and trifluoroacetylated with trifluoroacetic anhydride prior to instrumental analysis. Recoveries of spiked wastewater samples exceeded 90% between 1 and 10 pg. A method for determination of sterols in river water by gas chromatography/mass spectrometry has been studied by Ochi and Ninomiya (27R). These steroid derivatives are extracted with hexane, subjected to alkaline hydrolysis in ethanol, reextracted, and derivatized with N,O-bis(trimethylsily1)trifluoroacetamide prior to instrumental analysis. Whelan (4%) has presented a discussion of methodologies available for obtaining profiles of volatile organic compounds in marine sediments using head-space analysis with capillary column gas chromatography/mass spectrometry. Examples are given for C1-C8 compounds in marine sediments. The analysis of drinking water for the odorant substances geosmin and 2-methylisoborneol by gas
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chromatography/mass fragmentography is described in a report by Onodera et al. (31R). These organic materials are determined at sub-nanogram-per-literconcentrations following isolation on a resin matrix. Similarly, odorous compounds present in wastewater generated from prethickener and packed-tower operations at a chemical complex are analyzed by gas chromatography/mass spectrometry according to Ito and Matsushita (16R). Hwang et al. (15R) have developed a gas chromatography/mass spectrometric method for determination of nanogram-per-liter concentrations of earthymusty odorants in potable water supplies by a salted closedloop stripping method. An increase in both sensitivity and stripping rate was achieved by raising the ionic strength of samples through addition of sodium sulfate. Concentrations of 0-300 g/L sodium sulfate were studied. Closed-loop stripping analysis together with gas chromatography/mass spectrometry has been applied to the determination of geosmin, 2-methylisoborneol,2-isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine,and 2,3,6-trichloroanisole in water by Krasner, Hwang, and McGuire (19R). Liquid Chromatography and Hlgh-Performance Liquid Chromatography
Monohydric phenols have been determined in natural waters and wastewaters at both milligram-per-liter and microgram-per-liter levels as the 4-aminoantipyrine derivatives by high-performance liquid chromatography according to Bighi et al. (2s). Precision varied with concentration and interferences, with phenol in wastewater determined at the 250-600 p g / L level with a 12-20% accuracy. Meyer, Gaydosh, and Hartwick (16s)determined phenol in process streams by microbore high-performance liquid chromatography on 1 mm i.d. columns. Significant decreases in solvent consumption and analysis time were achieved. Similarly,Vonach (28s)has determined polycyclic aromatic hydrocarbons and phenols together with anions in water by high-performance liquid chromatography on microbore columns (1-2 mm diameter) with ultraviolet detection. Carlson et al. (6s)has evaluated 2-fluorenesulfonyl chloride as an ultraviolet-fluorescent derivatizing agent for determination of phenols in aqueous media by high-performance liquid chromatography. This reagent lowers detection limits approximately 10-fold to a minimum detectability for phenol of 0.05 ng at signal-to-noise ratio of 5:l. A method for identification of chlorophenols in wastewater based upon extraction and microbore high-performance liquid chromatography with time-programmed multiplewavelength UV detection is presented by Schuster (23s). Wegman and Wammes (29s) have used high-performance liquid chromatography to determine nitrophenols in water. Paired-ion chromatography is used both for extraction and instrumental analysis with detection limits between 0.1 and 1.0 pg/L for different compounds. Schultz (22s)has developed a liquid chromatographic method for direct determination of Priority Pollutant nitrophenols in water based upon ion-pair formation and reversed-phase mode separation. Lichrosorb RP-18 and tetra-n-butylammonium nitrate are used in methanol/water. Buckman et al. (5s)have outlined the isocratic high-performance liquid chromatographic separation of a wide range of substituted phenols, including Priority Pollutants. Separations were achieved by careful selection of eluant mixtures. This method is particularly suitable to phenolic aqueous sample matrices. Analytical techniques for determination of substituted phenols in municipal sludges by high-performance liquid chromatography are described by Phillips, Zabik, and Leavitt (18s).Unique problems encountered while sampling, handling, and analyzing are also discussed. Reversed-phase mode separation together with electrochemical detection was employed for phenolic materials. Koshima and Onishi (13s) have developed a high-performance liquid chromatographic method for determination of phenolic compounds in wastewater following preconcentration on Amberlite XAD-4 resin columns. Phenol, cresols, and chloro- and nitrophenols were recovered at the 92-9670 level from distilled water spiked at 10 pg/L. Application of time-resolved fluorometry to the detection of ultratrace concentrations of polycyclic aromatic hydrocarbons in lake waters by high-performance liquid chromatography is the subject of a report by Furuta and Otsuki (9s). Replacement of the xenon lamp of a conventional fluorometer
WATER ANALYSIS
with a nitrogen laser-pumped dye laser as an excitation source improves the detection limit for polycyclic aromatic hydrocarbons by 2 orders of magnitude. Minimum detectability of this system for benzo[a]pyrene was 180 fg. Analyks in lake water were determined at 0.001 ng/L levels. Symons and Crick (26s) have used high-performance liquid chromatography for determination of polyc clic aromatic hydrocarbons in refinery effluents. Compoun s of interest are isolated by trace enrichment on C18Sep-PAK cartridges and separated in the reversed-phase mode with photometric and fluorometric detection. The detection limit is between 0.1 and 50 pg/L. A class-specificscreening method for total polycyclic aromatic hydrocarbons in wastewater which is based upon high-performance liquid chromatography is presented by Riggin, Strup, and Billets (20s). Mertens and Rittman (15s)compared gas chromatographic approaches to high-performance liquid chromatography for determination of polycyclic aromatic hydrocarbons in water and sludge. Liquid chromatography is presented as an alternative to capillary column gas chromatography for wastewater matrices. Murray, Gibbs, and Kavanaugh (17s)have described an approach to estimation of total aromatic hydrocarbons in environmental samples by high-performance liquid chromatography. This method employs an amine column to separate mixtures into groups of compounds with similar spectrophotometric response. An estimate of total aromatics is obtained by comparison of the response of each group with that from suitable reference compounds. This approach has been applied to refinery effluents. Donkin and Evans (8s) have developed a method for determination of steam-distillable petroleum hydrocarbons in water by high-performance liquid chromatography in the normal-phase mode on aminocyano packings. The potential of high performance liquid chromatography for the analysis of industrial effluents was evaluated by Zygmunt et al. (30s). Twenty selected pollutants in both standard solutions and wastewater samples at the 1ng/L level in effluent matrices were examined. Liquid chromatographic techniques are not suitable for fingerprinting purposes, their major strength lies in the isolation and determination of specific compounds or classes of compounds. Fluorescent whitening agents have been determined in river water using high-performance liquid chromatography in the reversedphase mode employing fluorescence detection. Simultaneous determination of 2,6-dichlorobenzonitrile and 2,6-dichlorobenzamide in aqueous samples by high-performance liquid chromatography has been investigated by Connick and Bradow (7s). Separation is accomplished in the reversed-phase mode on a C18 radial compression column using acetonitrile-water as mobile phase. Ultraviolet detection at 205 nm provided a detection limit of 0.01 mg/L. Venesky and Rudzinski (27s) have developed a liquid chromatographic determination of ethylenediaminetetraacetic acid in boiler water. Ethylenediaminetetraacetic acid is measured as its iron complex and yields accurate results in the presence of nickel, copper, calcium and magnesium ion. The detection limit is 0.3 mg/L with a linear dynamic range of 0.5 to 1000 mg/L. High-performance liquid chromatographic analysis of wastewater for the explosive agents SEX, HMX, TAX, RDX, and TNT has been described by Brueggemann (4s).These materials are separated on a Rad-PAK A C18reversed-phase column using a methanol-water mobile phase and ultraviolet detection at 240 nm. A detection limit of 0.2 pg/mL is reported. Dual column liquid chromatography has been used by Russell and McDuffie (21s) for the analysis of phthalate esters in environmental samples. Phthalate esters are separated from polychlorinated biphenyls and other organochlorine materials by partitioning on an alumina column. Sun (25s) has determined polychlorinated biphenyl content in environmental samples as biphenyl following reductive dechlorination with lithium aluminum hydride and instrumental analysis by high-performance liquid chromatography. Sensitivity is 0.5 ng with recoveries of better than 90%. The use of @-naphtholas a chromophore and fluorophore-forming reagent in the high-performance liquid chromatographic determination of alkyl halides as contaminants in water is discussed by Street and Hocson (24s). The method is applicable to concentrations in the milligram-per-liter range with ultraviolet detection and in the microgram-per-liter range with fluorescencedetection. Brown, Rhead, and Braven (3s)have applied rapid reversed-phase high-performance liquid chro-
d
matographic methodology to the estimation of polar dissolved organic compounds in wastewater treatment plant influents and effluents. The method is based upon elution with phosphoric acid (pH 2.65) and with sodium dihydrogen phosphate/disodium hydrogen phosphate buffer (pH 7.5). A method for routine determination of chlorophyll A in water samples by high-performance liquid chromatography has been developed by Hoyer and Clasen (10s).Fluorescence detection is employed with excitation and emission wavelengths of 435 nm and 600 nm, respectively. In a 1-L sample, the detection limit is 0.2 pg/L. Kanazawa, Nakano, and Tanaka (11s)have described a method for the determination of biotin in natural water by high-performance liquid chromatography following its derivatization by 9-anthryldiazomethane. This derivative is separated on an octadecylsilane column in the reversed-phase mode with acetonitrile-water mobile phase and measured by fluorescence at 254-nm excitation and 412-nm emission. The method exhibits a linear relationship between 3 and 400 ng of biotin. This approach is more sensitive than conventional chemical methods and more reliable than microbiological methods. Khim-Heang and Haerdi (12s) have developed a gradient elution, reversedphase method for determination of 19 amino acids in natural water at picomole levels. The technique employs postcolumn derivatization with o-phthaldialdehyde followed by fluorometric detection. Manahan and Stephens (14s)have used high-performanceliquid chromatography to measure dissolved organic compounds in bivalve aquaculture systems. Concentrations of specific free amino acids at points in the seawater systems of two aquaculture laboratories were measured by liquid chromatography. Preston (19s) has discussed the application of high-performanceliquid chromatography to the analysis of seawater with emphasis on the determination of amino acids. Bartak ( I S )has developed a technique for determination of metal complexes in natural water samples. By use of modified size exclusive and reversed-phase ion-pair chromatography,metal complexes are separated and detected with an electrochemical flow-cell device. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and ethylenediaminetetraacetic acid were the polyaminocarboxylic acids used in developing this approach. Extraction and Concentratlon Technlques
An isolation/fractionation scheme for determination of dissolved organic substances in natural and drinking water has been developed by Giabbai et al. (62'). Organic solutes are separated and fractionated on XAD-8, AG-MP-50, and Carbopack B under varying pH conditions. Test solutions containing 22 model compounds were used for process evaluation. Determination of polychlorinated biphenyls in seawater has been studied by Zhang, Gu, and Xu (317'). Analytes are isolated on Amberlite XAD-4 resin, eluted with warm acetone, and back extracted with petroleum ether. Recovery is approximately 66% at the nanogram-per-liter level. Yan et al. (307') have evaluated the use of GDX-102 porous polymer beads for enrichment of trace organics from water. Phenol and cresols recoveries are 95%. The use of XAD-2 resin for simultaneous extraction and derivatization of organic acids in water has been investigated by Rosenfeld, MureikaRussell, and Phatak (2279. Impregnation of the resin with benzyl or pentafluorobenzyl bromide effects simultaneous extraction and derivatization of the acids. Reaction occurs in an aqueous-solid matrix with ester derivatives remaining sorbed onto the resin until eluted with a volatile organic solvent. A discussion of artifacts and losses resulting from sampling of chlorinated waters by XAD adsorption is given by Cheh (113. Sampling losses of some mutagenic compounds were observed. The use of Chromosorb T, an aggregate polymer of tetrafluoroethylene, to concentrate trace organic materials from aqueous solution has been studied by Josefson, Johnston, and Trubey (Ion.Recovery experiments indicate that this material gives quantitative results with a variety of solutes at the 50 pg/L level in aqueous solutions containing 2 mg/L of humic acid. Janicke (9T) has studied the absorption effects of plastics upon organic water pollutants. Sorption is primarily a function of the nature of the plastic and secondarily, on the hydro- or oleophilicity of the compound. A low-surface area polypropylene has been evaluated by Rice and Gold (192') as an adsorbent for trace enrichment ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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of organic compounds in water. Good recovery was exhibited for compounds of limited aqueous solubility; however, the capacity was lower than other types of adsorbents. Chriswell et al. (27') have evaluated the adsorptive properties of silicalite for isolation of polar low-molecular-weight organics in drinking water. Characteristics of this molecular sieve material for accumulation of analytes from aqueous streams were elucidated and an analytical protocol presented for compounds such as dichloroacetonitrile. Zhang et al. (327') have reported a new technique for enrichment of organomercury compounds in river water. Pressurized adsorption is used for on-site field sampling followed by a second enrichment in the laboratory using a sulfuryl cotton column. The detection limit is below 0.3 ng/L. Resin extraction is a feasible technique for screening organic compounds present in effluent waters according to Zygmunt, Brinkmann, and Frei (347'). Resin extraction is time- and solvent-saving and provides an alternative check method based upon different chemical principles; however, it is probably not ideal for determination of pollutants in heavily contaminated samples. A purge-and-trap method has been developed by Warner and Beasley (2977 for determination of four Priority Pollutants in aqueous samples. Water samples are purged a t 50 "C with helium, the analytes trapped on Tenax GC and analyzed by gas chromatography following thermal desorption. The method was laboratory validated over the 20-500 pg/L concentration range for acrylonitrile, chlorobenzene, ethylbenzene, and 1,2-dichloroethane. The application of the Grob procedure to the gas stripping analysis of volatile hydrocarbons in water has been studied by Marchand and Caprais (132"). Analytes are eluted from charcoal with 15 pL of carbon disulfide and analyzed by gas chromatography. The recoveries of the method were calculated for various types of volatiles. In another modification of the Grob technique, odorous compounds present in drinking water were determined by Saevenhed et al. (237'). Recoveries of compounds determined increased substantially at elevated stripping temperatures and polarized stripping times. At higher temperatures, the use of an open-loop rather than a closed-loop stripping system simplifies analysis. Simmonds (257') has described a simplified purge-and-cryotrap approach to the determination of halocarbons in natural waters. The usual Tenax adsorption trap is replaced with a cryoloop preceded by a permeation dryer which selectively removes water vapor thereby preventin freezing in the loop. With this method, previously unreporte halocarbons were detected in natural waters. Gershey (57') has designed a new sampling device which employs a bubble adsorptive technique to produce aerosols from seawater that are enriched with respect to surface active organic matter. Concentration factors of greater than 100-fold are obtained. Static headspace or vapor equilibrium analysis, in which the aqueous solution is allowed to equilibrate with the gaseous phase above it, was recently reported by McNally and Grob (147'). Solubility limits for halogenated alkanes and alkenes, and volatile aromatic Priority Pollutants were determined by this approach. Thomason and Bertsch (287') have investigated the applicability of a closed-loop gas-stripping apparatus for determination of trace organic compounds in water. The effects of extraction solvent, stripping temperature, stripping time, pH, and salt content on the closed-loop system were studied. Carbon disulfide was found to be the best solvent for extraction at 40 "C. A direct comparison of the closed-loop stripping method with the purge-and-trap on Tenax GC method was performed on river water. Extraction of dissolved hydrocarbons in water by gaseous stripping is improved by addition of sodium chloride and methanol according to Rimmelin et al. (2011.Solvent-solute interactions are promoted which improve analytical results. Polynuclear aromatic hydrocarbons present in water have been determined by spectrofluorometry following foam separation by Mori and Naito (162"). Recoveries in river water ranged between 20 and 80% at the 20-ng level and 56 and 98% at the 200-ng level. Smith et al. (267') have discussed the pitfalls of using a micro liquid-liquid extraction system for isolation of polyaromatic hydrocarbons in water samples. Incomplete solvent recovery precluded reliable results. Thin-layer chromatography with preconcentration by hexane extraction is reported by Polishchuk and Gorbonos (177') to be more effective in determining 2-trichloromethyl-6-chloropyridine in wastewater than a spectrophotometric method
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based upon the Fujiwara ring cleavage. The chromatographic method permits detection of 0.3 pg of material with no interference from 2-picoline. A technique for separation, concentration, and identification of 34 organic compounds in drinking water has been described by Zhou et al. (337'). Concentration factors of 104-105are claimed. Fujimoto (411 has determined chloroform, bromodichloromethane, dibromochloromethane, trichloroethane, carbon tetrachloride, and tetrachloroethylenesimultaneously in river and municipal waters by combing two kinds of chromatographic packings into a headspace method. The effect of membrane filtration upon estimates of microbial adenosine triphosphate in freshwaters is discussed by Pridmore, Hickey, and Hewitt (187'). Adenosine triphosphate was found in both particulate and dissolved fractions of water samples with higher concentrations of particulate adenosine triphosphate obtained when extracted directly from samples rather than following preconcentration through membrane filters. Polyaromatic hydrocarbons have been determined in wastewater by onedimensional thin-layer chromatography employing fluorescence spectrometry with computing integration according to Schoessner, Falkenberg, and Althaus (247'). In a similar approach, Thielemann and Grahneis (277') have described a thin-layer chromatographic method for separation and identification of carcinogenic aromatic hydrocarbons in drinking water based upon activated carbon adsorption, ethyl ether extraction, and chromatography in a solvent of hexane/ chloroform with fluorometric detection. Kozlowski, Sienkowska-Zyskowska, and Biziuk ( I 17') have applied countercurrent thin-layer headspace chromatography to continuous determination of volatile organic compounds in water. This technique results in better conditions of transfer of volatile components from liquid to gaseous phase through significant limitation of the concentration diffusion effect in a thin layer. Fractionation, isolation, and characterization of Ames-mutagenic compounds in Kraft pulp chlorination-stage effluents are outlined in a report by Holmbom et al. (87'). The mutagenic components were concentrated to a narrow band by thin-layer chromatography on silica and by reversed-phase mode high-performance liquid chromatography. Optimization of liquid-liquid extraction methods for organic analysis in water is discussed by Glaze and Linn (77'). Effects of choice of solvents, solvent-to-water ratio, matrix pH, ionic strength, and the presence of quenching agents and methanol on extraction efficiency were studied. The determination with a detection level of 0.10 bg/L of trihalomethanes in water based upon liquid-liquid extraction by vigorous agitation of a pentane-water mixture is the subject of a report by Mehran, Slifker, and Cooper (157'). Lyatiev, Zaklinskii, and Sokolova (127') have designed and tested an apparatus which permits direct liquid-liquid extraction of contaminants by a specific volume of solvent from any volume of water. It can be used with extracting agents both lighter or heavier than water and recovers pollutants in natural water at trace levels as well as at higher concentrationsin industrial wastewaters. Multistage extractions can be done. A process for extraction of organic contaminants from aqueous samples by injection of an organic solvent under pressure to form uniform droplets in the sample has been developed by Rogers, Parker, and Loucks (217'). Solvent drops are then collected and analyzed. A method for determining hydrocarbons dissolved in seawater including fractionation into 5 homogeneous classes has been described by Desideri et al. (3T). Hydrocarbons are separated from polar compounds by adsorption chromatography in a two-step sequence on silica gel and alumina. Photometry and Spectrophotometry
Disinger et al. (5U) have investigated several approaches to the chromatographic and spectrophotometric analysis of underground coal gasification byproduct waters. Emphasis is placed on the phenols because of their abundance, water solubility, and potential environmental effects. An extractive spectrophotometric method for determination of submicrogram amounts of phenol based upon oxidative coupling with o-tolidine using potassium dichromate-ferricyanide as oxidizer in buffered sodium carbonate solution (pH 11.5) is presented by Verma and Gupta (33U). The purple isoamyl alcohol extract exhibits an absorption maximum at 535 nm. Beer's law linearity is demonstrated between 0.1 and 0.7 pg for phenol
WATER ANALYSIS
present in polluted river water. A similar photometric determination of phenols in wastewater by the 4-aminoantipyrine method with iodine has been described by Kurihara (14U). The effect of six different oxidizing agents on the condensation reaction was studied. The adduct is extracted into chloroform and measured colorimetrically at 460 nm. Detection range for phenol was between 1 and 50 pg. Goodwin and Marton (9U) have described an improved distillation apparatus for continuous-flowdetermination of phenol in wastewater. Ten samples per hour can be processed with a detection limit of 5 pg/L. A real-time, field-portable derivative ultraviolet absorption spectrometer has been designed and evaluated as a wastewater monitor by Hawthorne et al. (11U). The instrument is microprocessor controlled and offers several operating modes for determination of phenols, cresols, and xylenols at microgram-per-liter concentrations. Sun (27U) has determined volatile phenols in natural water by extraction with butyl acetate followed by back extraction with sodium hydroxide for colorimetric determination. This approach is not suitable for high turbidity or colored samples and is subject to interference by sulfur compounds which can be eliminated by stabilizing with bismuth nitrate solution. Burakov et al. (4U) have proposed the determination of phenols in natural water by alkalizing and oxidizing parallel samples and measuring the absorbance of both the alkaline and acid Samples. Absorbance differences between alkaline and acid portions of the water sample at 290 nm and 400 nm permit calculation of phenol content. Kuptsova et al. (13U) have concluded from their studies that determination of volatile phenols in wastewaters by the colorimetric method using 4-aminoantipyrine was more precise and sensitive than the colorimetric method using pyramidon. Ultraviolet spectrophotometry has been used by Pavlova, Dashkovskii, and Kostenko (21U) to estimate the degree of contamination of brewery wastewaters. Correlations are shown between chemical oxygen demand and ultraviolet absorbance in biologically treated fermentation effluents. Riggin and Strup (23U) have developed a screening method for determination of total polynuclear aromatic hydrocarbons in industrial effluents. This approach involves solvent extraction, chromatographic cleanup on alumina, and analysis by ultraviolet spectrophotometry. The UV detection step utilizes a band-pass filter in order to obtain more uniform responses for all analytes. The method utilizes considerably less expensive equipment and requires half to one-third the time and effort of Environmental Protection Agency's Method 610. Colorimetric determination of trihalomethanes in drinking water has been reported by Huang and Smith (12U). The techniques is based on the Fujiwara reaction and involves pentane extraction, reaction with sodium hydroxide and pyridine, and colorimetric measurement of the bluish pink color formed upon heating. Verma and Gupta (32U) have described a spectrophotometric method for determination of methanol in water. Methanol is oxidized to formaldehyde which is measured colorimetrically following reaction with p-aminoazobenzene and sulfur dioxide in acidic medium. Beer's law is obeyed between 100 and 600 pg at 505 nm with a detection limit of 5 pg/L methanol. Minenko (17U) has developed a method for determinatin of p-chlorobenzotrichloride in wastewater by extraction and colorimetric measurement using the Fujiwara pyridine ring cleavage reaction. Relative error is below 20% at a detection limit of 0.05 mg/L. Psaltyra and Cheremukhin (22U) have presented an extraction-photometric method for determination of hexabromo2-butene in rinse waters generated from polystyrene manufacture. The detection limit is 0.1 mg/L with analysis time of 1.5 h. Spectrophotometry has been applied to the determination of small amounts of aromatic hydrocarbons and arylmonosulfonicacids in dye-manufacturing wastewaters by Baloiu, Visan, and Costove (10. Aromatic hydrocarbons are determined by their absorption bands a t 270 nm and arylsulfonic acids at 565 nm following complexation with a basic dye. A colorimetric method for determination of acetylene in p-ionone production wastewaters containing high concentrations of ammonia has been presented by Staroverov et al. (26U). Relative standard deviation is below 1% at a detection limit between 1.0 and 10 pg/L. The effect of sample temperature upon ultraviolet absorption photometry of wastewater has been examined by Nakagawa and Ariga (18U). Studies focused on the effect of humic acid, lignin, and tannic
acids contained in the sample. A comparison of optical methods to other conventional techniques for determination of organic matter in natural waters has been made by Bikbulatov (2U). Measurement of absorbance does not allow for determination of absolute concentrations of organic matter in natural waters but does permit monitoring of relative changes in composition. Polyelectrolytes in wastewater can be estimated by measurement of their transmittance at 554 nm according to Hanasaki ( I O U ) . Optimum pH for measurement is less than 7 and optimum temperature is between 10 and 30 "C. Addition of sodium nitrate and sodium chlorate increases sensitivity. The infrared spectrophotometric determination of oil pollutants present in water has been described by Xin, Moldoveau, and Lepadatu (36U). Examination of a carbon tetrachloride extract at a fixed wavenumber common to many components is used. Differences in infrared characteristics permit both qualitative and global assessments, and with suitable standards quantitative measurements can be made. Tanaka et al. (29U) have developed a screening method for determination of oil content of river water by nondispersive infrared spectrophotometry, Recovery of oil was about 80% at 0.5 mg L. Determination of trace organic compounds in seawater y a Raman scattering apparatus using the 514.5-nm line of an argon-ion laser source to record spectra from 1070 to 1406 wavenumbers is reported by Mann et al. (16U). Sensitivity ranges between 1and 400 mg/L depending upon the nature of the compound. Estimation of hydrocarbons in water (methylene index) has been investigated by Rochat, Albert, and Alary (24U). This approach involves extraction with carbon tetrachloride, purification on an adsorbent, and infrared spectrophotometric measurement. The influence of various parameters upon improvement of the methylene index was examined. Bramsoe (3U) has described an improvement in a sensitive infrared spectrophotometric method for determination of mineral oils in drinking water. It is based upon use of ultrapure alumina-cleaned carbon tetrachloride for extraction and on a &fold ordinate expansion with a 60-min scan time on the spectrophotometer. Duve (6U) has designed an apparatus in which organic compounds in water are continuously determined by decomposition of the inorganic carbon with acids followed by oxidation of organic compounds with ultraviolet radiation. Fluid decomposition products are continuously removed by a circulating gas followed by infrared spectrophotometricanalysis of the gas or conductivity analysis following solution of the gas in desalinated water. This device allows measurement of organic content in water at 1 pg/L in less than 1 min. Maggi, Stella, and Ciceri (15U) have used infrared spectrophotometry for characterization of organic matter in river water. Amberlite resins are used for fractionation into humic acid, fulvic acid, and alcohol-soluble fractions. Interactions of these purified fractions with cupric and cadmium ions were also studied by Getsen, Bachurin, and Kalachnikova @U),who employed comprehensive infrared spectrophotometric analysis in the determination of organic matter dissolved in stratal waters attendant to prospecting for petroleum and natural gas. Vagina, Dorokhova, and Poletaev (30U) has used infrared spectroscopy for studying the composition of wastewater during its biological purification. An on-stream standard-addition spectrofluorometric technique has been developed by Velapoldi et al. (31U) for determination of polynuclear aromatic hydrocarbons in the effluents from generator columns used to prepare National Bureau of Standards reference compounds. It is suitable for determination of polyaromatic hydrocarbon concentrations, aqueous solubilities, and octanol-water partition coefficients. Jet fuel, kerosene, gas oil, and heavy fuel oil, present as contaminants in water, have been differentiated and identified by fluorescence spectroscopy, index of refraction, and ultraviolet spectrophotometry by Ogawa (20U). Fluorescence spectroscopy was used to estimate number of days elapsed since occurrence of the spill. Phenol and cresols in seawater have been determined by direct fluorometric examination of the water phase without extraction by Naley (19U). The use of laser-induced pumping of quasi-linear spectra of low-temperature luminescence in the analysis of organic matter in stratal waters was evaluated by Vershinin et al. (34U). Individual compounds can be determined at 0.001% concentration in a 5-mg sample. Ewald, Berger, and Belin (7U) have described the technical requirements for direct observation
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of fluorescence of dissolved fulvic acid in natural waters. Ultrafiltration experiments suggest that the observed fluorescence originates from macromolecular substances. Watanabe et al. (35U) has presented a rapid method for determination of organosilicones in water by inductively coupled plasma emission spectroscopy. A petroleum ether extract is evaporated to dryness and the residue dissolved in methyl isobutyl ketone and aspirated directly into the plasma. The detection limit is approximately 0.01 pg/mL and is adequate for most environmental samples. Yu (37U) has determined microamounts of butyl xanthonate in wastewater as the copper xanthonate complex in methyl isobutyl ketone by absorption spectroscopy. The method has a sensitivity of 0.062 pg/mL and permits samples to be processed at the rate of 10 samples per hour. Tanaka et al. (28U) have reported a method for determination of monomethylarsonic acid and dimethylarsinic acid in water which is based upon borohydride reduction to methylamine and dimethylarsine, respectively. These compounds are isolated in a liquid nitrogen trap and separated by sequential vaporization prior to atomic absorption spectrometric measurement. The detection limit is 14 and 26 ng/L, respectively. Rudischer (25U) has described a rapid method for determination of fats in wastewater by chloro- or bromonaphthalene extraction followed by refractometric determination. Other Instrumental Techniques and Devices
The feasibility of using fiber optics for monitoring groundwater contaminants has been discussed by Hirschfeld et al. (5V). Fluorometric analysis combining long-range communication fiber optics, laser excitation, and Raman spectroscopic measurement techniques has been applied to determination of organic pollutants in groundwater. Fluorescent dyes are detected a t microgram-per-liter levels over distances greater than 1000 m. Kawahara et al. (7V) have described a device for monitoring hydrocarbons in water. An unclad fiber optic inserted through a stainless steel capillary is coated with an organophilic compound radiated at 632.8 nm by a low-power laser. Normal total internal reflection is degraded by adsorption of hydrocarbons upon the coating so that variation in the output si nal can be related to concentration of the hydrocarbons #owing through the capillary. Aromatics, crude oil, and oil products dispersed in water can be measured direct1 ,without the need for solvent extraction. In a report by LeLeva, Pruger, and Rivlin ( I O V ) , a mass spectrometer is described for computer-assisted analysis of multicomponent aqueous solutions of or anic compounds. The instrument comprises a monopolar rafio frequency mass spectrometer combined with a vacuum chamber with flanges for connection to a zeolite pump for preevacuation, a pump €or high evacuation, measuring lamps, and an inlet system. The mass spectrum of a water supply sample revealed ions at 29 organic compounds. The use of gel chromatography for evaluation of river quality has been investigated by Maruyama et al. (11V). Samples are fractionated through Sephadex G-15 and analyzed by ultraviolet absorption to evaluate degrees of pollution. Absorbance is correlated with biological oxygen demand. Byers, Anderson, and Hickam (3V)have used ion exclusion chromatographyfor the determination of formic and acetic acids in steam generator condensates and blowdowns. Barber and Braids (1V) have reported the field application of an organic vapor analyzer, based on gas chromatography, and its use in three specific case studies of groundwater contamination. Mussmann (12V) has used Draeger tubes for rapid estimation of chemical contaminants in soil and water. These tubes are available for field use in a wide variety of chemical reactions suitable for many constituents. A device has been designed by Bystrovzorov, Ivanov, and Chel'tsov (4V)for determination of volatile phenols in wastewater. In consists of a measuring device, an automation unit, and a power source. A distillate from a pH adjusted sample is titrated coulometrically with electrically generated bromine to an amperometrically determined equivalence point. Quasi-linear luminescence and excitation spectra have been used by Khesina, Khitrovo, and Gevorkyan (8V) for determination of polycyclic aromatic hydrocarbons in industrial motor transport effluents. Procedures for extraction, chromatographic cleanup, and qualitative and quantitative analysis are presented. Determination of vitamin Blz in beer and 76R
ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
pharmaceutical preparation wastewaters by chemiluminescent measurement of cobalt(I1) content has been studied by Jia and Zhang (6V). Content of Bl2 from two plant wastewaters ranged between 77 and 144 pg/L. A method based upon isotachophoresis for determinatron of chlorinated acetic and maleic acids in chlorinated wastewater has been reported by Onodera et al. (15V). Potential unit values for 24 compounds in four different electrolyte systems are presented. A microprocessor-controlled, multichannel fluorometer has been described by Oldham, Patonay, and Warner (14V). Advantages of multichannel fluorescenceare discussed in the context of continuous monitoring of chlorophyll fluorescence in seawaters. Sensitivity is 5 X M with linearity over 3 orders of magnitude. Scully, Oglesby, and Buck ( 1 7 0 have applied cyclic voltammetry to organic N-chloroamines in aqueous solution. Mechanism of the electrode process is discussed in reference to the effect of varying voltage scan rates on peak currents and potentials. Shen and Wang (18V) have used cathode-ray polarography to determine hexogen in water at the 1.0 pg level. The calibration curve is linear at concentrations between 0.08 and 40.0 pg/mL at peak current of -0.56 V. Recoveries range between 90 and 109%. Manometric respirometry has been applied to estimation of biodegradability of chemicals in water by King and Painter (9V).Five of the eight compounds studied are recommended as candidates for use in validation of new biodegradability methods. Neupert (13V) has provided a method for determination of total extractable, organically bound chlorine in water based upon solvent extraction, combustion of the extract, resolution of the residue, and chloride determination by ion-selective electrode. The selection of a standard substance for determination of lignosulfonic acids in water has been investigated by Pilipenko et al. (16V). A low-molecular-weight fraction is reported to be a better standard than sulfite liquors or any high-molecular-weight fraction for electron paramagnetic resonance and ultraviolet instrumental methods. Pesticides and Detergents
A method has been developed by Hill et al. ( l o w ) for determination of chlorophenoxy acid herbicides in wastewater and sludges. Following 2-chloroethylation of purified extracts, both packed and capillary column gas chromatography were evaluated for detection by electron capture or mass spectrometry. Goewie et al. (7W) determined phenylurea herbicides and their corresponding anilides by employing precolumn technology together with high-performance liquid chromatography on metal-loaded phases. A special platinum loaded phase in a short column acts as an aniline trap for group separation of the herbicides. Workability of this approach was demonstrated on polluted river water. In a similar report, Senin, Volkov, and Berezkin (25W) have determined phenylureas in natural water by high-performance liquid chromatography following preconcentration on Chromosorb 102 and elution with acetone. Detection limit is approximately 0.10 pg/L. Steinheimer and Brooks ( 2 0 have described a multiresidue technique for determination of triazine herbicides in natural water samples. Seven compounds are determined simultaneously at a nominal detection limit of 0.1 pg/L in a 1-L sample. Bonded-phase extraction is demonstrated to be a viable alternative to liquid-liquid partition for removal of these analytes from a water sample. A sample enrichment method for herbicide residues in water which is based upon chromatographic extraction on graphitized carbon black has been presented by Mangani and Bruner (14W). The advantages and limitations of carbon black are discussed. Wells, Michael, and Neary (32W) have described a procedure for determination of picloram in environmental water by trace enrichment on C18Sep-PAK followed by high-performance liquid chromatographic analysis with ultraviolet detection at 254 nm. The detection limit is reported at 2 pg/L. Pentachloronitrobenzene and dichloronitrobenzene in water were determined at the microgram-per-liter level by Kondo, Murada, and Ando (11W) employing hexane extraction and gas chromatography. A method for determination of two fungicides, etaconazole and propiconazole, in water was studied by Buettler (3"). Recoveries from 76 to 100% indicate that this approach is suitable for residue analysis at 1pg/L when using gas chromatography with alkali flame ionization detection in the nitrogen-sensitive mode. Other nitrogen and
WATER ANALYSIS
phosphorus containing fungicides, herbicides, and insecticides did not interfere. Burchill et al. (4W) have discussed the application of electron capture, mass spectrometric single ion, and flame photometric detectors in gas chromatography to the determination of haloforms and herbicides in water. The determination of organochlorine insecticides in water by concentration on Wofatit Y29, Y55, and Y56 was reported by Seefeld and Florstedt (24W). Lindane, methoxychlor, and @-endosulfanwere determined at 0.10 ng/L with greater than 80% recovery by elution from Y56 with ethyl acetate. Xue (33W)has analyzed water samples for organophosphorus and organochlorine insecticides following concentration on XAD-4 and instrumental analysis by gas chromatography. The resin approach gave results comparable to liquid-liquid partition approaches. Organochlorine pesticides were determined in groundwater following concentration on XAD-2 resin according to Bian and Ding (2W). Recoveries from the resin itself range between 90 and 111% with the exception of abenzene hexachloride which was much lower. G mini-ion exchange column can be used to eliminate ammonia interference during the purge-and-trap determination of organochlorine compounds in water according to Cooper et al. (5W). This technique has been successfully applied to chlorinated groundwater and secondary treatment effluents. Chlorinated hydrocarbons includin both insecticides and polychlorinated biphenyls have been fetermined by Mohnke et al. (17W) in waters of the Baltic Sea using gas chromatography. Imrovements in methodology for pesticide detection in oceans y capillary column techniques are also discussed. An analytical method for detection of aldicarb and its derivatives in drinking water has been developed and refined by Lemley and Janauer (12W). Methanollwater was used with preconcentration procedures to provide reliable techniques which do not require bulk extraction or cleanup of sample extract prior to aldicarb analysis. A new gas chromatographic method was perfected for quantitation at microgram-per-liter levels. A rapid method for determination of l-naphthylmethyicarbamate in water and wastewater sludge has been developed by Ogino et al. (20W). A methylene chloride extract is washed with alkali, purified by alumina microcolumn chromatography, hydrolyzed to 1-naphthol, monochloroacetylated,and analyzed by gas chromatography/mass spectrometry. The insecticide aminocarb and ita derivatives have been determined in water by isolation on Amberlite resins followed by gas chromatographic analysis employing a nitrogen-phosphorus detector according to Levesque and Mallet (13W). Analytes are removed from water at pH 7 by XAD-4 with greater than 80% efficiency. Methods developed for ethoxyquin, thiabendazole, and maleic hydrazide in water have been reported by Victor et al. (28W). Following membrane filtration, samples are analyzed by direct aqueous injection-high-performance liquid chromatography with fluorometric detection for ethoxyquin and thiabendazole, and electrochemical detection for maleic hydrazide, each a t an estimated sensitivity of 1pg/L. The techniques are applicable to industrial wastewater with little or no cleanup. Dekker and Houx (6W)have published a method for determination of residues of aldicarb, aldicarb sulfoxide, aldoxycarb, oxamyl, and methomyl in both groundwater and surface water. Compounds are detected by high-performance liquid chromatography using either variable-wavelength ultraviolet or fluorometric devices following postcolumn derivatization. Recoveries varied between 77 and 99% at typical residue concentrations. High-performance liquid chromatography has been used by McCown (15") for determination of the insecticide rotenone and its degradation product rotenonone in freshwater. Ultraviolet detection a t 229 nm is used for both compounds with response-linearity expressed over 4 orders of magnitude between 10 and lo6 pg. Nakamura, Fujisawa, and Namiki (19W) have presented a method for determination of anionic surfactants in river water and sewage. It is based upon extraction of the ion-pair complex of the surfactant with potassium dibenzo-18-crown-6 into methyl isobutyl ketone followed by determination of the potassium by atomic absorption spectrometry. While sodium and potassium and interferences are eliminated by washing the methyl isobutyl ketone phase with potassium sulfateammonium acetate solution, cationic surfactants interfere. In a similar approach described by Zhang and Yang (35w),anionic detergents in water are indirectly determinated by extraction with methyl isobutyl ketone in the presence of sodium
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chloride and estimated by atomic absorption spectrometry of sodium. Recoveries range between 93 and 100% for 30 pg of sodium alkylbenzenesulfonate in a 0.1-L sample. Hamane and Adachi (3W)have analyzed water and wastewater for anionic detergents by a Technicon automated analysis procedure using methylene blue. Addition of sodium bisulfite effectively masked residual chlorine in the samples. Some of the problems of removing interfering substances in the determination of anionic surfactants in a water sample are discussed by Mukai et al. (18W). Pretreatment with XAD-2, followed by hydrolysis with hydrochloric acid prior to methylene blue determination, removed most interferences. Foam concentration followed by colorimetricanalysis with methylene blue for determination of ionic surfactants is presented by Minagawa, Sato, and Morita (16"). The foam concentrate is extracted with 4-methyl-2-pentanone and hexane prior to colorimetry. Recovery ranges between 96 and 10170at sensitivities between 5 and 100 pg. In a procedure described by Grasso et al. (8W), oils and fats are determined in water in the presence of surfactants by continuous liquid-liquid extraction with petroleum ether followed by silica gel fractionation to isolate oils and fats, which are determined gravimetrically on porous cellulose septa. A new approach to identification of cationic and anionic surfactants in surface water by combined field desorptioncollisionally activated decomposition mass spectrometry has been presented by Schneider et al. (23W). The three types of surfactants each desorb at distinctly different emitter heating currents; so that nonionic surfactants can be characterized at 5 mA, cationic surfactants at 20 mA, and anionic surfactants at 23 mA. Proper choice of emitter heating current permits partial separation of each class. High-performance liquid chromatography has been applied to the determination of dodecylbenzenesulfonate in water by Yao, Yu, and Fang (34W). The detection limit is 0.014 pg with a recovery of 103%. Waters and Garrigan (30W)have reported on an improvement in the microdesulfonation/gas chromatographic procedure for determination of linear alkylbenzenesulfonates in river water. Compounds are extracted as the methylene blue complex, desulfonated with phosphoric acid, and analyzed by gas chromatography at a sensitivity of 10 pg/L with recovery greater than 90%. Similarly, determination of alkybenzenesulfonates in river water by methyl isobutyl ketone extraction and high-performance liquid chromatographic analysis as the methylene blue complex has been reported by Ohkuma (21W). Reversed-phase mode chromatography was employed with ethanol as mobile phase in a phosphate buffer. Wee (31W) has compared methods for determination of ditallow dimethylammonium chloride in river water and concluded that high-performance liquid chromatographic approaches are more sensitive and rapid and as specific as disulfine blue based methods. Indirect determination of nitrilotriacetic acid in water has been evaluated by Voulgaropoulos, Valenta, and Nuernberg (23W). Bismuth ion is added in excess along with ethylenediaminetetraacetic acid to form stable complexes with both at pH 2. The uncomplexed bismuth is then deposited into a hanging Hg drop electrode at a potential of -0.015 V vs. standard calomel electrode and subsequently stripped anodically in the differential-pulse mode. The detection limit is 0.1 pg/L. Polyoxyethylenetype nonionic surfactants in water were determined using atomic absorption spectrophotometry with a graphite furnace atomizer by Adachi and Kobayashi (I W). This approach is based upon determination of cobalt in a chelate complex formed by reaction of nonionic surfactants with ammonium cobalt tetrathiocyanate reagent. Sensitivity in various environmental waters was 1pg/L with recoveries between 93 and 111% on spiked samples. Sodium picrate has been used by Saito and Hagiwara (22W)for complexation of polyoxyetkylenenonionic surfactants in water prior to extraction and spectrophotometric determination. Recoveries range between 93 and 107% at a sensitivity of 4 pg/O.l L following removal of iron and cadmium interference by addition of cyclohexane diaminetetraacetate. Tanaka, Kobayashi, and Numada (27") have described the determination of polyethylene glycol alkylamides in water. The method involves chloroform extraction, removal of interferences by ion exchange and adsorption chromatography, esterification, and instrumental analysis by gas chromatography. ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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Total Elemental Analysis and Oxygen Demand
An automated determination of dissolved organic carbon in seawater in the sub-milligram-per-liter range has been reported by Cauwet (3X). This continuous-flow technique is based upon dithionate and ultraviolet oxidations and permits direct measurement with high sensitivity by flame ionization detection. A conventional wet digestion infrared spectrophotometric detection procedure for determination of total organic carbon in groundwater has been modified by Barcelona (1x1 to include a volatile organic fraction. Volatile organic carbon is isolated by purge-and-trap instruments similar to those used for other specific organic separations. The use of a carbon dioxide electrode in the automatic determination of dissolved organic carbon in water is the subject of a report by Princz, Gelencser, and Kovacs (21X). An oxidized sample is introduced into a flow cell equipped with a carbon dioxide gas sensing electrode. The electromotive force of this electrode is proportional to the logarithm of the dissolved organic carbon concentration so that dissolved organic carbon levels can be measured in the range from 1 to 100 mg/L carbon. Instrumentation and methods for determination of total organic carbon representing trace organic substances in high-purity semiconductor manufacturing water are discussed by Poirier (2OX). Ultrafiltration has been used by Cole, McDowell, and Likens ( 4 X )to determine the origin of the dissolved organic carbon in an oligotrophic lake. An input/output budget for each molecular weight class is presented. Profe (22x1 has modified a method for determination of particulate organic carbon in seawater. Samples are fiitered on glass fibers, oxidized with potassium dichromate in sulfuric acid, diluted with distilled water, centrifuged, and measured spectrophotometrically at 445 nm against a glucose solution as blank. The method is accurate for 0.5-1.0 mg of carbon per filter. Problems related to accurate carbon measurements in marine sediments and particulate matter associated with seawater are discussed by Weliky et al. (32X). An approach is described which permits direct measurement of both organic and carbonate carbon in a single particulate matrix. Any instrument relying on combustion furnace and thermal conductivity or infrared absorption for carbon dioxide may be converted to use this approach. The use of surrogate methods for determination of total organic halides, purgeable organic halides, and solvent extractable organic halides in wastewater is discussed by Riggin et al. (23X). A pyrolysis-microcoulometric instrumental system was used for comparison of this approach to compound specific gas chromatographic or gas chromatography/mass spectrometric methods. Advantages and limitations of surrogate methods are presented. Gebhardt (6x1 has developed instrumentation for direct determination of total organic chlorinated compounds in aqueous samples without preconcentration. One approach involves isolation by flash evaporation, and a second approach involves the use of a piezoelectric crystal as a detection device. A number of crystal coatings were tested, and Amine 220 was found to have appropriate characteristics. Okamoto and Shirane (19x1 have described a method for determination of extractable organic halogen materials in water and sediment. Compounds of interest are extracted with hexane and separated by vaporphase reduction over a palladium catalyst and resulting halide ions are measured by ion chromatography. High recovery is obtained for chlorine derivatives with a sensitivity of 0.005 hg L in water and 0.005 pg/g in dry sediment. Total organic ch orine determination based upon XAD-8 resin adsorption and particle-induced X-ray emission has been developed by Hemming et al. (9X). This approach was successfullyapplied to recipient waters from a kraft bleach plant effluent at a detection limit of approximately 10 hg/L. Three different methods for determination of organohalogen in effluents from bleacheries in the pulp and paper industries have been compared by Carlberg and Kringstad (OX). One method determines extractable organohalogen directly, one determines purgeable and carbon-adsorbable organohalogen, and one determines high- and low-molecular-weight organohalogen following preseparation. A method for simultaneous determination of organically bound halogen and sulfur in water has been presented by Schnitzler et al. (24X). It is based upon adsorption on activated carbon, displacement of interfering ions with nitrate, combustion of the carbon, scrubbing of the
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acidic gases with hydrogen peroxide-alkali solution, and ion chromatography. In the determination of total organic chlorine in water, both the Wickbold method of combustion in an oxygen/hydrogen flame and the modified Dohram method of mineralization in an oxygen stream gave 90% recovery of low-molecular-weightsubstances according to Stachel et al. (26x1. However, the Wickbold method gave a 2-fold lower organohalogen value for higher-molecular-weightcompounds. Ishimaru and Tanaka (11X)determined the chemical oxygen demand of sludge by strong phosphoric acid-potassium iodate decomposition. The resulting solution was boiled to expel free iodine, and the excess iodate was determined by iodometry using standard thiosulfate. Values were determined to range from 2 to 3% relative standard deviation for 10 to 160 mequiv/L chemical oxygen demand per liter. A fully automated flow injection method for the measurement of dissolved chemical oxygen demand was described by Korenaga and Ikatsu (13X). They employed a potassium dichromatesulfuric acid solution for oxidation of the sample. After the reaction was completed, the sample was passed to a spectrophotometer where the absorbance was measured at 445 nm. With this technique, a detection limit of 0.5 mg/L and a precision of 2% were achieved. Ying and Wen (34X) determined chemical oxygen demand using a sealed flask. They showed that the relative standard deviation and accuracy were equivalent to those obtained by the reflux method. Watts and Adams (31X) stated that by the addition of manganese(I1) ion and oxygenation, sulfur dioxide could be removed from wastewater samples, thereby eliminating the interference in chemical oxygen demand determinations. Mrkva ( I 7 X ) correlated the results of the determination of chemical oxygen demand by permanganate/dichromate oxidation with the measurement of absorbance a t 254 nm. A linear regression showed a close correlation between the two techniques and resulted in a recommendation by the author that absorbance measurements could be used as an indicator of organic pollution. Wagner and Ruck (30X)suggested that chloride interference in the determination of chemical oxygen demand could be minimized by diffusion of hydrochloric acid from the sample containing weak sulfuric acid. They reported that the nitrate interference is also minimized by the use of weak rather than strong sulfuric acid. Friege ( 5 X ) suggested that the homogenized samples of municipal and industrial wastewaters yielded higher chemical oxygen demand values. Lloyd (15X) reported a sealed flask procedure for the determination of chemical oxygen demand in wastewater. The sample was digested at 150 "C in a glass stoppered flask. He stated that this procedure improved the suppression of chloride interference. Chemical oxygen demand has been shown to be a useful pollution indicator when compared to other parameters such as total organic carbon, total oxygen demand, ultraviolet absorbance, or fluorescence,according to Matsuzaki et al. (16X). Total oxygen demand and ultraviolet absorbance showed particularly wide fluctuation among various wastewater samples. Removal of silver and mercury from spent chemical oxygen demand test solutions has been suggested by Hendrickson et al. (IOX). Silver is removed by precipitation as silver chloride and mercury removed by reduction with iron and mercurous chloride-elemental mercury precipitation. Both processes are inexpensive and easy to perform, and removal efficiency is high for both metals. Development of standard reference materials for calibrating titrimetric analyzers for determination of chemical oxygen demand in water is discussed by Shaevich et al. (25X). An approach to biological treatment of wastewaters by monitoring for possible effects on various stages if water purification processes downstream of the discharge point has been investigated by Haltrich et al. (8X). Effluents are treated in an aerobic biological filter and on activated carbon columns and characterized as dissolved organic carbon and chemical oxygen demand. Yang, Wu, and Qn (33X) reported the principle and application of a rapid biochemical oxygen demand monitor. Ji and Cai (12X) described the rapid determination of 5-day biochemical oxygen demand in wastewater. The principle is based on the difference between the respiratory rates of microorganisms in the sample. Hall and Foxen ( 7 X ) discussed nitrification in 5-day biochemical oxygen demand tests. They
WATER ANALYSIS
suggested that carbonaceous 5-day biochemical oxygen demand would provide a more acceptable standard for compliance reporting. Wagner (29X) described a computer program for the evaluation of biochemical oxygen demand data from the dilution method. The determination of the maximum nitrification oxygen demand under standardized laboratory conditions is an analog value for the biomass of suspended nitrifiers according to Mueller and Kirchesch (18X). It consists of the difference between 5-day biochemical oxygen demand of untreated samples and that of samples treated by a nitrification inhibitor and of the oxygen demand of samples with added ammonium ion. An analytical protocol for measurement of different nitrogenous organics in water has been proposed by Le Cloirec et al. (14X).It permits determination of the nature and concentrations of the principal materials found in surface waters and in various stages of drinking water treatment. Definitive analyses are then possible for 60-95% of the organic nitrogen. A modified method for determination of ammonifying bacteria in natural waters using Nessler’s reagent as an indicator of ammonia formation in incubated samples has been studied by Stavskii et al. (27X).No significant differences in results were observed when comparing open and hermetically sealed samples. Acidic preservation at pH 2 of water samples for total organohalogendetermination was more effective than preservation with azide or molybdate ions as bacteriocides, according to Tsai and Tuovinen (28X). Miscellaneous
Winter (15Y)has described the Environmental Protection Agency’s reference materials program for water and wastewater analyses carried out under Agency guidelines. The Quality Control Sample Program provides samples for use as calibration standards for trace organic determinations. Stable standard solutions for phenols determination have been described by Belen’kaya et al. (3Y). Phenol, cresols, and guaiacol were prepared for water and and wastewater analysis using ethanol as solvent and antiseptic and maleic acid as stabilizing agent. The determination of quinones formed by disinfection of phenol-containing surface waters with chlorine dioxide is the subject of a report by Thielemann and Grahneis (13Y). Thin-layer chromatography is used for separation. Determination of the intermediate products from levomycetin synthesis and their chemical stability in natural waters has been studied by Dyatlovitskaya et al. (5Y). Five intermediate p-nitrophenyl compounds were determined by extraction and thin-layer chromatography on silufol. Pringle (IOY) has examined the chemistry associated with ozonolyRis of organic contaminants in water using dibenzofuran as a model compound. Spectroscopic techniques have been tested including a linear array Reticon detector system for measurement of weak energy-resolved fluorescence bands at high resolution. This device is several orders of magnitude more sensitive than a photomultiplier tube. Adams and Giam (I Y) have determined polynuclear azaarenes in creosote wood preservative wastewater and emphasized the need to develop an analytical protocols for azaarenes in hazardous wastes. An examination of the factors involved in the determination of phosphatase activity in estuarine waters has been carried out by Huber and Kidby (6Y).The effects of assay pH, magnesium addition, temperature, sodium azide, and sample storage and filtration were studied. The effects of assay conditions are discussed in relation to procedures. Activated-sludge treatment of wastewaters from five chemical plants removed toxic organic compounds to concentrations below accepted detection limits of recommended methodology according to Tischler and Kocurek (12Y). Analytical laboratory uncertainty was an important factor in regulating discharges. Delmas, Parrish, and Ackman ( 4 Y ) have described a method in which concentrations of lipid classes present in seawater are determined by thin-layer chromatography with h e ionization detection. A three-step separation on silica-coated Chromarods is used to resolve dissolved and particulate seawater lipids into five neutral and two polar classes. Detector response is curvilinear in the range between 0.2 and 20 pg. An analytical method has been developed by White et al. (14y) for the determination of organic compounds in aqueous leachates of fossil fuel solid wastes. The method was evaluated using two synthetic leachates as well as solvent refined coal
still bottom residues. Longbottom and Lichtenberg (8Y)have published an updated version of the Environmental Protection Agency’s Methods for Organic Chemical Analysis of Municipal and Industrial Wastewater. A gravimetric method has been presented by Maksimov et al. (9Y) for the determination of organic substances in alumina production wastes. A sample is acidified, extracted with methyl isobutyl ketone, evaporated to dryness, and weighed. Banovic and Mair (2Y) have conducted a trihalomethane formation study based upon monthly composite sampling. The data were sufficiently accurate to permit multiple regression analysis with good agreement to grab sampling. Khristoskova (7Y) has determined formaldehyde in wastewater by titration using sodium sulfite and verified the data by satistical treatments. Ramsey, Montgomery, and Maddox (11Y) have discussed the important factors to be considered in monitoring a landfill site for groundwater contamination citing the importance of geological conditions, materials selection, drilling techniques and procedures, and monitoring strategy. Sampling Methods
A review of three continuous sampling techniques for trace organics determination in water has been prepared by Bruchet, Cognet, and Mallevialle (42).A composite liquid sampler +th closed-loop stripping, a continuous liquid-liquid extraction cell, and a contactor on macroporous resin is discussed. In a review with 12 references, Gudernatsch (92) has discussed sampling as an essential part of analysis of water and wastewater. The effect of sampling variables on the recovery of volatile organics in water was studied by Ho (102). A peristaltic pump sampler was used to estimate the relative importance of transport-line material, pumping rate, and concentration of organic compounds. The transport-line material showed a statistically significant effect on recovery of all compounds studied. Pumping rate and concentration level affected recovery of those compounds with Henry’s law constants greater than atm m3/mol. Design, construction, and characteristics of a marine in situ trace organic compounds sampler has been described by Brandau et al. (32). The device can be lowered to depths of lo00 ft and programmed to sample a t regular intervals. Carignan (52) has commented on the methodological uncertainty in sampling of interstitial water by dialysis. Cellulose-based membranes can lead to underestimation or overestimation of porewater solutes. Polycarbonate materials were found unsuitable for dialyzer construction because of iron precipitation problems. Gibb and Barcelona (82) have prepared a review, with 18 references, of sampling techniques for organic compounds in groundwater. Both public water supply and monitoring wells are addressed. In a similar report, Barcelona et al. (12)have evaluated in the laboratory a sampling apparatus for the determination of gases and purgeable organic compounds in groundwater. Positive displacement bladder devices gave better performance and suction devices gave poorer performance than grab Samplers, bailers, syringe pumps, and gas and mechanical positive displacement devices. Chemical time series sampling of roundwater for chemical analysis is the subject of a report y Keely and Kerr (122). Dynamic sampling from discharging monitoring wells yields more information concerning the state of the aquifer than does monitoring of stagnant wells since contaminant arrival patterns as a function of pumping rate gives insight into location and source of contamination plumes. A syringe and cartridge technique for down-hole sampling of groundwater for trace organic compounds is the subject of a report by Pankow et al. (172).The device, which is lowered down piezometers with a tube, consists of a cylindrical cartridge of sorbent attached to a syringe. The volume of the syring determines the volume of sample passing through the cartridge. The device is retrieved, residual water is removed, and analytes are determined by gas chromatography/mass spectrometry. An application of new environmental sampling techniques for monitoring chemical hazards has been presented by Paasivirta et al. (152). Water is sampled by direct pumping through an adsorbent followed by thermal desorption/cold trap injection onto several capillary gas chromatographic columns configured with multiple detectors. A brief review of groundwater sampling is provided by Neumayr (142). Storage a t 5 “C following drying of a cyclohexane extract over anhydrous sodium sulfate is recommended by
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Chen and Zhu (62) for preservation and treatment of wastewater samples for benzo[a]pyrene determination. Bolarin, Romero, and Caro (22) have discussed methods for the determination of phenols in the context of conditions for preservation and pretreatment of phenol samples and recommends adjustment to pH 2 with sulfuric acid. Development of sampling and preservation techniques for retardation of chemical and biological changes in water samples is the subject of a report by Miller, Crook, and Spigarelli (132). A protocol for munitions chemicals involves acetonitrile addition to achieve 10% solution, adjusting to pH 3.5 with glacial acetic acid, and storage in amber glass bottles under Teflon seal at 4 "C in the dark. The design and application of a rain sampler with a large surface area has been described by Pankow, Isabelle, and Asher (162).This device, which is controlled electronically, provides in situ filtration and preconcentration of nonpolar compounds on Tenax GC packing prior to instrumental analysis. Curran and Tomson (72) have reported the results of their studies on the leaching of trace organics into water from five common plastics. Teflon, glued and unglued poly(viny1 chloride),polyethylene, polypropylene, and Tygon were tested for aqueous leaching and sorption of trace organics in samples from monitoring wells. Teflon showed the least contaminant leaching. Sampling procedures were discussed by Huber and Kidby (112) in conjunction with the examination of factors involved in determination of phosphatase activity in estuarine waters. Implications of observed variations in activity are discussed for canying out an adequate sampling program and data assessment. Registry No. Water, 7732-18-5. LITERATURE CITED APPENDIX WATER ANALYSIS REVIEWS
(1) Water Analysis. Fishman, M. J.; Erdmann, D. E.; Garbarino, J. R. Anal. Chem., 55, 102R-133R (1983). 665 Refs. Inorganlc
(2) ICP-AES, a new method for muitleiement determination in water, wastewater and sludge. Huber, L. Vom Wasser, 58, 173-85 (1982). 6 Refs. (3) Application of flow injection analysis to environmental monitoring. Ma, H.; Yon, H. Huanjing Kexue, 4, 59-65 (1983). 53 Refs. (4) Flow-through methods for the determination of the main components in waters, rain water and drinking water. RelJnders, H. F. R.; Meiis, P. H. A. M.; Grieplnk, B. Fresenius' 2.Anal. Chem., 314, 627-33 (1983). 194 Refs. (5) Possibilities of misinterpretation in ASV-speciation studies of natural waters. Kramer, C. J. M.; Yu, G. H.; Duinker, J. C. Fresenlus' 2.Anal. Chem., 317, 383-4 (1984). 14 Refs. (6) Preconcentratlon methods for the analysis of water by x-ray spectrometric techniques. Van Grieken, R. Anal. Chim. Acta, 143, 3-34 (1982). 178 Refs. (7) The use of physical separation techniques in trace metal speciation studies. De Mora, S. J.; Harrison, R. M. Water Res., 77, 723-33 (1983). 98 Refs. (8) Sorption methods for preconcentration of trace elements for their determination in natural waters. Myasoedova, G. V.; Shcherbinina, N. I.; Savvin, S. B. Zh. Anal. Khlm., 38, 1503-14 (1983). 137 Refs. (9) Sampling for chemical analysis. Kratochvii, B.; Wallace, D.; Taylor, J. K. Anal. Chem., 56, 113R-129R (1964). 541 Refs. (10) Sampling as an essential part of analysis of water and wastewater. Gudernatsch, H. Vom. Wasser, 60, 95-105 (1983). 12 Refs. (11) Inorganics (in water analysis). Poicyn, D. S. J . Water follut. Control Fed., 55, 555-73 (1983) 319 Refs. (12) Study of chemical forms of elements in surface waters. Varshol, G. M.; Veiyukhanova, T. K.; Koshchecva, I.Ya.; Dorofeeva, V. A.; Buachidze, N. S.;Kasimova, 0. G.; Makharadze, G. A. Zh. Anal. Khim., 38, 1590-600 (1983). 23 Refs. (13) Determinatlon of trace chromium. Liu, X.; Yan, H. Huanjing Kexue, 5, 75-7 (1984). 21 Refs. Organlc
(14) Water analysis in the last twenty-five years. Development and expectations. Quentin, K. E. GWF, Gas-Wasserfach: GaslErdgas, 125, 179-82 (1984). (15) Development in 1982 of methods for the determination of organic components in waters. Terietskaya, A. V. Khim. Tekhnol. Vody, 6 , 38-47 (1948). 110 Refs. (16) Methods for water analysis. Treatment of results. Campaneiia, L.; Ghersini, G.; Liberatori, A,; Macchi, G.; Mastino, 0.; Spaziani, F. M. Ouad1st. Rich. Acque, 11, 22 (1983). (17) Chemical Speciation. Braman, R. S. Chem. Anal., 64 Anal. Aspects Environ. Chem., 1-59 (1983). 165 Refs. (18) Methods for water analysis. Outlines of analytical techniques. Campanelia, L.; La Noce, T.; Liberatori, A. Quad.-Ist. Rlc. Acque, 1 1 , 60 (1983).
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(19) Chromatographic analysis of pollutants with selective sample treatment and detection techniques. Frei, R. W.; Brinkman, U. A. T. R o c . rnst. Pet., London, (2, Petroanal. '61), 261-7 (1982). 10 Refs. (20) High-resolution gas chromatography in environmental analysis. Baiischmiter, K. Euroanai. 4, Rev. Anal. Chem., (Conf.), 4th, 139-56 (1982). 55 Refs. (21) Capillary gas chromatography in the analysis of environment. Novotny, M. Chem. Anal. (N.Y.),61-112 (1983). 158 Refs. (22) Possible applications of combined gas chromatography-mass spectrometry in water laboratories. Karrenbrock, F.; Haberer, K. Vom Wasser , 60, 237-54 (1983). 14 Refs. (23) Application of LC-MS to the analysis of water. Games, D. E.; Foster, M. G.; Meresz, 0. Anal. f r o c . (London), 2 1 , 174-7 (1984). (24) The electroanalysis of organic pollutants in aquatic matrixes. Smyth, W. F.; Heaiy, J. A. Sci. TotalEnviron., 37, 71-81 (1984). 28 Refs. (25) Characterization of dissolved organic matter in water by ultrafiltration and three-stage diafiitration. Hoyer, 0. 2.Wasser Abwasser Forsch., 16, 191-8 (1983). 25 Refs. (26) Analysis of water-soluble organics. Sadowski, L. H.; Harris, J. C. ADL82480-19, EPA-600/2-84-012; Order No. PB84-141225, 166 pp. Avaiii NTIS. (27) The problem of priority pollutant analysis in aquatic ecosystems. Picer, M. Vodoprlvreda, 16, 23-30 (1984). 28 Refs. (28) Analysis of organic pollutants in seawater. Fukui, F.; Yanagi, K.; Okabe, S. Nippon Kaisui Gakkaishl, 36, 346-54 (1983). 63 Refs. (29) Formaldehyde, methanol, and related compounds, in raw, waste and potable waters, 1982 tentative methods. Methods Exam. Wafers Assoc. Mater., 47 (1983). 8 Refs. (30) Problems in the biomonitoring of oil poilution in seawater. Mironov, 0. G. Razrab Vnedrenie Kompleksn . Fonovykh Stn . Metodov Biol. Monit ., ( T r . Mezhdunar. Shk. Blol. Monk.), 1st 1980, 2 , 61-6 (1983). 10 Refs. (3 1) Polycyclic aromatic compounds of environmental and occupational importancefheir occurrence, toxicity, and the development of high purity certified reference materiels. Part I. Jacob, J.; Karcher, W.; Wagstaffe, P. J. Fresenius' Z.Anal. Chem., 317, 101-14 (1984). 195 Refs. (32) Poiycyciic aromatic hydrocarbons. 111. Analysis of environmental sampies by computerized gas chromatography-mass spectrometry. Grmait, J.; Cuberes, M. R.; Albaiges, J. Afinidad, 41, 222-6 (1984). 18 Refs. (33) Analytical determination of organic halogen compounds. Schnitzler, M.; Koehn, W. Commun. Eur. Communities, EUR 8515,Anal. Org. Micropollut. Water, 191-204 (1984). 19 Refs. (34) The analysis of organohalldes in water-an evaluation update. Dressman, R. C.; Stevens, A. A. J. Am. Water Works. ASSOC.,75, 431-4 (1983). (35) Analyticai aspects of the characterization and monitoring of banked samples with special reference to organohaiogens. Balischmitter, K. Environ Specimen Banking Monit Relat Banking, f r o c I n t Workshop 1982, 264-70 (1984). 10 Refs. (36) Nonspecific organic analysis of water for reuse facilities. Cooper, W. J.; Suffet, I. H. Proc. Water Reuse Sysm. 1981, 2299-324 (1982). 93 Refs. (37) TOC-the best gauge for organic matter. Dahi, I. wemi, 29-30 (1984). 4 Refs. (38) Process for the oxidation of organic carbon in water. Lacour, G.; Carnoy, A. Eau, Ind., Nuisances, 75, 59-63 (1983). 6 Refs. (39) Determination of organotin compounds in waterways and seaways. Chapman, A. H. Anal. f r o c . (London), 2 0 , 210-12 (1983). 21 Refs. (40) Determination of water quality in environmental measuring technology. Bonfig, K. W.; Kramp, E. Tech. Mitt., 76, 541-5 (1983). 16 Refs. (41) Water quality monitoring: a system's perspective. Ward, R. C. IIASA Collab. R o c . Ser. 1982, CP-8244, 163-205. 65 Refs. (42) Physical-chemical methods-quality assurance. Jensen, V. B.; Reuss, M. Miooevaardsserien, 269-79 (1983). (43) Sediment study with regard to monitoring water quality. Pheiffer Madsen, P. Miooevaardsserien, 251-67 (1983). 16 Refs. (44) The use of environmental risk analysis for ranking hazardous substances released to soli of groundwater. McKone, T. E. Proc.-Inst. Envlron. Scl., 19th, 380-9 (1983). (45) Organization and evaluation of interlaboratory comparison studies among southern African water analysis laboratories. Smith, R. Tahntt, , 31, 537-45 (1984). (46) Analysis and monitoring of steam and water impurities in the parts per billion range. Bellows, J. C.; Carison, G. L.; Pensenstadler, D. F. J. Mater. Energy Syst., 5 , 43-52 (1983). (47) Experience in monitoring domestic water sources and process waters for trace organics. Zororski, J. S.J. Environ . Scl. Health, Part A , A 19, 233-49 (1984).
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WATER ANALYSIS (11A) Rollemberg, M. C. E.; Curtlus, A. J. Mikrochim. Acta, 2, 441-7 (1982). (12A) Shamaev, V. I.; Chudinovsklkh. T. V. Anal. Chim. Acta 139, 177-86 (1982). (13A) Sitnlkova, R. V.; Krylova, A. N.; Zellchenok, S. L.; Dzimoko, V. M.; Ostrovskaya, V. M.; Zhukova, Zh. Anal. Khim., 3 7 , 611-13 (1982). (14A) Thompson, K. C.; Cummlngs, P. M. Analyst (London), 109, 511-14 (1984). (15A) Sugiyama, M; Fujlno, 0.; Matsui, M. BunsekiKagaku, 33, E123-E129 (1984). (18A) Wada, H.; Yuchi, A.; Nagagawa, G. Anal. Chlm. Acta, 149, 291-6 (1983). (17A) Yoshida, H.; Hattorl, T.; Arai, H.; Taga, M. Anal. Chim. Acta, 152, 257-63 (1983).
TRANSITION METALS (18) Aneva, 2. Zavod. Lab., 48, 16-17 (1982). (28) Atsuya, I.; Ito, K.; Otomo, M. Anal. Chim. Acta, 147, 185-92 (1983). (38) Becher, G.; Oestvold, G.; Paus, P.; Seip, H. M. Chemosphere, 12, 1209-15 (1983). (48) Billkova, A. Zh. Anal. Khlm., 37, 1886-8 (1982). (58) Bloom, N. S.; Crecelius, E. A. Anal. Chim. Acta, 156, 139-45 (1984). (68) Bond. A. M.; Wallace, 0.0. Anal. Chem., 5 5 , 718-23 (1983). (78) Box, J. D. Water Res., 18, 397-402 (1984). (88) Brown, L.; Haswell, S. J.; Rhead, M. M.; O’Nelll, P.; Bancroft, K. C. C. Analyst(London) 108, 1511-20 (1983). (98) Burakov, V. S.; Verenlk, V. N.; Malashonok, V. A.; Nechaev, S. V.; Puko, R. A. Zh. Anal. Khim., 38, 90-3 (1983). (108) Carpenter, P. D.; Smith, J. D. Anal. Chim. Acta, 159, 299-308 119841. , . (118) Cirvera, J.; Cela, R.; Perez-Bustamante, J. A. Analyst (London), 107, 1425-30 (1982). (128) Chikryzova, E. G.; Mashlnskaya, S. Y.; Bardin-Shtein. S.; Soblna, N.; Romanov, N.; Khelfets, L. Zh. Anal. Khim., 3 7 , 1996-2001 (1982). (138) Clzek, A.; Sulcek, 2.; Dolezal J. Chromatographie, 15, 760-4 (1982). (148) Cole, P. C.; Eckert, J. M.; Williams, K. L. Anal. Chlm. Acta, 153, 61-7 (1983). (158) Culberson, C. H.; Llang, Y. J.; Church, T. M.; Wood, R. H. Anal. Chlm. Acta, 139, 373-7 (1982). (168) Dornemann, A.; Kleist, H. fresenius’ Z . Anal. Chem., 313, 319-23 (1982). (178) Dubinlna, L. F.; Llpunova, G. N.; Medvedeva, L. U.; Mertsalov, S. L. Zh. Anal. Khim., 38, 94-98 (1983). (188) Dzhafarova, T. A.; Zhdanov, S. I.; Sharafieva, M. K. Zavod. Lab., 49, 24-5 (1983). (198) Fang, 2. L.; Xu, S. K. Anal. Chlm. Acta, 145, 143-50 (1983). (208) Gladllovich, D. 8.;Stolyarov, K. P. Zh. Anal. Khim., 38, 878-80 (1983). (218) Hamilton, T. W.; Ellis, J.; Florence, T. M. Anal. Chlm. Acta, 148, 225-35 (1983). (228) Ichljo, 0. Bunseki Kagaku, 32, 339-41 (1983). (238) Ilyas, S. Q. R.; Joshi, A. P. Mikrochim. Acta, 3, 271-6 (1983). (248) Inoue, S.; Sasaki, M. BunsekiKagaku, 3 1 , E127-E130 (1982). (258) Isozakl, A.; Kumagal, K.; Utsumi, S. Anal. Chlm. Acta, 153, 15-22 (1983). (268) Itoh, Y. BunsekiKagaku, 31, E25-E32 (1983). (278) Ivanova, I . F.; Ganago, L. I.; Pushkareva, T. M.; Ezerskaya, T. V. Gig. Sanit., 57-8 (1983). (288) Karyakln, A. V.; Anlklna, L. I.; Vasll’ev, E. M.; Malofeeva, G. I. Zh. Anal. Khim., 38, 260-4 (1983). (298) Kataeva, S. E. Gig. Sank., 46 (1983). (308) Kataml, T.; Hayakawa, T.; Furukawa, M.; Shlbata, S. Analyst (London), 109, 159-62 (1964). (318) Ke, J.; Li, X. Huanjing Kexue, 3. 31-3 (1982). (328) Macalady, D. L.; Putman-Granlund, C.; Granlund, J. 0.; Vervacke, S. L. Water Res., 18, 1277-83 (1982). (338) Menon, K. S.; Agrawal, Y. K. Analyst (London), 109, 27-30 (1984). (348) Mok, W. M.; Wai, C. M. Anal. Chem., 5 6 , 27-9 (1984). (358) Morgen, E. A.; Dimova, L. M. Zh. Anal. Khlm., 38, 2181-8 (1983). (368) Mori, H.; Fujimura, Y.; Takegaml, Y. Bunseki Kagaku, 31, 261-4 11982). (37’8) -Marl, I.; Fujlts, Y.; Sakaguchl, K.; Kitano, S. Bunseki Kagaku, 3 1 , E239-E242 (1982). (388) Mortattl, J.; Krug, F. J.; Pessenda, L. C. R.; Zagatto, E. A. G.; Joergensen, S. S. Analyst (London), 107, 859-63 (1982). (398) Motomizu, S. BunseklKagaku, 32,191-8 (1983). (408) Nagaosa, Yuklo; Sana, Toshikazu Anal. Lett., 17, 243-9 (1984). (418) Nakano, S.; Odzu, M.; Tanaka, M.; Kawashima, T. Mikrochim. Acta, 1 , 403-11 (1983). (428) Nakeno, S.; Tanaka, M.; Fushihara, M.; Kawashlma, T. Mikrochim. Acta, 1 , 457-65 (1983). (438) Nelson, A.; Mantoura, R. F. C. J. Electroanal. Chem. InterfaclalElectrochem., 164, 237-52 (1984). (448) Nelson, A.; Mantoura, R. F. C. J. Nectroanal. Chem. InterfacialElectrochem., 164, 253-64 (1984). (458) Nelson, A.; Mantoura, R. F. C. J . Electroanal. Chem. InterfacialElectrochem., 164, 265-72 (1984). (488) Nonova, D.; Stoyanov. K. Anal. Chim. Acta, 38, 321-8 (1982). (478) O’Halloran, R. J. Anal. Chim. Acta, 140, 51-8 (1982). (488) Osaki, S.; Setoyama, M.; Takashlma, Y. J . Chromatogr. 257, 180-4 11983). (496) Pilipenko, A. T.; Karentnikova, E. A.; Trachevskli. V. V. Zh. Anal. Khim, 38, 1787-92 (1983). (508) Pilipenko, A. T.; Terletskaya. A. V.; Bogoslovskaya, T. A. Zh. Anal. Khim., 38, 807-10 (1983). (518) Przeszlakowskl, S.; Habrat, E. Analyst (London), 107, 1320-9 (1982).
(528) Qiang, W. Anal. Chem., 5 5 , 2043-7 (1983). (538) Rajendrababu, Satram; Kumar, Nanguneri V. Nada J. Assoc. Off. Anal. Chem., 65, 1375-8- (1982). (548) Reggers, G.; Van Grieken, R. Fresenius’ 2.Anal. Chem., 317, 520-6 (1984). (558) Reinhoid, F. Vom. Wasser, 6 1 , 289-303 (1983). (568) Roston, D. A. Anal. Chem., 5 6 , 241-4 (1984). (578) Rueter, J.; Schwedt, G. Fresenius’ Z . Anal. Chem., 311, 112-15 (1982). (588) Ruzic, I. Anal. Chim. Acta, 140, 99-113 (1982). (598) Sawamoto, H. J . Nectroanal. Chem., 147, 279-88 (1983). (608) Shljo, Y.; Ide, K.; Sakal, K. BunsekiKagaku, 32, E353-E359 (1983). (618) Shljo, Y.; Klmura, Y.; Shimlzu, T.; Sakai, K. Bunsekl Kagaku, 3 2 , E285-E291 (1983). (628) Silva, M.; Valcarcel, M. Analyst (London), 107, 511-18 (1982). (638) Simoes Goncalves, M. L. S.; Correla dos Santos, M. M. J. Necfroanal. Chem., 143, 397-411 (1983). (648) Siu, K. W. M.; Bednas, M. E.; Berman, S. S. Anal. Chem., 5 5 , 473-6 (1983). (658) Smith, R.; Bezuidenhout, E. M.; Van Heerden, A. M. Water Res., 17, 1483-9 (1983). (668) Stryjewska, E.; Rubel, S. Chem. Anal. (Warsaw),26, 615-21 (1981). (678) Stryjewska, E.; Rubei, S. Chem. Anal. (Warsaw), 16, 815-25 (1981). (688) Tanaka, H.; Nakano, T.; Kanazawa, Y. Bunseki Kagaku, 3 2 , 649-5 (1983). (698) Tarafdar, S. A.; Rahman, M. fresenius’ Z . Anal. Chem., 316, 715 (1983). (708) Terada, K.; Matsumoto, K.; Kimura, H. Anal. Chim. Acta, 153, 237-47 (1983). (718) Terada, K.; Matsumoto, K.; Tanlguchi, Y. Anal. Chim. Acta, 147, 411-15 (1983). (728) Ternero, M.; Gracla, I . Analyst (London), 108, 310-15 (1983). (738) Tslngarelil, R. D.; Gaidadymov, V. 8.; Tabakova, 0. M. Zh. Anal. Khim., 38, 265-8 (1983). (748) Ueda, K.; Yoshlmura. 0.; Yamamoto, Y. Analyst (London), 108, 1240-6 (1983). (758) Uiakovlch, N. A.; Postnova, I. V.; Budnikov, G. K. Zh. Anal. Khim., 36,245-9 (1983). (768) Uzawa, A.; Yoshlmura, W. Bunseki Kagaku, 32, 115-19 (1983). (778) Vlnarova, L. I.; Mallnka, E. V.; Stoyanova, I. V. Zh. Anal. Khim., 3 8 , 2013-15 (1983). (788) Wada, H.; Nakagawa, G.; Ohshita, K. Anal. Chim. Acta, 153, 199-206 (t983). (798) Walte, T. D.; Morel, Francois M. M. Anal. Chem., 5 8 , 787-92 (1984). (808) Wan, A.; Zhang, Y.; Luo, F. Huanjing Kexue, 4 , 36-8 (1983). (818) Wang, S.; Jia, S.; Zheng, L.; Wang, H. Huanjing Kexue, 4 , 50-2 (1983). (828) Watanabe, H.; Tachlkawa, K.; Ohmorl, Bunseki Kagaku, 31, 471-3 (1982). (838) Willie, S. N.; Sturgeon, R. E.; Berman, S. S. Anal. Chem., 5 5 , 981-3 (1983). (848) Yamada, K.; Aoyama, M.; Hobo, T.; Suzuki, S. Bunseki Kagaku, 3 3 , 99-103 (1984). (858) Yamane, T.; Mottola, H. A. Anal. Chim. Acta, 146, 181-90 (1983). (868) Yoshlmura, K.; Hlraoka, S.; Tarutani, T. Anal. Chim. Acta, 142, 101-7 (1982). (878) Zeinalova, S . A.; Guseinov, I . K.; Rustamov, N. K. Zh. Anal. Khim., 38, 241-4 (1983). (888) Zhang, H. F.; Holzbecher, J.; Ryan, D. E. Anal. Chim. Acta, 149, 385-9 (1983). (898) Zhou, L. Huanjing Kexue, 4, 57-9 (1983). GROUP 12 METALS
(IC) Barbina, T. M.; Podchalnova, V. N. Zh. Anal. Khim., 38, 1222-9 (1983). (2C) Beaupre, P. W.; Holland, W. J.; McKenney, D. J. Mikrochlm. Acta, 2 , 415-20 (1983). (3C) Chlba, K.; Yoshida, K.; Tanabe, K.; Haraguchl, H.; Fuwa, K. Anal. Chem., 5 5 , 450-3 (1983). (4C) CUI, C. Huanjing Kexue, 3, 47-51 (1982). (5C) Degtev, M. I.; Toropov, L. I.; Zhivoplstsev, V. P. Zavod. Lab.. 49, 7-9 (1983). (6C) Dmitrlev, M. T.; Granovskll, E. I.; Slashchev, A. Ya. Gig. Sanit., 50-3 (1983). (7C) Freimann, P.; Schmidt, D. Fresenius’ Z . Anal. Chem., 313, 200-2 (1982). (8C) Goto, M.; Shibakawa, T.; Artla, T.; Ishil, D. Anal. Chlm. Acta, 140, 179-85 (1982). (9C) Heiden, R. W.; Aiken, D. A. Anal. Chem., 5 5 , 2327-32 (1983). (1OC) Ishli, H.; Koh, H.; Satoh, K. Analyst (London), 107, 647-53 (1982). (11C) Kanzaki, T.; Tonolke, H.; Katsura, T. BunsekiKagaku, 3 1 , E207-E210 (1982). (12C) Kimoto, T.; Morimune, H.; Morlta, H.; Sakurai, H.; Shimomura, S. BunsekiKagaku, 3 1 , 637-41 (1982). (13C) Kimura, M.; Arlkado, T. Bunseki Kagaku, 3 2 , E157-El60 (1983). (14C) Kupchella, L.; Syty, A.; Mahfood, J. J. J. Assoc. Off. Anal. Chem., 66, 1117-20 (1983). (15C) Llu, S . Huanjlng Kexue, 4 , 44-8 (1983). (16C) Lo, J. M.; Wel, J. C.; Yang, M. H.; Yeh, S. J. J. Radioanal. Chem., 7 2 , 571-85 (1982). (17C) Lobanov, F. I.; Terent’eva, E. A,; Yanovskaya, I . M.; Makarov, I. V. Zavod. Lab., 49, 11-12 (1983). (18C) Matslbura, G. S.; Ryabushko, 0. P.; Plllpenko, A. T. Zh. Anal. Khlm., 38, 1008-13 (1983). (19C) Mizuike, A.; Hiraide, M.; Mizuno, K. Anal. Chlm. Acta, 148, 305-9 (1983). ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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WATER ANALYSIS (20C) Morlta, H.; Mitsuhashi, T.; Sakurai, H.; Shimomura, S. Anal. Chim. Acta, 753, 351-5 (1983). (21C) Nakashima, S.; Yagi, M. Anal. Chlm. Acta, 747, 213-18 (1983). (22C) Onoue. Y.; Morishige, K.; Hiraki, K.; Nlshikawa, Y. Bunseki Kagaku, 33. E23-E28 (1984). (23C) 'Pruszkowska, E.: Carnrick, G. R.; Siavin, W. Anal. Chem., 55, 182-6 (1983). (24C) Robinson, J. W.; Skeiiy, E. M. Spectrosc. Lett.. 76, 33-58 (1983). (25C) Santiago, J.; Navas, A.; Laserna, J. J.; Garcia-Sanchez, F. Mikrochim. Acta, 2 , 197-204 (1983). (26C) Schmldt, D.; Freimann, P. Fresenius' 2.Anal. Chem., 377, 385-7 (1984). Beiyaev, Yu. I.; Demkin, A. M. Zavod. Lab., 49, (27C) Shcherbakov, V. I.; 35-6 (1983). (28C) Simeonov, V.; Andreev, G. Fresenius' 2.Anal. Chem., 314, 761-2 (1983). (29C) Smejkal, 2.; Tepia, 2. J . Radioanal. Chem., 77, 49-56 (1983). (30C) Thompson, M.; Coles, B. J. Analyst (London), 709, 529-30 (1984). (31C) Wang, J.; Greene, B. Wafer Res., 77, 1635-8 (1983). (32C) Wang, T.; Liu, S.; Zhao, L.; Feng, F. Huanjing Kexue, 3 , 42-5 (1982). (33C) Wrembei, H. S. Chem. Anal. (Warsaw), 2 6 , 827-35 (1981). (34C) Yamamoto, J.; Kaneda, Y.; Hikasa, Y. Int. J . Envlron. Anal. Chem., 16. 1-16 (183). (35C). Yao, T.; Akino, M.; Musha, S. Bunseki Kagaku, 3 7 , 409-12 (1982). (36C) Zebreva, A. I.; Matakova, R. N.; Zhoklybaeva, R. B. Zh. Anal. Khim., 3 8 , 942-4 (1983). QROUP 13 ELEMENTS (1D) Bekov, G. I.; Egorov, A. S.; Letokhov. V. S.; Radaev. V. N. Nature (London), 307, 410-12 (1983). (2D) Campbell, P. G. C.; Bisson, M.; Bougie, R.; Tessler, A,; Viiieneuve, J. P. Anal. Chem.. 55.2246-52 119831. (3D) Hoefiich, L. K.'; Gale, R. 2.; Gdod, M. L. Anal. Chem., 55, 1591-5 (1983). (4D) Isozaki, A.; Kawakami, T.; Tusuml, S. Bunseki Kagaku, 3 1 , E311E318 119821. (5D) Makzenko, 2.; Jarosz, M. Analyst (London), 107, 1431-8 (1982). (6D) Nemodruk, A. A.; Supatashvlli, G. D.; Arevadze, N. G.; Kikabidze, T. A. Zh. Anal. Khlm., 37, 1028-32 (1982). (7D) Wyganowski, C.; Motomizu, S.; Toei, K. Anal. Chim. Acta, 740. 313-17 (1982). (ED) Wyganowski, C.; Motomizu, S.; Toei, K. Mikrochim. Acta, 1 , 55-64 (1983). (9D) Zoeltzer, D.; Schwedt, G. Fresenius' 2. Anal. Chem., 377, 422-6 (1984). QROUP 14 ELEMENTS (1E) Acebal, S. A.; De Luca Rebelio, A. Anal. Chim. Acta, 748, 71-8 (1983). (2E) Alonso, A.; Gallego, M.; Valcarcei, M. Bunseki Kagaku, 3 2 , E387-E394 (1983). (3E) Andreae. M. 0.; Byrd, J. T. Anal. Chim. Acta, 756,147-57 (1984). (4E) Camail, M.; Loiseau, B.; Margaillan, A.; Vernet, J. L. Analusis, 7 1 , 358-9 (1983). (5E) Chau, Y. K.; Wong, P. T. S.; Kramar, 0. Anal. Chlm. Acta, 146, 211-17 (1983). (6E) De Jonge, W. R. A.; Van Mol, W. E.; Adams, F. C. Anal. Chem., 55, 1050-4 (1983). (7E) De Mora, S. J.; Harrison, R. M. Anal. Chlm. Acta, 753, 307-11 (1983). (8E) Estes, S. A.; Uden, P. C.; Barnes, R. M. Anal. Chem., 5 4 , 2402-5 (1982). (9E) Fletcher, I.J. Anal. Chlm. Acta, 754, 235-49 (1983). (10E) Fukushi, K.; Hiro, K. BunsekiKagaku, 3 2 , 688-92 (1983). (11E) Jin, K.; Taga, M. Anal. Chim. Acta, 143, 229-36 (1982). (12E) Matthews, K. M. Anal. Lett., 16, 633-42 (1983). (13E) Mueiler, M. D. Fresenius' 2.Anal. Chem.. 377, 32-6 (1984). (14E) Nishikawa, Y.; Hiraki, K.; Morishige, K.; Murata, Y.; Shigematsu, T. Bunseki Kagaku, 3 2 , 729-35 (1983). (15E) Omar, M.; Bowen, H. J. M. Analyst (London), 707, 854-8 (1982). (16E) Rowley, A. G.; Law, I.A.; Husband, F. M. Anal. Chlm. Acta, 143, 265-8 (1982). (17E) Shrivastava, A. K.; Tandon, S. G. Int. J. Environ. Anal. Chem., 72, 169-76 (1982). (WE) Tao, D.; Liu, Y.; Xu, M. Huanjlng Kexue, 3 , 43-7 (1982). (l9E) Zou, S.; Yu, X.; Lian, X. Huanjlng Kexue, 3 , 41-4 (1982). GROUP 15 ELEMENTS (1F) Lee, D. S. Anal. Chem., 54, 1682-8 (1982). (2F) Shlmizu, T.; Kawamata, Y.; Kimura, Y.; Shijo, Y.; Sakai, K. Bunseki Kagaku. 3 7 , 299-303 (1982). METALLOIDS (1G) Aggett, J.; Kadwani. R. Analyst(London) 708, 1495-9 (1983). (20) An, J.; Zhang, Q. Int. J . Envlron. Anal. Chem. 74. 73-80 (1983). (3G) Aznarez, J.; Bonllia, A.; Vidal, J. C. Analyst (London) 708, 368-73 (1083). (4G) Bushee, D. S.; Kruii, I. S.; Demko, P. R.; Smith, S. B., Jr. J. Liq. Chromatogr., 7 , 861-76 (1984). (5G) Charkraborti, D.; Irgolic, K. J.; Adams. F. J . Assoc. Off. Anal. Chem., 6 7 , 277-80 (1984). (6G) Dodoo, D. K.; Vrchlabsky. M. Chem. Anal. (Warsaw), 26, 867-76 (1981). (7G) Elson, C. M.; Miiiey, J.; Chatt, A. Anal. Chlm. Acta, 742, 269-75 (1982).
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ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
(8G) Hambrick, G. A., 111; Froelich, P. N., Jr.; Andreae, M. 0.; Lewis, B. L. Anal. Chem., 56, 421-4 (1984). (90) Hudnik, V.; Gomiscek, S. Anal. Chim. Acta, 757, 135-42 (1984). (10G) Maher, W. A. Spectrosc. Lett. 16, 865-70 (1983). (110) Motomlzu, S.; Sawatanl, I.; Oshlma. M.; Toei. K. Anal. Chem.. 55. 1629-31 (1983). (12G) Motomizu, S.; Oshima, M.; Toei, K. Bunseki Kagaku, 3 2 , 458-63 f1983l I
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WATER ANALYSIS (88L) Xie, Y.; Xie, K. Huanjing Kexue, 4, 55-7 (1983). (89L) Yamada, E.; Sato, M. BunsekiKagaku, 32,654-8 (1983). (9OL) Yamamoto, M.; Yamamoto, H.; Yamamoto, Y.; Matsushlta, S.; Baba, N.; Ikushige, T. Anal. Chem., 56,832-4 (1984). (91L) Yu, J. C.; Lo, J. M.; Wal, C. M. Anal. Chim. Acta, 754,307-12 (1983). (92L) Zebreva, A. I.; Matakova, R. N.; Zholdybaeva, R. B. Zh. Anal. Khim., 38, 1325-7 (1983). (93L) Zhu, X. Huaning, Kexue, 4, 62-4 (1983). (94L) Zolotov, Yu. A,; Shpigun, 0. A.; Bubchlkova, L. A. Fresenlus' Z. Anal. Chem., 376,8-12 (1983). ANIONS (1M) Aieta, E. M.; Roberts, P. V.; Hernandez, M. J. Am. Water Works AsSOC., 76,64-70 (1984). (2M) Akiyama, K.; Nagashima, M.; Okumoto, C.; Terashima, K.; Haglwara, T. Bunsekl Kagaku, 3 7 , 402-4 (1982). (3M) Alawi, M. A. Fresenius' Z.Anal. Chem., 377,372 (1984). (4M) Ando, M.; Sayato, Y. Water Res., 77,1823-7 (1983). (5M) Aoki, T.; Uemura, S.;Menumori, M. Anal. Chem., 55, 1620-2 (1983). (6M) Aoyama, M.; Hobo, T.; Suzuki, S. Anal. Chim. Acfa, 74f, 427-30 (1982). (7M) Aoyama, M.; Hobo, T.; Suzuki, S. Anal. Chim. Acta, 753,291-5 ( I 983). (EM) Atkinson, G. F.; Byeriey, J. J.; Mitchell, B. J. Analyst (London), 707, 398-402 (1982). (9M) Baechmann, K.; Matusca, P. Fresenius' Z.Anal. Chem., 375,243-4 (1983). (10M) Barkauskas, Y. K.; Ramanauskas, 2. Zavod. Lab., 49,22-4 (1983). ( l I M ) Basel, C. L.; Defreese, J. D.; Whittemore, D. 0. Anal. Chem., 54, 2090-4 (1982). (12M) Bashir, W. A.; Flamerz, S.; Ibrahlm, S. K. I n t . J. Envlron. Anal. Chem., 15, 65-71 (1963). (13M) Baveja, A. K.; Gupta, V. K. Chem. Anal. (Warsaw), 28, 693-9 (1983). (14M) Beiyavskaya, V. 6.; Ryabinin, A. I. Zh. Anal. Khim., 38, 747-9 (1983). (15M) Bhat, S. R.; Eckert, J. M.; Geyer, R.; Gibson, N. A. Anal. Chim. Acta, 708,293-6 (1979). Smith, J. L. J. Chromatogr. Sci., (16M) Buchholz, A. E.; Verplough, C. I.; 70,499-501 (1982). (17M) Chaube, A.; Baveja, A. K.; Gupta, V. K. Anal. Chim. Acta, 743, 273-6 (1982). (18M) Cox, J. A.; Kulesza, P. J. Anal. Chim. Acta, 758,335-41 (1984). (19M) Cslkai, N. J.; Barnard, A. J., Jr. Anal. Chem., 55, 1677-82 (1983). (20M) Darimont, T.; Schulze, G.; Sonneborn, M. Fresenius' Z. Anal. Chem., 374,383-5 (1983). (21M) Deguchi, T.; Tanaka, A.; Sanemass. I.; Nagai, H. Bunseki Kagaku, 32,23-8 (1983). (22M) Dilll, S.;Patsaiides, E. J. Chromatogr., 280,59-68 (1983). (23M) Fakhri, N. A.; Rahim, S. A.; Bashir, W. A. I n t . J. Envlron. Anal. Chem., 76,131-8 (1983). (24M) Funazo, K.; Kusano, K.; Wu, H. L.; Tanaka, M.; Shono, T. J. Chromafogr., 245,93-100 (1982). (25M) Funazo, K.; Hirashima, T.; Wu, H. L.; Tanaka, M.; Shono, T. J. Chromatogr., 243,85-92 (1982). (26M) Fu-Sheng, W.; Bai, H.; Nai-Kui, S. Analyst (London), 709, 167-9 (1984). (27M) Gao, G.; Huang, A.; Zhao, J.; Zhao, C. Huanjing Kexue, 4, 43-5 (1983). (28M) Gardner, W. S.;Malczyk, J. M. Anal. Chem., 55, 1645-7 (1983). (29M) Garoff, T. Anal. Chem., 54. 2143 (1982). (30M) Gaugush, R. F.; Heath, R. T. Water Res ., 78,449-50 (1984). (31M) Gebauer, P.; Deml, M.; Bocek, P.; Janak, J. J. Chromatogr., 267, 455-7 (1983). (32M) Goto, M.; Miura, Y.; Yoshida, H.; Ishii, D. Mikrochim. Acta, 7, 121-30 (1983). (33M) Grandet, M.; Weil, L.; Quentin, K. E. Z. Wasser Abswasser Forsch., 76 66-71 (1983). (34M) Guterman, H.; Ben-Yaakov, S.;Abeliovich, A. Anal. Chem., 55, 1731-4 11983) (35M)- Haiung Quentin, K. E. Z. Wasser Abwasser Forsch., 77,50, 55-7. 59-82 (1984). (36M) Haskins, i.E.; Kendall, H.; Baird, R. B. WaterRes.,78, 751-3 (1984). (37M) Hefter, 0. T.; Longmore, A. R. I n t . J. Environ. Anal. Chem., 16, 315-23 (1984). (38M) Heumann, K. G.; Unger, M. Fresenius' Z. Anal. Chem., 375,454-8 (1983). (39M) Hllton, J.; Rlgg, E. Analyst(London), 708,1026-8 (1983). (40M) Hori, M.; Hlrako, M.; Ishll, K.; Kogayashi, Y. Bunsekl Kagaku, 33, 203-9 (1984). (41M) Hori, M.; Kobayashi, Y. BunsekiKagaku, 32,75-9 (1983). (42M) Imasaka, T.: Kamlkubo, T.: Kawabata, Y.: Ishibashi, N. Anal. Chim. Acta. 753,261-3 (1983). (43M) Janse, T. A. H. M.; Van der Wlel, P. F. A.; Kateman, G. Anal. Chlm. Acta. 155. 89-102 119831. (44M) Jenke,'D. R.; Mlichell,' P. K.; Pagenkopf, G. K. J. Chromatogr. Sci, 27,487-9 (1983). (45M) Johnson, K. S.; Petty, R. L. Llmnol. Oceanogr., 28, 1260-6 (1983). (46M) Jones, M. N. Water Res., 78,643-6 (1984). (47M) Jones, S.D.; Spencer, C. P.; Truesdale, V. W. Analyst (London), 107, 1417-24 (1982). (48M) Jupille, T.; Burge, D.; Togaml, D. Chromatographia, 76, 312-16 (1982). (49M) Katoh, K. BunsekiKagaku, 32,567-70 (1983)
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GASES
(1N) Aokl, T.; Munemori, M. Anal. Chem., 55,209-12 (1983). (2N) Barbolani, E.; Piccardl, G.; Pantani, F. Anal. Lett., 76, 987-98 (1983).
WATER ANALYSIS (3N) Barcelona, M. J.; Garske, E. E. Anal. Chem., 5 5 , 965-7 (1983). (4N) Barrenstein, A.; Eckrich, W.; Obermann, P. Vom Wasser, 60, 85-93 (1983). (5N) Carlson, R. M.; Weberg, R. T. Chemosphere, 12, 125-8 (1983). (6N) Chrostowski, P. C. Anal. Lett., 16, 1177-86 (1983). (7N) Cooper, W. J.; Gibbs, P. H.; Ott,E. M.; Patel, P. J. Am. Water Works ASSOC., 75, 625-9 (1983). (EN) Cooper, W. J.; Mehran, M. F.; Siifker, R. A.; Smith, D. A,; Viiiate, J. T.; Glbbs, P. H. J . Am. Waters Assoc., 74, 546-52 (1982). (DN) Hatch, G. L.; Yang, V. J. Am. Water Works Assoc., 75, 154-6 (1983). (ION) Hertkorn-Obst, U.; Printer, I.; Schmitz, W. Vom Wasser, 58, 13-15 (1982). ( l l N ) Hirose, S.;Hayashi, M.; Tamura, N.; Kamidate, T.; Karube, I.; Suzuki, S.Anal. Chem., 54, 1690-2 (1982). (12N) Horner, S. M. J.; Smith, D. F. Limnol. Oceanogr. 17, 978-83 (1982). (13N) Kikuchi, T.; Furusaki, S. Bunseki Kagaku, 37, 469-70 (1982). (14N) Kuiin, G.; Schuk, W. W.; Kugelman, I.J. J. Water Pollut. ControlFed., 55, 178-86 (1983). (15N) Leggett, D. J.; Chen, N. H.; Mahadevappa, D. S.Fresenius’ 2.Anal. Chem., 315. 47-50 (1983). (16N) Otsuki, A.; Sekiguchi, K. Anal. Lett., 16, 979-85 (1983). (17N) Rudenko, B. A. Zh. Anal. Khim., 37, 1037-42 (1982). (18N) Smart, R. 6.; Freese, J. W. J. Am. Wafer Works Assoc., 74, 530-1 (1982). (19N) Toei, K.; Ono, Y.; Wakimoto, T.; Miyata, H. Bunsekl Kagaku, 31, 458-61 (1982). (20N) Tomiyasu. M.; Gordon, G. Anal. Chem., 56, 752-4 (1984). (21N) Wong, 0. T. F. Envlron. Sci. Technol., 16, 785-90 (1982). (22N) Zakharov, I. A,; Grishaeva, T. 1. Zh. Anal. Khim., 37, 1753-5 (1982).
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WATER ANALYSIS (29U) Tanaka, T.; Ichimura, K.; Mlzobuchi, M.; Umoto, F.; Nakaoka, H.; Ueda, E.; Itano, T. Sulshltsu Odaku Kenkyu, 5 , 267-71 (1982). (30U) Vagina, A. L.; Dorokhova, G. N.; Poletaev, E. V. Sb. Nauch. Tr. N.4. i froekt. I n 4 po Obogashch. Rud Tsv. Met. Kazmekhanobr, 65-73, 1982. From Ref. Zh., Metall., Abstr. No. 5K62 (1984). (3lU) Veiapokli, R. Z.; White. P. A.; May, W.; Eberhardt, K. R. Anal. Chem., 55, 1898-901 (1983). (32U) Verma, P.; Gupta, V. K. Talanta, 37,394-6 (1984). (33U) Verma, P.; Gupta, V. K. J. Indlan Chem. SOC.,60, 591-3 (1963). (34U) Vershinin, V. I.; Kuzovenko, I. V.; Baranov, 0. I.; Sizikov, A. M. Issled Ob/. Org. Gldrogeokhim. Neftegazonosn Basselnov. (Mater. Vses Semln.), 3rd, 164-9, 1979 (Pub. 1982). (35U) Watanabe, N.; Yasuda, Y.; Kato, K.; Nakamura, T.; Funasaka, R.; Shlmokawa, K.; Sato, E.; Ose, Y. Sci. TotalEnvlron., 34, 189-76 (1984). (36U) Xln, X. Y.; Moldoveanu, S.; Lepadatu, C. I. Rev. Roum. Chim., 28, 83-9 (1983). (37U) Yu, Y. FenxiHuaxue, 7 7 , 932-5 (1983).
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OTHER INSTRUMENTAL TECHNIQUES AND DEVICES (1V) Barber, A. J.; Braids, 0. C. R o c . Natl. Symp. AquiferRestor. Ground Water Monlt., Znd, 129-32 (1982). (3V) Byers, W.; Anderson, S.; Hickam, W. Roc.-Int. Water Conf. Eng. SOC.West. Pa., 44th, 436-41 (1983). (4V) Bystrovzorov, Yu. A.; Ivanov, V. S.; Chel’tsov, A. V. Izmer. Tekh.. 765-6 (1983). (5V) Hirschfeld, T.; Deaton, T.; Mlianovich, F.; Klainer, S. Opt. Eng., 22, 527-31 (1983). (6V) Jia, S.; Zhang, Z. Huaxue Shgie, 24, 204-6 (1983). (7V) Kawahara, F. K.; Fiutem, R. A.; Siivus, H. S.; Newman. F. M.; Frazar, J. H. Anal. Chlm. Acta, 757, 315-27 (1983). (8V) Khesina, A. Ya.; Khitrovo, I. A.; Gevorkyan, 8. Z. Zh. frlkl. Spektrosk., 38,926-34 (1983). (9V) King, E. F.; Painter, H. A. Comm. Eur. Communities, (Rep .) EUR, EUR 8831, 31 pp (1983). (IOV) Ledneva, N. N.; Pruger, Kh. I.; Riviin, A. A. Khlm. Tekhnol. Vody, 5 , 554-7 (1984). ( l l V ) Maruyama, S.; Furukawa, M.; Koyanagl, K.; Shibuya, N.; Sato, R. Nilgata Rlkagaku, 9 , 15-21 (1983). (12V) Mussmann, 6. Draeger Rev.. 57, 17-19 (1983). (13V) Neupert, L. Acta Hydrochim. Hydroblol., 77, 595-601 (1983). (14V) Oldham, P. B.; Patonay, G.; Warner, I. M. Anal. Chlm. Acta, 758, 277-85 (1984). (15V) Onodera, S.; Udagawa, T.; Tabata, M.; Ishikura, S.; Suzuki, S. J. Chromatogr., 287, 176-82 (1984). (16V) Piiipenko, A. T.; Zul’flgarov, 0. S.; Medvedev, M. I.; Tsapyuk, E. A. Khlm. Tekhnol. Vody. 6 . 47-50 (1984). (17V) Scully, F. E., Jr.; Oaiesbv. . D. M.; Buck, H. J. Anal. Chem., 56, 1449-51 11964). (18V) Shen, Z.; Wang, W. Fenxl Huaxue, 77, 269-90 (1963).
PESTICIDES AND DETERGENTS (1W) Adachi, A.; Kobayashi, T. EiselKagaku, 2 9 , 123-9 (1983). (2W) Bian, Y.; Ding, T. Huaxue Tongbao, (1). 18-19 (1984). (3W) Buettier, B. J. Agrlc. FoodChem., 37,762-5 (1983). (4W) Burchill, P.; Herod, A.; Marsh, K.; Pritchard, E. Water Res., 77, 1905-16 (1983). (5W) Cooper, W.; Mehran, M.; Slifker, R.; Savoie, D. Roc.-AWWA Water Qual. Technol. Conf., 191-6, 1982 (Pub. 1983). (8W) Dekker, A.; Houx, N. J. Envlron. Sci. Heaffh, Part B , 878,379-92 (1983). (7W) Goewie, C.; Kwakman, P.; Frei, R.; Brlnkmann, U.; Maasfleid, W.; Seshadri, T.; Kettrup, A. J. Chromatogr., 284, 73-86 (1984). (8W) Grasso, G.; Ummarino, 0.; Navlgiio, 6.; Bufalo, G. Cuolo, fell/, Mater. COflCbnti. 59, 73 1-40 (1983). (9W) Hamane, T.; Adachi, T. Kyoto-fu €isel Kogai Kenkyusho Nenpo, 2 7 , 85-92 (1982). (IOW) HIII, N.; McIntyre, A.; Perry, R.; Lester, J. Int. J. Environ. Anal. Chem., 75, 107-30 (1983). (1 1W) Kondo. S.; Murada, K.; Ando, K. Sulshltsu Odaku nl Kansuru Kenkyu ShUhO, 72,67-71 (1982). (12W) Lemley, A.; Janauer, G. Report W83-03725. OWRT-A-093-NY( 7). Order No. fB83-249649, Avail. NTIS, 9 pp (1982). (13W) Levesque, D.; Mallet, V. Int. J. Environ. Anal. Chem., 76, 139-47 (1963). (14W) Mangani, F.; Bruner, F. Chromatographla, 77, 377-80 (1983). (15W) McCown, S. LC, Llq. Chromatogr. HfLC Mag., 2 , 318-19 (1984). (18W) Minagawa, S.; Sato, H.; Morita, H. Nlgata Rlkagaku, 9 , 27-36 (1983). (17W) Mohnke, M.; Franz, P.; Bruegmann. L.; Rhode, K. Instrum. Anal. Toxikol., (Haupttell Vortr. Symp.) 188-200 (1983). (l6W) Mukai, H.;Murayama, H.; Mizushlma, Y.; Yukl, 0.; Ozaki, K. Ni/gataken Kagai Kenkyusho Kenkyu Hokoku 7 , 80-3 (1982 (Pub. 1983). (19W) Nakamura, E.; Fujisawa, I.; Namikl, H. Bunsekl Kagaku, 32,332-8 (1983).
(20W) Ogino, Y.; Imanaka, M.; Hata, H.; Ishida, T. Okayama-ken Kankyo Hoken Senta Nenpo, 7 , 139-42 (1983). (21W) Ohkuma, T. Fukuoka-shi €isel Shikenshoho 7 . 75-80 1982 (Pub. 1981). (22W) Saito. T.; Hagiwara, K. Fresenlus’s Z . Anal. Chem. 315, 201-4 (1983). (23W) Schnelder, E.; Levsen, K.; Boerboom, A.; Kistemaker, P.; McLuckey, S.; Przybyiskl, M. Anal. Chem., 5 6 , 1987-8 (1984). (24W) Seefeld, F.; Fiorstedt. I . Z . Gssamte Hyg. Ihre Grenzgeb., 29, 332-5 (1983). (25W) Senln, N.; Voikov, S.; Berezkln, V. Zh. Anal. Khlm., 39, 106-10 (1984).
(26W) Stelnheimer, T.; Brooks, M. Int. J . Environ. Anal. Chem., 77, 97-111 (1984). (27W) Tanaka, H.; Kobayashi, K.; Numada, K. Yamenashi-kenrltsu Eisel KogalKenkyusho Nempo, 26, 40-2 1982 (Pub. 1983). (28W) Victor, D.; Hall, R.; Shamis, J.; Whitlock, S. J. Chromatogr., 283, 383-9 (1984). (29W) Voulgaropoulos, A.; Vaienta, P.; Nuernberg, H. Freslnius’ Z . Anal. Chem.. 377,367-71 (1964). (30W) Waters, J.; Garrigan, J. Water Res., 77, 1549-62 (1983). (31W) Wee, V. Water Res., 78,223-5 (1984). (32W) Wells, M.; Michael, J.; Neary, D. Arch. Envlron. Contam. Toxlcol., 73,231-5 (1984). (33W) Xue, J. Huanjlng Hauxue, 3, 43-9 (1984). (34W) Yao. S.; Yu, S.; Fang, X. Fenxl Huaxue, 77, 830-2 (1983). (35W) Zhang, H.; Yang, X. FenxlHuaxue, 72,159 (1984).
TOTAL ELEMENTAL ANALYSIS AND OXYGEN DEMAND (IX) Barcelona, M. J. Ground Water, 22, 18-24 (1984). (2X) Cariberg, G. E.; Kringstad, A. Comm. Eur. Communities, (Rep.) EUR, EUR 8578,Anal. Org. Micropollut. Water, 276-9 (1984). (3X) Cauwet, G. Mar. Chem., 74,297-306 (1984). (4X) Cole, J. J.; McDoweli, W. H.; Likens, G. E. Olkos, 42, 1-9 (1984). (5X) Friege, H. Z . Wasser Abwasser Forsch., 75,266-72 (1982). (6X) Gebhardt, J. A. Report, €PA-600/4-84-003, 7983; Order No. fB84729727, 34 pp., Avail. NTIS. From Gov. Rep. Announce. Index (US.), 84, 301 (1984). (7X) Hall, J. C.; Foxen, R. J. J.-Water follut. Control Fed., 55, 1180-2 11983). (EX) Haitrlch, W. G.; Sonthelmer, H.; Voelker, E.; Weisbrodt, W. Vom Wasser. 67. 305-17 11983). (9%- Hemming. J.; Holmbom, B.; Jarnstrom, S.; Vuorlnen, K. Chemosphere, 73,513-20 (1984). ( l o x ) Hendrickson, K. J.; Benjamin, M. M.; Ferguson, J. F.; Goebei, L. J.Water follut. Control Fed., 5 6 , 468-73 (1984). (11X) Ishimaru, A.; Tanaka, K. BunsekiKagaku, 32,493-7 (1983). (12X) Ji, 0.; Cai, X. Huanling Kexue, 4, 64-6 (1983). (13X) Korenaga, T.; Ikatsu, H. Bunsekl Kagaku, 37,517-23 (1982). (14X) Le Clolrec, C.; Le Clolrec, P.; Morvan, J.; Martln, G. Rev. Fr. Scl. Eau, 2 , 25-39 (1983). (15X) Lloyd, A. Ana/yst (London), 707, 1316-19 (1982). ( l e x ) Matsuzakl, Y.; Sugiyama, K.; Shiegeta, M.; Tanaka, K.; Torli, K.; Suemura, R. Yamaguchl-ken Kogal Senta Nenpo, 7,65-71 (1981). (17X) Mrkva, M. Water Res., 77, 231-5 (1983). (18X) Mueller, D.; Klrchesch, V. Vom Wasser, 56, 145-51 (1981). (l9X) Okamoto, T.; Shirane, Y. Hiroshlm-ken Kankyo Senta Kenkyu HokokU, 5 , 39-43 (1983). (20X) Pokier, S.J. Roc.-Inst. Environ. Sci., 29th, 274-8 (1963). (21X) Prlncz, P.; Gelencser, P.; Kovacs, S. Anal. Chem. Symp. Ser. 78 (Mod. Trends Anal. Chem., f t . A ) , 375-63 (1984). (22X) Profe, 0. Acta Hydrochlm. Hydroblol., 77, 631-6 (1983). (23X) Riggln, R. M.; Lucas, S. V.; Lathouse, J.; Jungclaus, G. A.; Wensky, A. K. Report, €PA-60014-84-008, 7984; Order No. fB84-734337, 126 pp., Avail. NTIS. From Gov. Rep. Announce, Index (US.), 84, 67 (1984). (24X) Schnltzler, M.; Levay, G.; Kuehn, W.; Sontheimer, H. Vom Wasser. 67,263-76 (1983). (25X) Shaevlch, A. B.; Dunaevskaya, L. A.; Viktorova, T. S.; Amusina, Kh. M.; Shumiiova, N. P. Zh. Anal. Khlm., 39, 751-4 (1984). (26X) Stachei, B.; Lahi, U.; Schroer, W.; Zeschmar, 8. Chemosphere, 73, 703-14 11984). (27Xj-Stavskii, A. V.; Berdnlkova, I. V.; Bushneva, L. I.; Sharlot, Yu. M. G/g. Sanit., 40-7 (1984). (28X) Tsai, Y. L.; Tuovinen, 0. H. Envlron. Technol. Len., 4 , 469-74 (1983). (29X) Wagner, R. Vom Wasser, 58, 231-65 (1982). (30X) Wagner, R.; Ruck, W. Z . Wasset Abwasser Forsch., 75,286-90 (1982). (31X) Watts, R. J.; Adams, V. D. WaterRes., 77, 715-18 (1983). (32X) Weiiky, K.; Suess, E.; Ungerer, C. A.; Mueller, P. J.; Fischer, K. Limno/. Oceanogr., 28, 1252-9 (1983). (33X) Yang, L.; Wu, Z.; Qu, W. Huanjlng Kexue, 4, 50-3 (1983). (34X) Ying, C.; Wen, H. Huan/lng Kexue, 4, 59-60 (1983). %
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MISCELLANEOUS (IY) Adams, J.; Giam, C. Envlron. Sci. Technol., 78,391-4 (1984). (2Y) Banovic, J.; Mair, D. Roc.-AWWA Water Qual. Technol. Conf. 1981 (Pub. 1962), 73-91. (3Y) Belen’kaya, I.; Goritskaya, E.; Saponzhnlkov, V.; Andronati, S. Khlm, Teknol. vody, 5 , 233-6 (1983). (4Y) Delmas, R.; Parrlsh, C.; Ackman, R. Anal. Chem., 56, 1272-7 (1984). (5Y) Dyatlovitskaya, F.; Maktaz, E.; Botvinova, L.; Gorshkova, L.; Kruchinlna, A. Khlm. Tekhnol. Vody, 5 , 441-2 (1983). (6Y) Huber, A.; Kldby, D. Hydroblologla, 7 7 7, 3-1 1 (1984). (7Y) Khristoskova, S.Nauchni Tr.-Plovdlvskl Unlv., 20, 153-8 (1982). (8Y) Longbottom, J.; Llchtenberg, J. Methods for Organic Chemical Analysis of Munlclpal and Industrial Wastewater 61 pp (1982). (9Y) Maksimov, 0.; Krasovskaya, N.; Kulesh, N.; Bunchuk, L.; Ardasheva, A.; Gol’dman, M. Otkrytiya, Izabrot ., from. Obraztsy, Tovaryne Znakl. 75, 153-4 (1984). (1OY) Pringie, W. Report W83-04747, OWRT-B-O17-CONN(Z); Order No. PB84-705394, Avall. NTIS, 81 pp (1983). (1 1Y) Ramsey, R.; Montgomery, J.; Maddox, G. Proc. Nati. Symp. Aquifer Restor. Ground Water Monlt., 2nd 7982, 198-204. (12Y) Tischler, L.; Kocurek, D. Water Resour. Symp. 7983, 70 (Toxlc Mater .: Methods Control) 25-51. (13Y) Thieiemann, H.; Grahneis, H. Z.Gesamte Hyd. Ihre Grenzgeb., 29, 427-20 (1983). ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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Anal. Chern. 1985, 57,8 8 ~ - 9 4 ~ (14Y) Whlte, C.; Avery, M.; Blanton, W.; Hilpert, L.; Jackson, L.; Junk, G.; Maskarinec, M.; Paule, R.; Raphaellan, L.; Rlchard, J. Report DO€/ P€TC/TR-84/7; Order No. D€84001332, Avail NTIS, 81 pp (1983). (15Y) Winter, J. Report EPA-60010-84-035; Order No. PB84-149277, Avail. NTIS, 24 pp (1984). SAMPLINQ METHODS
(12) Barcelona, M. J.; Heifrich, J. A.; Garske, E. E.; Glbb, J. P. Ground Water Monk. Rev., 4 , 32-41 (1984). (22) Bolarln, M. C.; Romero, M.; Caro, M. An. €dafo/. Agrobiol. 4 1 , 2045-54 (1982) (32) Brandau, E. L.; Farland, R. J.; Bird, J. D.; Conte, J. A. Adv. Instrum., 3 8 , 143-50 (1983). (42) Bruchst, A.; Cognet, L.; Mallevialle, J. Rev. Fr. Sci. Eau, 2 , 297-309 (1983). (52j Carignan, R. Limnol. Oceanogr ., 29, 667-70 (1984). (62) Chen, X.; Zhu, 2. Huanjing Baohu (Beying), (8), 30 (1983). (72) Curran, C. M.; Tomson, M. E. Ground Water Monit. Rev., 3 , 68-71 (1983).
(82) Gibb, J. P.; Barcelona, M. J. J.-Am. Water Works Assoc., 78, 48-51 (1984). (92) Gudernatsch, H. Vom Wasser, 60, 95-105 (1983). (102) Ho, J. S. Y. J.-Am. Water Works Assoc., 75, 583-6 (1983). (112) Huber. A. L.; Kldby, D. K . Hydroblologia, 777, 13-19 (1984). (122) Keely, J. F.; Kerr, R. S. Proc. Natl. Symp. Aquifer Restor. Ground Water Monit., 133-47 (1982). (132) Mlller, H. H.; Crook, M. V.; Spigarelli, J. L. Report DRXTH-TE-CR82782; Order No. AD-A735365, Avall. NTIS, 231 pp (1984). (142) Neumayr, V. Comm. Eur. Communlties, EUR 8518,Anal. Org. Micropollut, Water, 5-14 pp. (1984). (152) Paasivitta, J.; Vihonen, H.; Salovaara, J.; Tarhanen, J.; Veijanen, A.; Lahtipera, M.; Paukku, R.; Kantolahti, E.; Laitinen, R. FOA Rep. 1983, C 40177-C2,C3, Proc. Int. Symp. Prot. Agalnst Chem. Warf. Agents, 37-44. (162) Pankow, J. F.; Isabelle, L. M.; Asher. W. E. Envlron. Sci. Techno/.. 78,310-18 (1984). (172) Pankow, J. F.; Isabelle, L. M.; Hewetson, J. P.; Cherry, J. A. Ground Water, 2 2 , 330-9 (1984).
Geological and Inorganic Materials Carleton B. Moore* and Julie A. Canepa Department of Chemistry, Arizona State University, Tempe, Arizona 85287
This review discusses publications describing methods for analysis of geological and inorganic materials during the period November 1982 through November 1984. The topical boundaries of the inorganic and geological materials are somewhat diffuse since closely related topics are reviewed in both the fundamental and application reviews. Articles of particular interest may be found in the reviews of air pollution, ferrous analysis, fuels, surface characterization, and water analysis in the application reviews and many of the fundamental reviews especially sampling, emission spectrometry, atomic adsorption and flame emission spectrophotometry, mass spectrometry, X-ray spectrometry, and surface analysis. The citations of this review may well, by necessity, include some of those listed in other reviews, but for the most part they have been selected from the many thousands available to give the reader an overview of recent advances in each specialty reviewed together with mentions of particularly interesting specific or specialized contributions. GENERAL REVIEW LITERATURE The publication of books and monographs directly related to this review seems to have been made at a rather steady state over the past decade. If we were to pick a ”must be read” publication in the past 2 years it would be “Studies in ”Standard Samples” of Silicate Rocks and Minerals 19691982” by Sydney Abbey (1). This excellent contribution includes not only the data but also discussions of the history of standard samples and data handling and evolution. Among the major publications is the publication of the papers presented at an international symposium a t the Bhabha Atomic Research Centre, Bombay, ublished as an edited volume, “Trace Analysis and Technof)ogicalDevelopment” by M. S. Das (2). This book has contributions on the analysis of high-purity materials as well as samples of interest to environmental, earth, and nuclear scientists. “Analytical Chemistry of Molybdenum” (3) by G. A. Parker and “Physical Methods of Modern Chemical Analysis, Vol. 3.” by T. Kuwana (4), both have materials as well as samples of interest to readers of this review. An analytical technique of particular interest to mineral chemistry is reviewed in “Nuclear Tracks” (5) edited by J. N. Goswami. Another standard geochemical technique “Principles of Quantitative X-Ray Fluorescence Analysis” (6) by R. Tertian and F. Claisse has a particularly good chapter on sampIe preparation. Many items of interest are included in the two volume 1984 “CRC Handbook of Atomic Absorption Analysis” (7) by A. Varma, “Trace Elements in Coal” (8)edited by V. Valkovic and ”Trace Elements
in Soils and Plants” (9)by A. Kabata-Pendias and H. Pendias may also be of interest. M. Thompson and J. N. Walsh have produced “A Handbook of Inductively Coupled Plasma Spectrometry” (10). In the handling of data area, “Pattern Recognition Approach to Data Interpretation” (11)by D. D. Wolff and M. L. Parsons is a good short review. Selected papers from the Tenth International Geochemical Exploration Symposium have been edited by A. Bjorklund in a volume “Geochemical Exploration 1983” (12) and ”ArchaeologicalChemistry-111” (13)by J. B. Lambert. Paul Henderson, editor of ”Rare Earth Element Geochemistry” (14), himself contributed a chapter on their analytical chemistry. The entire book, which is volume 2 of “Developments on Geochemistry”, is of importance to analytical chemists. ANALYTICAL TECHNIQUES Atomic Absorption Spectroscopy. Atomic absorption spectroscopy, both flame and flameless, continues to be a dominant and preferred method for the elemental analysis of geologic and inorganic materials. Van Loon (15) published a review emphasizing trace analysis titled, “Bridging the gaps in analytical atomic absorption spectrometry”. Many of the trace analytical AA techniques are improved by the pretreatment of the geologic and inorganic sample. Bartha and Fugedi (16) suggest that the cold vapor determination of Hg in rocks and soils is greatly improved if the preanalytical extraction procedures done to remove interfering ions be done under strongly alkaline conditions. The determination of Cd and P b in geological materials by Terashima (17) involved a three-step sample dissolution procedure with a subsequent solvent extraction. Similarly,Viets, Clark, and Campbell (18) use an organic solvent extraction after only a partial leach of geologic materials to determine weakly bound Ag, Bi, Cd, Cu, Mo, Pb, Sb, and Zn. These elements are used as pathfinders in the exploration of ores. Castledine and Robbins (19) describe a portable field atomic absorption analyzer. The analyzer is flameless but not a conventional C furnace, but rather the atomizer is a W ribbon. The thallium abundance in all types of environmental samples such as rocks, soils, and waste material was analyzed by Gorbauch et al. (20). Sample decomposition and pretreatment procedures are discussed. Smith (21) presents a laboratory manual for determining metals in water. This manual details the analysis of 19 metals. A universal method for the analysis of a variety of environmental, geologic, and inorganic materials is presented by Schinkel (22). Schinkel determined Cu, Mg, Sr, K, Na, Li, 0 1985
American Chemical Society
