Anal. Chem. 1981, 53, 182R-214R (578) Gioor, R., Johnson, E. L., and MaJors, R., Varian Pub/. #35, 1977. (588) Giger, W., Staub, E., and Schaffner, L., ACS Abstr., April 1979. (598) Taylor, P. and Nickiess, G., J. Chromafogr. 178, 259 (1979). NONIONIC SURFACTANTS
(1C) Daiichi Kogyo Seiyaku Kogyo K.K., Daiichi Kogyo Selyaku S h a h , 404, 10 (1979). (2C) Danes, E. J., Casanovas, A. M., Tenslde Deterg., 18(6), 317 (1979). (3C) Vonk, H. J., Van Weiy, A. J., Van der Ven, L. G. J., De Breet, A. J. J., Van der Maeden, F. P. B., Biemond, M. E. F., Venema, A,, Huysmans, W. G. B., Tr.-Mezhdunar. Kongr. Pov8rkhn.-AM. Veshchestvam, 7th, 1, 435 (1977). (4C) Yamanaka, M., Yukagaku, 27(12), 821 (1978). (5C) Daradics, L., Rev. Chem. (Bucharest), 29(8), 764 (1978). (6C) Kirby, 0. H., Barbuscio, F. D., Metzger, W., Hourihan, J., Cosmef. Perfum., go@), 19 (1975). (7C) Nichikova, P. R., Rud, A. N., Tember, G. A,, Getmanskaya, 2. I., Ivanov, V. N., Zerzeva, I. M., Martynushkina, A. V., Neffepererab. Neffekhirn (Moscow),(3), 46 (1979). (8C) Favretto, L., Stancher, B., Tunis, F., Analyst(London), 103(1230), 955 f,l .P-7.R-1,. (9C) Broniarz, J., Wisniewskl, M.. Szymanowskl, J., Abh. Akad. Wiss. DDR 1976. 125 119771. (IOC). Stancher, B., Tunis, F., Favretto, L., J . Chromatogr.,131, 309 (1977). (11C) O'Conneii, A. W., Anal. Chem., 49(8), 835 (1977). f12C) Kaduii. 1. I.. Stead. J. B.. A n a h t (London). lOl(12061. 728 (19781. ~, (l3C) Oka, 'H., Kojima, T.; Bunsekl Kigaku, 25(11), 757 (1976). (14C) Stancher, B., Gabrlelii, L. F., Favretto, L., J. Chromatogr.,111(2), 459 (1975). (15C) Tsuji, K., Konoshi, K., J. Amer. Oil Chem. SOC.,52(3), 106 (1975). (16C) Nazawa, A,, Ohnuma, T., J. Chromafogr. 187(1), 261 (1980). (17C) Brueschweiier, H., Miff. Geb. Lebensmlffelunters. Hyg., 88(1), 46 (1977). (18C) Nakamura, K., Matsumoto, I., Yukagaku, 26(8), 464 (1977). (19C) Nakamura, K., Matsumoto, I., Nlppon Kagaku Kalshl, (E), 1342 (1975). (20C) Cassidy, R. M., Niro, C. M., J. Chromatogr., 126, 787 (1976). (21C) Kunkel, E., Tenside Deterg., 17(1), 10 (1980). (22C) Safiuiiina, L. A,, Asanbaeva, D. N., Shtangeev, A. L., Tr. Bashk. Gos. Nauchnoissled. Proektn. Inst. Neff. Prom.-Sf., 53, 64 (1978). (23C) Bergueiro, J. R., Bao, M., Casares, J. J., Ing. Quim., 10(115), 275 (1978). (24C) Kofanov, V. I., Kiimenko, N. A,, Zavod. Lab., 43(6), 668 (1977). (25C) Fischesser, G. J., Seymour, M. D., J. Chromatogr., 135(1), 165 (1977). (26C) Vertyullna, L. N., Subbotina, A. I., Leonov, M. R., Bobinova, L. M., Trofimov, N. N., Tr. Khim. Khim. Tekhnoi., (3) 112 (1975). ( 2 7 0 Goretti, G., Liberti, A., Petronio, B. M., Rlv. Itai. Sostanze Grasse, 52(5), 165 (1975). (28C) Subbarao, R.,Harigopal, V. P., Feffe, Selfen, Ansfrichm., 77(5), 197 119751 (29C) Carunchio, V., Liberatori, A., Messina, A,, Petronio, B. M., Ann. Chim. (Rome), 69(3), 165 (1979). f30C1 Werner. G.. Tenside Detero.. 16151. 247 (1979). b i c j Anthony, D. H. J., Tobin, R: s., &ai. them., 49(3), 398 (1977). (32C) Mancini, P., Racaneiii, E., Riv. Merceol, 17(2), 219 (1978). (33C) Parkhomovskii, V. L.. Dubrovskaya, N. Y., Otkryriva Izobret. Prom. Obraztsy Tovarnye Znaki, (17), 152 (1979). (34C) Schwarz, G., Leenders, P., Pioog, U., Feffe, Seifen, Ansfrichm., 81(4), 154 (1979). (35C) Sanchez, L. J., GarciaDomlnguez, J. J., Invest. Inf. Text. Tensiascfovos. 2014). 349. 119771. ..., - . ,, ~ ~ . . (36C) Sanchez, L. J., Sohns, C., Comelles, F., Invesf. Inf. Text. Tensioactovis, 20(3), 243 (1977). (37C) Waters, J., Longman, G. F., Anal. Chlm. Acta, 93, 341 (1977). (38C) Hannequin, C.,Lerenard, A., Analusis, 3(3), 177 (1975). (39C) Manaeva, A. I., Iiina, L. A., Bratchin, V. V., Vasiienko, G. V. Gig. Tr. Prof. Zaboi, (2),56 (1980). (40C) Huber, W., Froehike, E., Tenside Deterg. 12(1), 39 (1975). (41C) Krut, V. V., Enina, 0. N., Safina, L. G., Chistyakov, B. E., Neffepererab. Neftekhim. (Moscow),(I), 42 (1977). (42C) Heiimann, H., Frezenius 2.Anal. Chem., 300(1), 44 (1980). ( 4 3 3 Perov, P. A., Tember, G. A., Volkov. Y. M., Gerasimova, N. T., Neftepererab. Neftekhlm. (Moscow),(2), 47 (1979). (44C) Haensei, B., Otto, C.,Faserforsch. Textilfech., 28(2), 81 (1977). (45C) Klima, Z.,Winkler, W., Gega, H., Przegl. Wlok., 31(6), 297 (1977). (46C) Prati, G., Vicini, L., Seves, A,, Jus, A., Arpion, A,, Mezhdunar Kongr. Poverkhn-Akt. Veshchesfvam, 7th 1976, 1, 470 (1977). - r
\ . - . . I .
\ . - . - I .
~
(47C) Vinnikov, Y. Y., Kostareva, L. A., Zh. Anal. Khim., 53(3), 547 (1980). (48C) Sugawara, M., Maruyama, K., Kambara, T., Bunseki Kagaku, 24(9), 598 (1975). (49C) Lipchinski, A., Nikoiova, V., Frezenlus 2. Anal. Chem., 291(3), 223 (1978). t5OC) Gega, H., Wojcik, Z., Moniuk, D., Przegl. Wlok., 31(7), 352 (1977). (51C) Hoimqvist, P., Anal. Chim. Acta, 90(1), 35 (1977). (52C) Giacobetti, S.,Lagana, A., Petronio, 8. M., Russo, M. V., Riv. Ita/. Sostanze Grasse, 55(8), 176 (1978). (53C) LeBihan, A., Courtot-Coupez, J., Analusis, 6(8), 339 (1978). (54C) Lebihan, A., Courtot-Coupez, J., Anal. Lett., 10(10), 759 (1977). (55C) Chlebicki, J. and Garncarz, W., Tenslde Detergents, 15(4), 187 (1978). (56C) Wickboid, R., Tenside 9, 173 (1972). (57C) Helimann, H., Fresenius ZAnal. Chem. 297, 102 (1979). (58C) Greff, R. A., Setzkorn, E. A., and Leslie, W. D., J. Am. Oil Chem. SOC.42, 180 (1965). (59C) Boyer, S.L., Guin, K., Kelly, R., Mausner, M., Robinson, H., Schmitt, T., Stahi, C.,and Setzkorn, E., Env. Sci. Techno/. 11, 1167 (1977). (60C) Wickboid, R., Tenside 8, 61 (1971). (61C) Nozawa, A., Oknuma, T., and Sekine, T., Analyst(London) 101, 543 (1976). (62C) Favretto, L., and Tunls, F., Analyst(London) 101, 198 (1976). (63C) Favretto, L., Stancher, B., and Tunls, F., Analyst (London) 104, 241 (1979). (64C) Favretto, L., Stancher, B., and Tunis, F., Analyst (London) 105, 833 (1980). (65C) Crisp, P. T., Eckert, J. M., and Gibson, N. A,, Anal. Chim. Acta 104, 93 (1979). (66C) Chiebreckl, J., and Garncarz, W., Tenside 17, 13 (1980). (67C) Jones, P., and Nlckless, G., J . Chromafogr. 158, 87 (1978). (68C) Jones, P., and Nickiess, G., J. Chromafogr. 156, 99 (1978). (69C) Kozarac, Zutlp, V. and Cocovic, B., Tenside 13, 260 (1976). (70C) Wee, V. T., Advances in the Identification and Analysis of Organic Pollutants", L. H. Keith, Editor, in press. (71C) Tobin, R. S.,Onuska, F. I., Brownlee, B. G., Anthony, D. H. J., and Comba, M. E., Wafer Res. 10, 529 (1976). (72C) Otsuki, A., and Shiraishi, H., Anal. Chem. 51, 2329 (1979). CATIONIC SURFACTANTS
(ID) Maiat, M., Frezenius 2. Anal. Chem., 297(5), 417 (1979). (20) Masiennikov, A. S.,Shiikina, M. A., Lesokhim. Podsochka, (9), 10 (1979). (3D) Kawase, J., Yamanaka, M., Analyst (London), 104(1241), 750 (1979). (4D) Michelsen, E. R., Slefen, &/e, Feffe, Wachse, 104(4), 93 (1978). (5D) Waters, J., Kupfer, W., Anal. Chim. Acta, 85(2), 241 (1976). (6D) Nishida, M., Kanamori, M, Ooi, S., Miyagishi, S., Yukagaku, 25(1), 21 (1976). (70) LeBihan, A., Courtot-Coupez, J., Analusis, 4(2), 58 (1976). (ED) Wang, L. K., Aulenbach, D. B., Langley, D. F., Ind. Eng. Chem. Prod. Res. Dev., 15(1), 68 (1976). (9D) Zapior, B., Keilner, A., Czapklewlcs, J., Chem. Anal. (Warsaw),20(4), 823 (1975). (10D) Baloiu, L. M., Popescu, M., Cretu, S., Rev. Chim. (Bucharest), 30(8), 799 (1979). ( I I D ) Lepri, L., Desideri, P. G., Heimier, D., J. Chromatogr., 153(1), 77 (1978). (12D) Pustavaiova, L. M., Bogosiovskii, Y. N., Makarov, G. V., Tr. Mosk. Khim. Tekhnol. Inst., 88, 50 (1975). (13D) Batukova, G. I., Davydov. V. D., Rodimushklna, N. E., Suchkov, V. V., Koiomiets, B. S.,Kurlyaninova, L. P., Zh. Anal. Khim., 32(7), 1482 (1977). (14D) Takano, S.,Takasaki, C.,Kunihiro. K.. Yamanaka. M.. J. Amer. Oil Chem. SOC.,54(4), 139 (1977). (15D) Micheisen, E. R., Tenside Detergents, 15, 169 (1978). (16D) De Zeeuw, R. A., van der Loan, P. E., Greving, J. E., van Mansveit, F. J. W., Anal. Leff.,9, 831 (1976). (17D) Nakae, A., Kunjhiro, K., Mato, G., J. Chromatogr., 134, 459 (1977). (18D) Parris, N.. J. Li9. Chromafogr. 3, 1743 (1980). (19D) Kawase, J., Anal. Chem., 52, 2124 (1980). AMPHOTERIC SURFACTANTS
(1E) Takano, S.,Kuzukawa, M., Yamanaka, M., J. Amer. Oil Chem. SOC. 54, 11, 484 (1977). (2E) Dmitrieva, L. F., Koiomiets, B. S., Maksimikhina, T. I., Kudryavtseva, M. I., Shcherbik, L. K., German, V. K., Suchkov, V. V., Maslo-Zhir. PromSt., (6), 22 (1975).
Water Analysis M. J. Fishman," D. E. Erdmann, and T. R. Stelnheimer U.S. Geological Survey, Federal Center, MS 407, Denver, Colorado 80225
This nineteenth literature review of analytical chemistry applied to water analysis covers the period from October 1978 182 R
through September 1980. The present review follows the plan of previous reviews, the last of which appeared in ANALYTICAL
This article not subject to US. Copyright. Published 1981 by the American Chemical Society
WATER ANALYSIS Yarrln J. F M m . ban in Dsnww. CO. r 6 wived his B.A. degree (1954) and M.S. degree (1956) I r m me University 01 Worado. 4is.
has been employed by
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s o v w s Divisbn, US. Geo!+gicai Suvey. Denver. Sinw 1956. His rererch interesls are centered On devebpment 01 memods la watw analysis. including atomic absorption. He is a member 01 the Society tm A p piied SPBC~~OSCOPY and the American Society lor Testing and MaterDis (Mr. Fishman W N B S on ASTM Committee C-19 On water). He has published about 40 p a w s related to metlwds tar water analysis. He is recipient 01 me 1980 Outstanding Service Award presented by lhe Rocky Mountain Section 01 piied spctroscopy.
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DaM E. Ercmarn is presented labaatory director 01 me Naliinai water hraiity Lab ratory. Atlanta. He has been wilh me US. &O!+giCai SUNBY S h W 1968.
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his B.S. degree from Winona State Ccilege and his M.S. and h . D . degrees hom the Unlverrlly 01 Nebraska. HIS research interests are concerned vim the development
and in combination, is neither practical or in the best interest of the reader. Functional group-type classification is unacceptable because it would result in extensive overlap, less continuity of thought. and possible confusion for the reader. In addition, many citations would not conveniently fit into one or more of these subsections. This would necessitate a very large miscellaneous section which would be of little value to the reader in quickly obtaining needed information. Accordingly, the organics section, excluding Pesticides and Detergents, is divided into several headings based upon primary analytical technique used or on principal type of measurement; Le., GC and GC MS, HPLC, Photometry, Extraction & Concentration, To Element, Oxygen Demand, and Miscellaneous. This approach focuses attention on the central analytical utility of the citation with respect to water analysis rather than on individual compounds which can be analyzed. A review of literature on water pollution control, which includes a section on analytical methods and instrumentation, is published annually by the Water Pollution Control Federation. The 1978 reviews by Shuman, Fogleman, and Wavell (9).Chian and DeWalle (3),and Hensley et al. (7)include 541 references and cover such topics as inorganics, organics, continuous monitoring, automated analysis, and sampling procedures. The 1979 reviews by Shuman, Fogleman. and Wavell(10) and Chian et al. ( 4 ) cover inorganics (250 references) and organics (327 references), respectively. Electrochemical methods of chemical anal is are reviewed by Cavagnaro (2). A bibliography with 170 a c t r a c k covering polarographic, potentiometric, voltametric, and coulometric techniques, including electrochemical titrations, are reported. Skougstad et al. (13) repared a manual containing methods used by the GeologicafSurvey to analyze samples of water, suspended sediments, and bottom material for their content of inorganic constituents. Methods are included for determining dissolved, total recoverable and total concentrations of constituents in water-suspended sediment samples, and recoverable and total constituents in samples of bottom material. More t h 200 methods are given for the determination of 69 different inorganic constituents and physical pro rties of water. Essential definitions are included in the i n t r x c t i o n to the manual, along with a brief discussion of the use of significant figures in calculating the reporting analytical results. Quality control in the water-analysis laboratory is discussed, including accuracy and precision of analyses, the use of standard reference water samples, and the operation of an effective quality mwance program. Methods for sample preparation and pretreatment are given also. The third edition of "Methods for Chemical Analysis of Water and Wastes", which contains the chemical analytical procedures used in US. Environmental Protection Agency (EPA) laboratories for the examination of ground and surface waters, domestic and industrial waste effluents, and treatment-process samples was prepared by Kopp and McKee (8). Except where noted under "Scope and Application", the methods are applicable to both water and wastewaters, and both fresh- and saline-water samples. The manual provides test procedures for the measurement of physical, inorganic, and selected organic constituents. The test methods have been selected to meet the requirements of Federal legislation and to provide guidance to laboratories engaged in the protection of human health and the aquatic environment. Skougstad and Fisbman (12) stated that inorganic pollution com rises both major and minor constituents, although only 12 clemical elements may be considered major components. Twenty-eight elements constitute a group of common minor elements and an additional 13 elements comprise a group of less common minor elements. Reliable quantitative data are available on the occurrence of these substances in a wide variety of water types, usually at extremely low concentrations. Analysis of standard reference water samples provided information on the overall reliability of water-quality data. Although most major constituents were determined with acceptable reliability, determinations of certain minor constituents lacked comparable precision, for example, determinations of boron, nickel, and chromium. Few precision data are available on the determination of the less common trace elements. Several comparatively new analytical techniques, such as flameless atomic absorption spectrophotometry, voltam-
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sinw 1977. He rewived h k undergraduate baining in chemistry a1 Blackburn Cai!-3@ and obtained his Ph.0. dearee trom lhs University of Missour at R o i c His research interests include trace analysis of aganic p3iiutantS in wafer. ~ssociatbn01 (wganic contaminants with bad sediments, and envC ronmentai (wganic Chemistry 01 oil shale d e veioprnenl in the western United States. He is a member 01 American Chemical Society. Technical Cornminee 0.19 on Water ot lllLi mllmllull oYLm,y Testing and MBteriBis. and Society 01 Environmental Tarica!+gy and Chemistry.
me
CHEMISTRY for April 1979 (6). Editors of ANALYTICAL CHEMISTRY have requested that review authors cover their respective fields in a more selective manner and not attempt to provide an all-inclusivebibliography. Therefore, references used in preparing this review come mainly from major anal ical journals and United States Government publications. ?! c onference proceedings, obscure foreign journals, and most trade journals are generally excluded. Because of the increase in ublication of multiconstituent methods, a separate section is ievoted to those publications which would fall in more t h one section. Because of the environmental imoact of oreanic contaminants in water, the number of papers dealin- with organic methodology has increased tremendously. Atout one-third of this review is devoted to this area. Many new methods describe gas-liquid chromatographic separation and isolation techniques. Increased use of fused silica capillary columns has further increased the practical utility for GC, while eater use of the mass spectrometer as a detector has a g e d a measure of certainty to definitive characterization of eluted chromatographic peaks. High erformance liquid chromatography, with its various mo& of separation, has found a plicability to the determination of hydrophilic and hydroptobic organic compounds in water. Other areas of progress include automation of chromatography data processing and achievement of lower limits of detection for many pollutants. Organization of the organics section warrants comment. Because of the number and diversity of organic compounds covered in the references, the authors feel that organization parallel to that used for inorganic species, both individually
ANALYTICAL CMMISTRY. VOL. 53, NO. 5. APRIL 1981
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WATER ANALYSIS
metry, and emission spectroscopy with plasma excitation, appear capable of providing improved sensitivity. Several analytical techniques offer simultaneous determination of 5-40 elements. Of these techniques, two are receiwng extensive attention for analysis of water samples. Optical emission spectrometry utilizing plasma excitation has now evolved to a level in which 20-40 elements qan be simultaneously determined on a routine basis. Instrumentation utilizing ion exchange chromatography separations is available which allows the routine determination of several cationic and/or anionic species. Skogerboe ( I I ) described both of the above multielement analysis systems and summarized their respective capabilities and limitations with respect to water analysis and to projected areas of future development. Burba et al. (1) compared results obtained by X-ray fluorescence, neutron activation, and atomic absorption for determining trace elements in freshwater and seawater. For neutron activation analysis, samples were first preconcentrated by freeze-drying and shaking with a cellulose exchanger; for X-ray fluorescence analysis, preconcentration was achieved by separation of the elements in columns filled with cellulose exchanger, filtration through cellulose exchanger filters, or shaking with cellulose exchanger. Results of an International Atomic Energy Agency intercomparison test in the determination of 16 trace elements in simulated freshwater Sam les were reported by Dybczynski, and discussed with respect to Tugsavul, and Suschny accuracy and precision. The relative frequency of employment of various analytical techniques was discussed and a comparison of their accuracy presented. A review with 15 references on the determination and chemical forms of trace metals in natural water is given by Tseng (14).
8)
ALKALI METALS AND ALKALINE EARTH METALS Schulten, Bahr, and Lehmann (10A) determined lithium in microliter samples of mineral and tap water and other solvents by stable isotope dilution and field desorption mass spectroscopy without any sample pretreatment. Analysis time is approximately 20-30 min; lithium concentrations between 1 x lo-’ and 1 X mg/L are measured. To determine potassium in water, Menke (5A) used energy-dispersive X-ray fluorescence. Potassium is precipitated and measured as the tetraphenylborate. A tungsten X-ray tube and titanium as secondary target are employed to excite the fluorescence radiation. A silicon (lithium) detector is used for detecting the emissions. Potassium levels between 0.1 and 1000 pg can be determined. Nakamura, Takagi, and Ueno (7A) reported that crown deether reagents such as 4’-picrylaminobenzo-15-crown-5 rivatives can be used to extract alkali metal cations for photometric determination. Potassium is the most easily extracted, and determination of 10-800 ppm potassium is possible. Sun, Wang, and Ge (11A) prepared a polyvinyl chloride type, calcium ion selective electrode for determination of calcium in water. Details of preparation are given. Calcium results agreed with those obtained by the EDTA-ammonium violurate method, Hansen, Ruzicka, and Ghose (3A) reported on a flow-injection technique for determination of calcium in water. Either spectrophotometric or potentiometric detection can be used. Rates up to 110 samples/h are achieved by using 30-kL sample injections. Results are in good agreement with those obtained by atomic absorption and EDTA titration. A method is described by Ohzeki, Schumacher, and Uml;and (8A) for the successive complexometric titration of calcium and magnesium in water with EGTA using a thallium oxide electrode for amperometric end-point indication. A distinct increase in the anodic current indicates the calcium end point; a second increase indicates the end point for magnesium. Interferences due to ferrous and manganese ions can be suppressed by the addition of man anese(VI1) to the sample. A mixed indicator of Calcon anfMetani1 Yellow at a ratio of 2:l was used by Yavorskaya, Kazak, and Lebedev (15A) for complexometric determination of calcium in water and other geologic material. Sensitivity is 0.06 pg mL. Reijnders, Van Staden, and Griepin (9A) described a continuous flow system for the titrimetric determination of calcium in environmental samples using dipotassium 3,6-
k
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
dioxacotamethyldinitrilotetraacetic acid as titrant. The overall relative standard deviation of the method is better than 5%. The limit of detection is 7 pmol/L of calcium. At least 30 samples/h can be analyzed. A kinetic method is described by Ternero et al. (13A) for determination of magnesium in natural waters in the presence of calcium. The method is based on inhibition of manganese(I1)-catalyzed oxidation of 1,4-dihydroxyphthalimide dithiosemicarbazone by magnesium. Rate of change in absorbance is continuously measured at 594 nm. Epstein and Zander (2A) determined barium in seawater and estuarine waters directly by graphite furnace atomic spectrometry. The accuracy of the method was evaluated by a correlation of results with data from determinations using line source and wavelength-modulation continuum-source atomic absorption spectrometry and gra hite furnace atomization, as well as the analysis of a s t a n g r d reference water sample. Techniques to overcome interferences were discussed. To determine barium in seawater, Murozumi et al. (6A) applied isotope dilution-mass spectrometry. An aliquot of sample is isotopically equilibrated with 135Baspike and loaded g onto a sin le rhenium filament. A detection limit of is obtainei from the isotopic ratio, 138Ba/135Ba,measured in a spiked sample. Coprecipitation of barium with lead sulfate from homo eneous solution by the use of sulfamic acid was studied%y Takiyama and Ishii (12A) by electron microscopy and X-ray diffraction methods. The method was used to measure the content of barium in water. Cheney, Curran, and Fletcher (1A) determined water hardness based on the polarographic reduction of magnesium ion. The magnesium ion is displaced from its EDTA complex by cations contributing to water hardness and the liberated magnesium ion is reduced at a dropping mercury electrode via a catalytic process. The resulting enhanced diffusion current is about 100 times that obtained from a conventional diffusion-controlled process. Accuracy and precision are comparable to standard EDTA titrations and the technique is more rapid. A method for potentiometric end point detection in the chelometric titration of water hardness with EDTA is described by Virojanavat and Huber (14A). The electrode system consists of a wax-bound lead oxide electrode vs. a wax-bound lead sulfide electrode. The method was tested on samples with total hardness of 10-300 mg/L. Divalent (water hardness) ion selective electrodes based on polyvinyl chloride and polymethyl ac late matrix membranes were studied by Hassan, Moody, anyThomas (4A). Details on the membrane compositions were given.
ALUMINUM, IRON, AND MANGANESE Carrondo, Lester, and Perry (3B) determined total aluminum (including zeolite type A) in water and wastewater by direct electrothermal atomic absorption. When necessary, the samples are homogenized prior to analysis. Fluorescence properties of metal complexes of salicylaldehyde-semicarbazones was used by Morisige et al. (13B) for the fluorimetric determination of aluminum in seawater between 0.2 and 160 pg/L. Fluorescence of the 2,4-dihydroxysalicylaldehyde-semicarbazone chelate at pH 5.5, using quinine sulfate as reference, is excited at 353 nm and emission measured a t 413 nm. Korenaga, Motomizu, and Toei (IOB, 11B) modified the pyrocatechol violet and zephiramine method for determining aluminum in river water. Excess of coextracted reagent was removed in the solvent extraction of anionic metal complexes with a quaternary ammonium salt. Recovery of aluminum is 96-103% for concentrations of 78-230 wg/L in 4-mL aliquots of samples. Korenaga, Motomizu, and Toel (9B) used a similar technique for determining iron in water with pyrogallol red and zephiramine. Watanabe, Yoshizawa,and Kawagaki (18B)determined iron in tap water by solvent extraction of tris(1,lOphenanthroline)iron(II)-Bismuthiol I1 as an ion pair into chloroform. Under optimum conditions, the absorbance follows Beer’s law up to 25 pg of iron 10 mL of chloroform. A simple method is described by Gi bs (5B) for the rapid determination of iron in natural waters using the chromogen Ferrozine. The method is capable of analyzing samples with iron concentrations from less than 5 mg/m3 to 3 g/m3. In
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WATER ANALYSIS
addition to total dissolved iron, it is possible to determine iron(I1) and iron(II1). The synergistic effect of pyridine bases and trioctylphosphine ortide (TOPO) on the extraction of iron(I1) with dibenzoylmethane was examined by Akaiwa, Kawamoto, and Hiyamuta (1B).Iron(I1) was determined by measuring the absorbance of the benzene extract at 408 nm. Some interferences were encountered. The method was used to determine iron in hot-spring waters. Pakalns and Farrar (I4B) investigated the effects of pure cationic, anionic, and nonionic detergents; industrially prepared detergents, sodium tripolyphosphate, sodium yrophosphate, soap, and NTA in quantities up to 1000 mgrL on the determination of dissolved iron in water using phenanthroline, tripyridine, and lbiquinoline methods. The effect each surfactant has on each of the three methods is discussed. Mehra and Landry (12B)spectrophotometricallydetermined iron in samples of water and soil by a method based on its reaction with potassium hexacyanourthenate(I1).An intensely violet-blue complex is produced which absorbs at 550 nm. Beer's law is obeyed between 0.04 and 2 pg/mL of iron in acidic medium. Most common cations and anions give negligible interference. Hayashi et al. (7B) reported that the thiocyanate method for spectrophotometricdetermination of trace amounts of iron is unsatisfactory because iron(II1)-thiocyanate complexes are unstable in aqueous solution. The red complex is stabilized by the presence of a nonionic surfactant such as Triton X-100. Even after 12 h, absorbance decrease is minimal. Interferences of reducing agents are eliminated with a small excess of potassium permanganate. Copper also is complexes, but its color fades rapidly. Ditzler and Gutknecht (4B) determined trace levels of iron(II1) in water and other materials by homogeneous catalysis and gas chromatography. The method is based on the measurement of o-hydroryanisole, which is a product of the iron(II1)-catalyzed reaction between anisole and hydrogen peroxide. The method is linear to 1000 ppb with a detection limit of 0.25 ppb. Of several metal ions tested, only copper(I1) is found to significantly interfere. A dual-channel atomic absorption spectrometer was used by Takada and Nakano (l6B)to assess the internal standard technique for electrothermal atomization. Cobalt was a suitable internal standard for iron; it was used for determination of 7-330 ng/mL of iron in water samples. With this technique, fluctuations caused by atomizer variables are reduced, and interferences from many cations are also decreased. After coprecipitating iron imd manganese from drinking water with magnesium hydroxide and redissolving the precipitate in 6 N hydrochloric acid, Tsuyama and Nakashima (I7B) determined these constituents by atomic absorption spectrometry. Relative standard deviations of 1.32 and 3.75% were obtained for 0.15 and 0.08 mg/L of iron and manganese, respectively. Chelating agents such as polyphosphate or EDTA greater than 20 mg/L caused negative errors. Methods were described by Sturgeon et al. (15B) for the direct determination of iron and manganese in seawater by raphite furnace atomic albsorption spectrometry. A comination of furnace tube redesign, selective volatilization, and matrix modification techniques allow both elements to be determined by method of standard additions. The lower limit of detection for iron and manganese is 0.2 pg/L. Hydes (8B) reported that the addition of 1%ascorbic acid to seawater eliminates interferences when determining manganese by flameless atomic absorption spectrometry. The author does not explain the mechanism which eliminatesthe interferences. Two methods were compared by Weiss et al. (19B)for the determination of manganese in seawater. One method is based on the isolation of manganese by cocrystallization with 8quinolinol. The crystals are then irradiated with neutrons, and, after simple purification steps, %Mnis quantified by y-ray spectrometry. The other method involves chloroform extraction of manganese diethyldithiocarbamateand subsequent determination by atomic absorption spectrometry. Both methods are reported to be reliable. A rapid neutron activation procedure for the determination of manganese from seawater and rainwater is presented by Wijkstra and Van der Sloot (20B). Manganese prior to determination is preconcentrated as pyrrolidine-dithiocarbamate complex in a layer of active carbon. If the carbon blank can be kept low, the limit of detection is 50 ng/L with a 200-mL sample.
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Gine, Zagatto, and Bergamin (6B)determined manganese in natural waters by the formaldoxime method using flow injection analysis. With an injected volume of 0.35 mL, about 135 samples/h could be analyzed with a relative standard deviation better than 1% over the ran e of 0.2-2 pm. Akaiwa, Kawamoto, and Kogure (2BFreported t at manganese(I1) reacts with dithizone and 1,lO-phenanthrolineto form a mixed ligand complex which can be extracted into chloroform at a pH of 8 to 9. The absorbance is measured at 507 nm. The method is used to determine manganese in hot-spring waters. The relative standard deviation for 3 pg of manganese is 1.3%.
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BERYLLIUM, CADMIUM, CHROMIUM, COBALT, COPPER, LEAD, NICKEL, SILVER, THALLIUM, AND ZINC This is the first of three sections which deal with thpse parameters which are in the Environmental Protection Agency's priority pollutant list. Sperling (60C) determined cadmium in seawater by extraction with APDC using carbon tetrachloride and tetrachlorethylene; the organic phase is analyzed by flameless atomic absorption spectrometry. A raphite-furnace atomic absorption spectrometric metho using standard addition is described by Guevremont, Sturgeon, and Berman (25C) for the determinationof cadmium in Seawater. Addition of EDTA reduces the temperature of atomization of cadmium to below that of volatilization of other matrix components. A detection limit of 0.01 pg/L, a sensitivity of 0.034 pg L, and a precision of 10% at the 0.05 pg/L level were obtaine for 20-pL aliquots. Sperling and Bahr (61C) reported that precision and accuracy in flameless atomic absorption spectrometry can get progressively worse, especially for cadmium, because of varying quality and durability of the graphite tubes. Prior to determination by atomic absorption spectrometry, Skorko-Trybula and Kozinska (58C) concentrated cadmium from water by electrolytic deposition on a platinum electrode from 0.1 N electrolyte solution (pH 3.3-3.8) at -1 V vs. a standard calomel electrode. As little as 1 ng/mL cadmium in a 50-mL sample can be detected. A simplified polarographic technique to determine cadmium to 1 X lo4 M level was in water and seawater at the 1x developed by Guedes de Mota et al. (24C). Cadmium was f i s t concentrated by percolating approximately 2 L of sample over a column with an immobilized rea ent and dissolving the trapped cadmium in 0.1 M nitr.ic acid A concentration factor of 50 or more was achieved with 90% recovery. Rakhmonberdyev and Nazarov (52C) determined cadmium in water by inverse voltammetry with a mercury-film electrode using a second derivative. The APDC-MIBK atomic absorption spectrometricmethod for simultaneous extraction of chromium(II1 and VI) from water was modified by Bergmann and Hardt (6C). The solution is buffered to pH 4.7-5.5 with potassium acid phthalate and heated to 80 "C for 20 min before extraction. The authors also could determine the concentration of each of these ionic species in water. Yu and Chao (83C) extracted chromium(II1 and VI) from water with an anion-exchanger tertiary amine compound (N-235) into MIBK prior to determination by atomic absorption spectrometry. By the processes described in the publication, 50 ppb chromium(II1) and 50 ppb chromate in river water were determined with standard deviations of 4.5 and 2.370, respectively. Thompson and Wagstaff (66C) determined chromium in natural waters and sewage effluents by atomic absorption spectrometry using a near-luminous air-acetylene flame. The samples were first digested with ammonium perchlorate and hydrochloric acid. A flameless atomic absorption procedure for the determination of chromium species was develo ed by Cranston and Murray (13C) and applied to both fresiwater and seawater. The method utilizes preconcentration of total chromium, chromium(III), and particulate chromium at natural pH. De Jong and Brinkman (15C) used flameless atomic absorption s ectrometry to determine chromium(II1and VI) in seawater. hromium(V1) is extracted with Aliquat 336 from a weakly acidic sample and chromium(II1) is extracted at neutral pH with about 1M thiocyanate ion. The detection limits are 0.01 and 0.03 pg/L for chromium(V1) and chromium(III), respectively.
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Wang (74C) presented a modification of the diphenylcarbazide-spectrophotometric method for determining chromium in water. He stated that the modifications were made to overcome problems with the original method. Details are given. Yamazaki (80C) determined chromium(V1) in natural water by copreconcentration with barium sulfate and spectrophotometric determination with diphenylcarbazide. This technique isolates the chromium(V1) from chromium(1V). Salicylic acid is added to mask iron(III), aluminum(II1) and chromium(II1). The detection limit is 0.02 pg/L. To determine traces of chromium(V1) in river water and seawater, Yoshimura and Ohashi (81C) used ion exchange (Dowex 50W-X4) to concentrate the chromium from a liter of sample prior to spectrophotometric determination with 1,5-diphenylcarbohydrazide. Relative standard deviations were M and 3.2% at 2.0 X lo-' M. 6.5% at 1.5 X Determination of trivalent chromium in seawater by chemiluminescence using luminol is discussed by Chang et al. (12C). Major interference comes from ma nesium ions. Elimination of the interference is achieved by dilution of the sample and utilization of bromide ion for signal enhancement. The detection limit is 0.2 ppb for seawater with a salinity of 35%. Bause and Patterson (ZC) reported that the determination of trace amounts of metals by chemiluminescenceis affected by high concentrations of halide ions. A bromide concentration of 0.5 M yields an 8-fold increase in signal intensity for chromium(III),relative to the signal without bromide ions. The si nal enhancement lowers the limit of detection to 1.3 X 10-1 M for freshwater systems. Enhancements for other metals are also given. A spectrophotometric method for determining cobalt in brines is described by Kouimtzis, Apostolopoulou, and Staphilakis (35C). Cobalt concentrations equal to or greater than 1 ppb are selectively extracted as di-2-pyridyl ketone-2pyridylhydrazone complex into isoamyl alcohol and backextracted into dilute perchloric acid. The relative standard deviation for 2 ppb cobalt is 5%. A spectrophotometric procedure is reported by Beaupre and Holland (3C) for the determination of cobalt at the ppb level in natural water usin 2-pyridyl-2-thienyl-fl-ketoxime. Cobalt is first concentrate! with 2-nitroso-1-naphthol. The method allows the determinations of 0.2 to 1.0 ppb cobalt. Bonelli, Skogerboe, and Taylor (8C) reported that water samples subjected to differential- ulse anodic-stripping voltammetry for copper showed hig values relative to results obtained by atomic absorption and plasma-emission spectrometry when significant quantities of iron were present. The interference is decreased by increasing the deposition time. A method for making corrections is given. Shuman and Michael (57C) stated that cyclic voltammetry and anodicstripping voltammetry of copper in dilute carbonate solutions a proximatin natural freshwater indicated that carbonate arkalinity and pH affected copper reversibilit , possibly through variations in buffer capacity or rate of cargon dioxide hydration. An approximate but general theoretical treatment for reversible- and irreversible-strippingpolarographic systems is resented by Zirino and Kounaves (84C). The treatment is Eased on the development of an average current, which, at plating times exceeding 15 s, is analogous to the instantaneous current in dc polarography. From stripping polarography and anodic-stripping voltammetry, the overall reduction of cupric ion at the environmental pH of the sample is kinetically hindered; thus it is irreversible. Reversibility and the determination of cop er in seawater is im roved by acidification and (or) by the aidition of ethylene8amine. Two flow-through cupric-selective electrodes (dismountable and disposable) for the continuous and flow-injection determination of cupric iron are described by Van der Linden and Oostervink (716). The disposable type was used to monitor copper in tap water. Stella and Ganzerli-Valentini(62C) used a copper ion selective electrode for determinin inorganic copper species in freshwater. Assumin that hy roxide and carbonate are the most important ligan& and concentrations are known, the resence and distribution of CuOH', Cu2(OH)22+,CuCO,8aq), and Cu(C03)2- are deduced by measuring cupric ion concentration as a function of pH in controlled media. Westall, Morel, and Hume (79C) studied the effect of chloride on cupric ion selective electrode measurements. On the basis of their theory, the electrode is unsuitable for
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determination of cupric ion in seawater. Panova, Chekrii, and Filatov (50C) determined copper in boiler water by copper-induced fluorescence quenching of fluorexon. Fluorescence is quenced within 10 min, and the sample remained stable for 5 h. The method is applicable between 0.5 and 25 mg/L. Weiss et al. (78C) compared neutron activation and atomic absorption spectrometry for the determination of copper in seawater. The neutron activation method is based on the isolation of copper by cocrystallization with 8-quinolinol and irradiation of the crystals with neutrons. After purification, copper-64 is quantified by y-ray spectrometry. The atomic absorption method involves chloroform extraction of copper diethyldithiocarbamateand then aspiration of the chloroform extract. Nagatsuka and Tanizaki (45C) concentrated copper from river and groundwater samples on emission spectrographic carbon powder. The powder is dried and copper determined by neutron activation analysis. DuBois and Sharma (17C) described a radiometric method for direct determination of co per in natural waters. The level of radioactivity bound by sugstoichiometric amounts of 4 7 diphenyl-1,lO-phenanthroline from mixtures of constant amounts of radiolabeled ferrous ions (ferrous-59) and increasing amounts of cuprous ions is shown to be linearly but inversely related to the amount of cuprous ion in solution. Only one milliliter of sample is required. Relative standard deviations at 2 and 20 ng/mL are 30 and 2.5%, respectively. Kucharski and Sikorska-Tomicka (37C) described a spectrophotometric method for determining copper in water. Cuprous ion and binazine form a 1:2 complex which is extracted at pH 7.5-8.5 into chloroform. The absorbance of the complex is measured at 410 nm. Ishii and Koh (31C) reported that sensitivity in spectrophotometry can be enhanced by measuring the higher-order derivative value, instead of the absorbance value, by using an automatic-recording spectrophotometer and anal0 -differentiation amplifiers. The method was applied to the cfetermination of copper usin a,fl,y,Stetrakis( 1-methylpyridinium-3-y1)porphine. The aut ors state that as little as 1 ppb of copper in drinking water can be measured. An ion-selective cation-exchange indicator paper with a covalently bonded chromogenic reagent was used by Ostrovskaya et al. (49C) for a rapid, semiquantitative determination of 5 ppb to 500 ppm copper in water and wastewater by visual comparison with various color scales. Truitt and Weber (68C) reported losses of up to 79% copper from waters during filtration through various membrane filters. They also measured contamination from two types of filter membranes. Recursive estimation to the real-time determination of trace metal analytes by linear sweep, pulse, and differential-pulse anodic stripping voltammetry was applied by Seelig and Blount (56C) to the determination of lead in municipal and seawater samples. A critical comparison of this recursive estimate to other analytical techniques is presented. Case (11C) modified an anodic-strip ing voltammetric method to acquire data for lead from amiient seawater conditions. A chemical model was developed which used these data to identify inorganic lead species in saline environments. A chronopotentiometer is described by Makovetskii, Galinker, and Goronovskii (39C) for determining metal ions in natural water and wastewater, and for its use in development of anodic-stripping techniques. The method is illustrated by determining lead using 0.1 N hydrochloric acid as supporting electrolyte. Electrothermalatomization was studied by Ohta and Suzuki (48C) for determination of lead in water. Thiourea was used to lower the atomization temperature of lead and to eliminate interference from chloride. The absolute sensitivity was 1.1 X g of lead. Hirao et al. (27C) determined lead in seawater by graphite furnace atomic absorption spectrometr after extraction of lead with dithizone in carbon tetrachloriJi and back-extraction with 0.1 M hydrochloric acid. Lead-212 is added as a tracer to correct for yield. Mitcham (43C) also used the graphite furnace to determine lead in drinking water. Lead is extracted with ammonium tetramethylenedithiocarbamate and injected into the electrothermal atomizer. Vijan and Sadana (72C) reported that copper and nickel interfere in the hydride generation-atomic absorption method for lead. The interference is eliminated by coprecipitation of lead with manganic oxide from acidic solution. Results on
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WATER ANALYSIS
water samples were comlpared to results by differential pulse anodic-strippingvoltamnietry and flame and graphite-furnace atomic absorption spectrometry. Melzer, Jordan, and Sutton (41C) discussed the use of metastable energy transfer emission spectrometryto determine lead in water. The sample is evaporated by staged heating in a tantalum receptacle, the lead vapor is then mixed with active nitrogen, and the 283.3- and 405.8-nm lines in the emission spectrum are used for measurement. The calibration curve is linear for 10-10000 ng of lead. Culberson and Washburne (14C) used the change in pH that occurs when metals are complexed by EDTA to detect the end point in lead-EDTA titrations. With this technique, M in the presence of 7 X lead at a concentration of 1 X M magnesium or calcium is measured with a relative standard deviation of 0.6%. In synthetic seawater, the method is precise for lead concentrations as low as 5 X lo4 M. Epstein et al. (ZOC) determined nickel in river water by laser-excited atomic fluorescence spectrometry. Nonresonance nickel fluorescence near 340 nm is excited at several nickel lines near 300 nm. Factors which affect the detection limit and methods to improve it are discussed. Flora and Nieboer (i?2C) stated that dimethylglyoxime sensitizes the differential pulse polarographic determination of nickel(I1). The detection limit is 2 ppb and the analytical curve is linear to 85 ppb. Characterizationof the electroactive process included an examination of degree of reversibility, effect on the peak current of pH, buffer composition, dimethylglyoxime concentration, and presence of other metal ions. Analyses of tap arid lake water samples are reported. A dual direct method for the ultratrace determination o€ thallium in natural waters by differential pulse-anodic-stripping voltammetry is presented by Bonelli, Taylor, and Skogerboe (9C). The hanging mercury drop electrode and the mercury film electrode are used in the concentration ranges 0.5-100 pg/L thallium and 0.01-10 pg/L thallium, respectively. Quantificationis aided by ithe technique of standard additions. The response of the method is optimized for typical natural surface water matrices. An intercomparison of thallium determinations performed by the two anodic stripping methods and electrothermal-atomization atomic absorption spectrometry on normal and thallium-spiked surface water samples demonstrates equivalent accuracy within the range where atomic absorption is applicable. The method appears free from serious interferences. An atomic absorption nilethod is described by Korkisch and Steffan (34C) for the determination of thallium in natural waters. Hydrobromic acid is added to the sample. After filtration, bromine is added, and the solution is passed through a column of strongly basic anion-exchan e resin, on which thallium is adsorbed as tlhe anionic thalhm(II1)-bromide complex. Thallium is then eluted with an aqueous solution of sulfur dioxide, and after evaporation of the eluate, thallium is aspirated in an air-acetylene flame. Murozumi, Nakamura, and Igarashi (44C) reported that g, could be thallium, at concentrations as low as 1 X determined by isotope dilution-surface ionization mass spectrometry using thallium-203 as a spike. The method revealed that the concentration of thallium in the ocean increased with increasing depth at the ppt level. The method of standard addition in combination with raphite furnace atomic absorption spectrometry was used y Sturgeon et al. (63C) to determine zinc in seawater. The limit of detection is 0.4 pg/L, with a precision of 11% at the 2 pg/L level. Kritsotakis and Tobschall (36C) determined zinc in river waters containing high heavy metal sediment by differential-pulse anodic stripping voltammetry. Filtration through a membrane filter of 0.2-fim pore size remove surfactants which interfered with the determination. Miller (42C) used the colorimetric-zincon method to determine zinc in water and smelter wastewater. A sample is treated with zincon and cornplexed with potassium cyanide. Cyclohexane is added to develop the blue color. The minimum detectable concentration is 0.02 mg/L. An anion-exchange colorimetric method is described by Yoshimura, Waki, and Ohashi (82C) for determining zinc in water with zincon. Zinc is exchanged from a large volume of sample onto an acidified Dowex 1-X2 resin. The resin is se arated, made basic, and mixed with zincon and the absoriance of the resin slurry
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measured at 650 nm. A nonionic surfactant, polyoxyethylene nonylphenyl ether, was used by Watanabe and Tanaka (77C) and Watanabe, Yamaguchi, and Tanaka (75C) as a new solvent for liquid--liquid extraction of zinc in tap water with 1-(2-pyridylaz0)-2-naphthol.Watanabe and Yamaguchi (76C) also used 2-(8-quinolylazo)-4,5-diphenylimidazolewith a nonionic surfactant to determine zinc in water. Both are spectrophotometric methods. Igarashi et al. (30C)developed a highly sensitive spectrophotometric method for zinc using ~u,~,y,G-tetrakis(l-methylpyridinium-4-yl)porphine. The complex is formed within 1min at room temperature at a pH 9.2-10.8. Many metals interfere, but zinc can first be selectively separated by dithizone extraction. A number of investigators used flame atomic absorption for combinations of constituents discussed previously. Berndt and Messerschmidt (7C) introduced the sample into the flame on an electrically heated platinum loop. The method is illustrated by the determination of lead and cadmium in drinking water for concentrations as low as 5 pg/L. A procedure was developed by Vratkovskaya and Pogrebnyak (73C) for the determination of copper, lead, and zinc in natural waters, using preconcentrationby evaporationto a dry residue (mineral content, 5 g L). Guedes da Mota, Jonker and Griepink (23C) used co umn separation and preconcentration to determine copper, lead, and zinc in seawater. The sample is passed through a column filled with EDTA chemically bound to a glass support. The metals are eluted with 1 M hydrochloric acid and measured. Armannsson (1C) extracted cadmium, zinc, lead, copper, nickel, cobalt, and silver from seawater with dithizone. Tessier, Campbell, and Bisson (65C) evaluated the AFDC-MIBK extraction method for the determination of cadmium, cobalt, copper, and nickel in river water. A number of papers appeared in which the authors coupled electrothermal atomization with atomic absorption spectrometry for multielementdetermination. Bruland et al. (1OC) extracted copper, cadmium, zinc, and nickel from seawater with dithiocarbamate. Ryabinin and Lazareva (54C) determined copper, silver, and cadmium in seawater after extraction of the metals with diethyldithiocarbamate and chloroform. A dithizone-chloroform extraction technique for determining nanogram per liter levels of cadmium, copper, nickel, and zinc in seawater and freshwater is described by Smith and Windom (59C). APDC-MIBK was used by Mamontova and Pchelintseva (40C) to determine lead and cadmium in natural waters, suspensions, and sediments. Tanaka, Hayashi, and Ishizawa (64C) acidified samples with nitric acid, which they claim was effective in decreasin the nonspecific absorption caused by sodium chloride and potassium chloride, when determining cadmium and copper. Because of matrix effects and the inadequate detection limits for direct determination, Hudnik, Gomiscek, and Gorenc (28C) se arated cadmium, cobalt, chromium, copper, nickel, and leac r in mineral waters by precipitation of their tetramethylenedithioarbamateswith ferric iron as collector or by coprecipitation on ferric hydroxide. Lamathe (38C) discussed the extraction of copper, lead, nickel, zinc, cadmium, and cobalt from seawater with Chelex-100prior to determination. Bengtsson, Danielsson, and Magnusson (5C) investigated interferences from small amounts of sea salt when determining cadmium and lead. They found that the addition of lanthanum minimized interferences and that it is due to a change of the graphite tube surface. Tominaga and Umezaki (67C) used ammonium salts to suppress interferences in the determination of lead and cadmium. Hydes (29C) reported that the addition of 1% ascorbic acid reduces interferences when determining copper in seawater and eliminates interferences when determining cobalt. Nygaard ( 4 6 0 evaluated a dc plasma emission spectrometer for the determination of cadmium, chromium, copper, lead, nickel, and zinc in seawater and acid digests of ocean sediments. He reported that sodium, calcium, and magnesium increase the background and elemental line emission intensities. An inductively coupled argon lasma was used by Epstein et al. (19C) as a narrow-line ragation source for the excitation of atomic fluorescence in several analytical flames. Detection limits for 14 elements are compared to atomic fluorescence detection limits with other radiation sources and other atomic spectrometric techniques. The technique was applied to the determination of cadmium and zinc in simulated freshwater (NBSSRM-1643). Hiraide et al. (26C) pre-
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concentrated chromium, manganese, cobalt, copper, cadmium, and lead in water by coprecipitation and flotation with indium hydroxide prior to determination by inductively coupled plasma emission spectrometry. Because of the low levels of detection and sensitivity, anodic stripping voltammetry is being widely used. Dhaneshwar and Zarapkar (16C) determined thallium and lead in rainwater simultaneously by ASV. Thallium is determined in a tartrate buffer medium at pH 4.5 in the presence of EDTA, and a composite anodic peak is obtained in tartrate alone to account for lead. Valenta et al. (69C) used a mercury thin-film rotating glassy carbon electrode for the simultaneous determination of cadmium, lead, and copper in water. Poldoski and Glass (51C) also used a mercury thin-film electrode for the determination of cadmium, lead, and copper in selected natural waters. Valenta et al. (70C) presented a continuous on-line monitoring method for the determination of co per, lead, cadmium, and zinc in drinking water. Nygaard anBHill(47C) compared two methods for the determination of cadmium, copper, and lead in seawater. One employed ASV at controlled pH, and the other involved sample pretreatment with Chelex-100. Salim and Cooksey (55C) analyzed riverwater for lead, cadmium, and copper by ASV both in solution and adsorbed on suspended sediment. The use of Chelex to determine labile fractions of cadmium, copper, lead, and zinc aqueous solutions by ASV in the presence of nitrilotriacetic acid, EDTA, glycine, and humic acid was studied by Figura and McDuffie (21C). Jagner and Aaren (32C) reported detection limits of 0.03,0.03, 0.01, and 0.02 pg/L for zinc, cadmium, lead, and copper in seawater by potentiometric stripping analysis. Standardized procedures for simultaneous determination of copper, cadmium, lead, and zinc, and of lead and thallium in drinking water by ASV are described by Klahre, Valenta, and Nuernberg (33C). A difference chronoammetry method was developed by Romanov, Sobina, and Kheifets (53C) for nickel and cobalt determinations in water from catalytic hydrogen ion currents in solutions containing dimethylglyoxime. A simultaneous determination of copper and nickel by solvent extraction and gas-liquid chromatogra hy with bis(acetylpivaly1methane)ethylenediimine was escribed by Belcher, Khalique, and Stephen (4C). M) with Ejaz et al. (18C) extracted traces of zinc (1 X 0.1 M diphenyl(2-pyridy1)methanein benzene from neutral and acidic aqueous thiocyanate solutions in a single extraction. The method can also be employed for the simultaneous preconcentration of toxic metals (other than zinc), such as copper and mercury, from neutral aqueous solutions in water pollution studies.
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BISMUTH, GOLD, INDIUM, MOLYBDENUM, RHENIUM, THORIUM, TIN, TUNGSTEN, URANIUM, VANADIUM, AND ZIRCONIUM Toshimitsu, Yoshimura, and Ohashi (400) determined bismuth in natural water and industrial effluents spectrophotometrically. Bismuth-iodide complexes are specifically sorbed onto an anion-exchange resin in the sulfate form, and the resin-phase absorbance at 492 and 700 nm is measured directly. Relative standard deviations at 0.045 and 0.089 p M for a 1-L sample are 13 and 270, respectively. The detection limit is 1.3 ppb. Bismuth was determined by Rakhmonberdyev and Nazarov (340) in water by inverse voltammetry with a mercury-film electrode using a second derivative. Bismuth was preconcentrated at -0.7 V vs. a standard calomel electrode. The relative standard deviation is about 0.08 for determining and 1 X bismuth between 1 X A sensitive chemical-spectrographic determination of gold in natural water is described by Plyusnin, Pogrebnyak, and Tat'yankina (300). Gold is preconcentrated on finely ground charcoal, which is calcined at 600 "C. This step is followed by emission spectrographic analysis at 267.6 nm. The determinable range is 0.01-5.0 .ug/L with a relative standard -, deviation of 0.622-0.2270. Poerebnvak (310) determined gold in natural waters by neutqon activation. 'Gold is preconlcentrated by sorption o n activated carbon; the lower limit of the technique is 2 X 10-l' combination of electrodeposition on graphite followed y neutron activation analysis was used by Tateno and Ohta (380) to determine gold and indium in seawater; the detection limit for indium is 1 ppb. 188R
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A direct graphite-furnace atomic absorption spectrometric method for determining molybdenum between 0.1 and 4 ng is reported by Nakahara and Chakrabarti (250). The salt matrix is removed completely by selective volatilization a t 1700-1850 "C. Added magnesium chloride prevents decreases in absorbance from sodium chloride, potassium chloride, and sodium sulfate present in the samples. Ni, Chin, and Wu (270) extracted molybdenum from water with N-benzoyl-Nphenylhydroxylamine into chloroform and back-extracted molybdenum into ammonium hydroxide, prior to determination by graphite furnace-atomic absorption spectrometry. The concentration range of the method is 0.1-1 ppm molybdenum. Monien et al. (240) compared inverse voltammetry, atomic absorption, and X-ray fluorescence methods for the determination of molybdenum in seawater. The latter two methods required preconcentration prior to determination. Results from Baltic Sea samples compared favorably. A neutron activation method was developed by Kulathilake and Chatt (200) for the determination of molybdenum in seawater and estuarine water. Molybdenum was preconcentrated with P-naphthoin oxime; a detection limit of 0.32 pg/L was achieved. Ohta, Fujita, and Tomura (280) reported that traces of molybdenum in seawater can be determined spectrophotometrically at 392 nm after complexing molybdenum with 5-chloro-7-iodo-8-quinolinol. A new catalytic reaction of rhenium and its application to the determination of rhenium in mineral water is reported by Iordanov, Pavlova, and Stefanov (160). Acid hydrolysis of a-furil dioxime to di-a-furil diketone is catalyzed by rhenium concentrations between 0.0005 and 0.5 pg/mL in the presence of stannous chloride; the absorbance of the product is measured a t 320 nm. Caspito and Rigali (60) extracted thorium from natural waters with Aliquat-336. The organic phase is then extracted with acid; the acidic solution is treated with arsenazo-I11 solution; and the absorbance is measured at 665 nm. Standard deviations for 0.45-4.75 pg/L thorium ranged from 0.048 to 0.126. A method is described by Hodge, Seidel, and GoldbeTg (140) to determine inorganic and organic tin compounds in natural waters. The compounds described in the publication react with sodium borohydride to produce volatile hydrides which are separated on the basis of their differing boiling points. They are then measured by atomic absorption spectrometry. Detection limits range from 0.4 ng for stannic tin to 2 ng for tributylstannic chloride. Nakashima (260) determined tin from water and seawater by hydride generation and atomic absorption spectrometry after preconcentration. Tin is coprecipitated from a liter of sample with ferric chloride. The precipitate is then separated by flotation using sodium dodecyl sulfate and air and then dissolved in acid, and then tin is determined. An automated method for the determination of tin in water is reported by P en and Fishman (330). Dissolved tin is reacted with sodium orohydride and the tin hydride is determined by atomic absorption spectrometry. Twenty samples per hour can be analyzed; the detection limit is 1 pg/L tin. EDTA is used to mask interferences from copper, nickel, antimony, and arsenic. Tominaga and Umezaki (390) determined tin in wastewaters by atomic absorption spectrometry with electrothermal atomization. Ascorbic acid is added to the graphite furnace tube to suppress interferences from other ions. Blunden and Chapman (20) extracted triphenyltin compounds from natural water and seawater into toluene with 3-hydroxyflavone. The complex is then determined spectrofluorimetrically at 495 nm, using an excitation wavelength of 415 nm. Concentration of tin between 0.004 and 2.0 ppm is determined with average recoverles of 74-93.6% and wlth relative standard deviations of 4.2-11.9%. A gas chromatographic method was developed by Simon, Welebir, and Aldridge (370) for the determination of tin in water. A hydrogen-rich flame ionization detector, that was both sensitive and selective in the lower nanogram range for tin compounds, was modified to make it applicable to the determination of trace amounts of tetrabutyltin and tributylstannic chloride, Gifford and Bruckenstein (100) used gas chromatography with a gold gas- orous electrode detector to determine tin in water. The hychde was generated with
b'
WATER ANALYSIS
sodium borohydride and tlhen swept onto a Porapak Q Column and analyzed. The detection limit for a 5-mL sample is 0.8 ppb tin. The determination of tin by laser-excited atomic fluorescence spectrometry was studied by Epstein et al. (70) for the determination of tin in river water. Direct-line tin fluorescence at 317.5 and 380.1 nm is excited a t 300.9 nm in a nitrogen. separated air-acetylene flame. A method to concentrate organic tin from water was reported by Chin (50). The sample is passed through a column containing GDX-502 porous powder beads. The column is rinsed with ascorbic acid solution, the pH was adjusted to between 1 and 2 with 10 N sulfuric acid; organic tin was then desorbed with anhydrous ethanol. Cyclic and stripping voltammetry of tin at mercury hanging drop and film electrodes in acidic o-diphenol media in the presence of lead and cadmium was investigated b? Glodowski and Kublik (110). Stannous tin at the 1 X 10 mol/L level was detected in water samples in the presence of 5-fold amounts of lead and cadmium. Rigin and Rigina (36D) determined tungsten in water by atomic fluorescence spectrometry at 400.9 nm. The sample is evaporated under an infrared lamp and chlorinated with thionyl chloride at 553 K in a quartz Carius tube. Atomization is achieved a t 1100 K in a 5:l hydrogen:helium stream in a quartz reactor. The detection limit is 0.8 ng. Optimum conditions for the kinetic determination of tungsten in mine water based on the Landolt reaction in the hydrogen peroxide-iodide-ascorbic acid system are described by Voevutskaya, Pavlova, and Pilipenko (410). A study was made by Hal1 (120)to determine the stability of uranium in waters collected from various geological environments in Canada. Conventional fluorimetry and laserinduced fluorescence was used. Results showed that uranium was stable in all waters tested; preservatives were not needed. A method for the determination of uranium in natural waters based on preconcentration of uranium on activated carbon, irradiation with epithermal neutrons, and measurement by hi h resolution y spectrometry of neptunium-239 was Kuleff and Kostadinov (210). The limit of discussed g/L. Hirose and Ishii (130) predetection was 1.4 X concentrated uranium from seawater on Chelex 100 prior to determination by neutron activation analysis. The y-ray spectrum is measured with a Ge(Li) detector. Results of a single-laboratory evaluation and an interlaboratory collaborative study of a method for determining uranium in water are reported by Bishop, Casella, and Glosby ( 1 0 )and Casella, Bishop. and Glosby (40). Uranium is corecipitated with ferric hydroxide; uranium is then separated y anion-exchange chromatography and electrodeposition, followed by a pulse-height analysis. The fission track registration technique using Makrofol KG as a detector was developed by Gerald0 et al. (9D) for determining uranium in water. Uranium concentration between 0.4 and 8.0 bg/L can be determined. Campen and Baechmann (30) applied laser-induced fluorescence for determining uranium concentrations in water when the number of samples is very large (as in ore prospecting). Possible interferences by anions and cations present in natural water are discussed. McElhaney et al. (220)used a fluorometer for determinin uranium in water. Uranium is isolated from potentia7 quenching ions and concentrated by extraction with tri-noctylphosphine oxide in Varsol. A portion of the extract is placed on a sodium fluoride pellet, which is then dried, sintered, and cooled, and the fluorescence measured. The lower limit of detection is 0.20 p r /L. Putral and Schwochau (320) reported that silica gel can used to separate and concentrate uranium from seawater. TJranium is eluted with nitric acid and determined fluorimetrically in the range of 0.1-10 pg/L. To determine uranium in water, McHugh (230) developed a portable field kit. Forty-six samples can be processed in a day. A sample is evaporated to dryness, ignited, and fluxed. Uranium is then determined fluorimetrically; less than 0.2 ppb uranium is detected. The effect of surfactants, condensed phosphates, soap, NTA, citric acid, C8-Clo trialkylamines, and EDTA on the fluorimetric determination of uranium was studied by Pakalns and Lane (290). Reinhardt and Mueller (350) determined uranium in freshwater and seawater spectrophotometrically with Arsenazo
6,
%
k
I11 a t 665 nm. Uranium is co recipitated with aluminum phosphate at pH 6 and reduce to uranium(1V) with zinc in a hydrochloric acid medium in the presence of chromic acid, prior to forming the uranium-arsenazo complex. Keil(170) extracted uranium from natural water with triphenylarsine oxide in chloroform, and back-extracted the uranium with perchloric acid, before determining uranium with Arsenazo 111. Williams and Gillam (420) used titanium oxide as a collector in the separation of uranium from synthetic seawater by absorbin colloid flotation. Surfactant was added, foam was collected and dissolved in acid, and uranium determined spectrophotometrically by using Rhodamine B. A spectrochemical method was reported by Koval’chuk, Koryukova, and Andrianov (190) for determining uranium in seawater. Uranium was adsorbed on hydrated titanium oxide by thermal hydrolysis of metatitanic acid. The condensate was mixed 1:l with powdered carbon and uranium determined spectrogra hically. Ferguson et al. ( 8 0 )8veloped a method to rapidly analyze natural water samples for uranium using a custom-build thermal-emission mass spectrometer. Good agreement in results, compared to those obtained by fluorimetric analysis is obtained in the range 200-1000 ng/L. Hu and Gao (150) determined vanadium in water spectrophotometrically with 5-bromo-2-(2-pyridylazo)-5-diethylaminophenol. After color development and dilution, the absorbance of the solution is measured at 605 nm. If an organic extractant is used, the absorbance is measured at 620 nm. Iron(II1) interference is inhibited with sodium fluoride. Kimura et al. (180) described a spectrophotometric procedure using Arsenazo I11 for determining zirconium in water. Recovery of zirconium in the concentration step with TTA is monitored by the addition of zirconium-95. Zirconium found in natural waters ranged from 0.39 to 2.8 pg/L.
B
MERCURY A number of investigators have used, compared, or modified the cold-vapor atomic absorption s ectrometric technique for determining mercury in water an sediment. Agemian and DaSilva (1E) used acid-dichromate and UV digestion sequentially in an automated system to extract mercury from particulate matter and oxidize organomercurials in brine waters and sediments. Mercury is then reduced with stannous ion. Thiry samples per hour can be analyzed. The detection limit is 0.02 pg/L. Four cold-vapor techniques were compared by Lutze (19E). A dual-bubbler apparatus was the most rapid and sensitive method. Yamamoto, Kumamaru, and Shiraki (3923) compared sodium borohydride tablets and stannous chloride solutions for reduction of mercury. Sodium borohydride tablets are preferred and give more precise results. Two procedures for determination of total mercury based on the cold-vapor technique with and without a preconcentration step are presented by Aliseda et al. (2E). Results of an interlaboratory test involving 22 laboratories are reported. At 0.75 pg/L, the relative standard deviation for repeatability ranged from 3.8 to 10.9%, and the relative standard deviation for reproducibility ranged from 7.2 to 29.4% for the different methods. Bouzanne, Sire, and Voinovitch (3E) determined mercury after fixation of the mercury vapor on silver wool or activated carbon. The amalgam formed is thermally decomposed and carried by a gas into the measuring cell. At 4 ng/L, relative standard deviation is 6.8%. Once fixed on the silver wool, the mercury will remain stable for more than 15 days. Shiraishi and Kuroda (33E) determined mercury in seawater after collection of mercury on gold. Howard and Arbab-Zavar (13E)collected inorganic and methyl mercury on dithizonecoated polystyrene beads prior to analysis. Mizunuma et al. (26E)selectively determined inorganic mercury and organic mercury compounds. The method is based on selective reduction of inorganic mercury with sodium borohydride in an alkaline solution and on decorn osition and reduction of both inorganic and organic mercury f y a mixture of ferric iron and sodium borohydride in an acidified solution. Organic mercury is determined by difference. Approximately 0.2-8 ppb mercury can be determined with a relative standard deviation of 2% at 5 ppb. Yu, Liu, and Wang (40E) used sulfhydryl cotton to concentrate and collect inorganic and organic mercury compounds. Organic mercury is removed from the cotton with 2 N hydrochloric acid, and inorganic mercury is removed with
x
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
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WATER ANALYSIS
6 N hydrochloric acid saturated with sodium chloride. With a 1-L sample, the sensitivity is 0.003 ppb. Hsu and Tsai (14E) determined methyl mercury in water by extraction with benzene, sorption with a 3:4:10 cysteine-sodium phosphatesodium acetate mixture, elution with 1% sodium chloride solution and 50% sulfuric acid solution, and evaporation of the mercury by blowing air into the eluate to which stannous chloride and sodium chloride have been added. Egawa and Tajima (8E)determined methyl mercury after adsorption on synthesized macroreticular chelating resin containing episulfide groups. Elution with 4 N hydrochloric acid effectively separated methyl mercury from inorganic mercury and other contaminants. Minagawa, Takizawa, and Kifune (25E) collected inorganic and organic mercury in freshwaters simultaneously on a column of a dithiocarbamate-treated resin. The mercury was eluted with a slightly acidic aqueous thiourea solution. Stannous chloride is then used to generate mercury vapor. The range of the method for a 20-L sample is 0.2-5000 ng/L. A field method for preconcentration of mercury from natural waters onto gold was presented by Bricker (4E). Mercury was then determined by using a helium-dc plasma emission spectrometry system, set on the 253.7-nm mercury line. Wrembel (38E)determined mercury in water by ringdischarge emission spectrometry. Mercury is excited under reduced pressure (0.1torr) in a high-frequency electromagnetic field. The detection limit is 0.1 ng/L. Chemical models of freshwater and seawater were used by Millward and Le Bihan (24E) to examine the effect of humic material on the determination of mercury by flameless atomic absorption spectrometry. Chan and Ni (5E) reported on the use of graphite furnace-atomic absorption spectrometry for determining mercury. Gold, platinum, or palladium is added to the solution to stabilize the mercury and to raise the pyrolyzing temperature to 250, 300, or 500 "C, respectively, as a result of the formation of stable amalgams. The authors state that for a solution containing 0.1 pg/mL mercury and 20 pg/mL palladium, there are no significant interferences from most other ions. Slovak and Docekalova (34E)also reported that sample stabilization during the drying step is important for the determination of mercury by electrothermal-atomic absorption spectrometry. The use of a selective ion exchanger with thiol groups solves the problems of sample storage, separation, and stabilization. A method for preconcentration of mercury and methylmercury ions in water by batch methods using activated carbon and determination of mercury enriched on activated carbon by Zeeman effect atomic absorption spectrometry is described by Matsueda (23E). The detection limit is 0.5 ng on 10 mg of activated carbon. Rigin (30E)used nondispersive atomic fluorescence for the determination of mercury in natural water. The method is based on the electrolytic isolation of mercury as an amalgam on a gold cathode, conversion of the mercury from the amalgam into the gas phase by heating, and electrothermal atomization of mercury in the gas phase in a helium atmosphere. The limit of detection is 0.7 pg. Farey, Nelson, and Rolph (1OE)described a rapid technique to break down organic mercury compounds in natural waters. The compounds are treated with potassium bromate-potassium bromide in h drochloric acid; the bromine generated cleaved aryl- and a&ylmercury bonds. Determination is completed by atomic fluorescence spectrometry. To determine mercury in water by activation analysis, Nagatsuka and Tanizaki (27E) examined a simple preconcentration procedure. Mercury, as pyrrolidinedithiocarbamate at pH 6-8, is adsorbed on activated carbon powder. The powder, after adsorbing mercury, is filtered, dried, and analyzed. The limit of detection is 0.01 ppb mercury. Neutron activation analysis procedures without enrichment are described by Khakimov, Kutbedinov, and Abdullaeva (16E) and Jensen and Carlsen (15E). A review of gas chromato raphic methods for the determination of organomercury(I5) compounds in environmental matrices was presented by Rodriguez-Vas uez (31E). Determination of inorganic species can be male through their conversion to organomercury(I1) compounds. General considerations reviewed include thermal stability of the compounds and specifications for columns and detectors. Chemical and instrumental problems associated with various gas 190 R
ANALYTICAL CHEMISTRY, VOL. 53, NO.
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chromato raphic methods are delineated. Wang (37E) collected an concentrated methylmercury from water on sulfhydryl cotton fiber. The methylmercury is then extracted from the cotton with benzene and concentration determined by gas chromatography. MacCrehan, Durst, and Bellama (21E) studied organometal speciation in water using liquid chromatography with electrochemical detection. A column preconcentration procedure for methyl- and ethylmercury is outlined. A simple spectrophotometric procedure was described by Ueno et al. (35E) for the determination of 0.05-0.25 pg of mercury with solubilized cupric dithizonate. The sample was mixed with cupric dithizonate containing Triton X-100 at pH 1. After 5 min dual-wavelen h photometry is used to measure the absorbance a t 507 and@493 nm. The difference in absorbance readings is proportional to the mercury concentration. Silver and ferric iron interferences are masked by chloride and fluoride, respectively. Madej et al. (21E) used dithizone in carbon tetrachloride to determine mercury in water. Silver interferes but the interference is removed by reextractin the silver ion from carbon tetrachloride with an acidified so%um chloride solution. Podchainova, Barbina, and Dubinina (29E) studied the complex formation between mercuric ion and 1,3-diphenyl-5-(1-phthalaziny1)formaan and applied this approach to the determination of mercury in natural waters. Beer's law is obeyed between 0 and 2.5 pg/L. An indirect kinetic method is suggested by Rychkova and Dolmanova (32E) for mercury in water by using the exchange reaction between mercury and copper diethyldithiocarbamate, followed by the determination of the substituted copper by the catalytic oxidation of hydroquinone with hydrogen peroxide. Wang, Li, and Chang (36E) determined mercury in water by pulse-stripping polarography using a carbon anode and a silver-silver chloride reference electrode. A 1 M potassium thiocyanate-0.002 M nitric acid solution is used as the electrolyte. The mercury is deposited at the anode at -1.2 to -1.4 V and is stripped at -0.8 V. Mercury concentrations of 1 X to 1 X 10-l' g/mL are determined. Kritsotakis, Laskowski, and Tobschall (17E) used a glassy carbon electrode to determine as little as 1.5 ppb mercury in river water by differential-pulse anodic stripping voltammetry. The supporting electrolyte contained 0.1 M potassium thiocyanate, 0.025 N hydrochloric acid, and 20 ng/mL of copper. Optimum pH is 2.8, and the optimum deposition potential is -1.0 V. Pneumatoamperometry was used by Gifford and Bruckenstein (11E)to determine mercury in water. Mercury was chemically generated and flushed from the system and passed over a hydrophobic gas- orous electrode by nitrogen gas. Mercury was electrolyze a t constant potential, which gave a response proportional to the initial concentration. The detection limit is 5 ppb. Cragin (6E)re orted that the rate of mercury contamination is dramatic$ly increased, when oxidizing agents such as nitric acid or potassium permanganate are added to water samples as preservatives. He reported that freezing samples in plastic containers is an effective way to prevent contamination; or, when freezing is not practical, storage in glass containers minimizes contamination. To prevent adsorption of mercury on container walls when collecting seawater samples, Matsunaga, Konishi, and Nishimura (22E) acidify the samples to 0.2 M with sulfuric acid. Mercury is stable for a t least 60 days. Glass bottles are recommended. Heiden and Aikens (12E) stated that pretreatment of polyolefin bottles by leaching the interior with chloroform, followed by exposure to the vapors of aqua regia, is superior to chemical preservatives in reducing mercury losses from 1 pb mercuric ion solutions. Liu and Huang (18E) reporte that river water samples containing 50 pg/L of mercury in the presence of 5% nitric acid and 0.05% potassium dichromate are stable for 20 days. The bromate-bromide technique for decomposition of organomercury com ounds in natural water for total mercury determination is 8scussed by Farey and Nelson (9E). Seawater samples spiked with 8.3 pg/L of methylmercury gave mercury recovery greater than 96 % . Nelson (BE)also stated that the brominating solution is a suitable absorbing medium for preconcentration of mercury from natural waters. Duerr, Oliver, and Winkler (7E) reported on mercury results from an International Standard Organization interlaboratory
d
B
B
WATER ANALYSIS
comparison study. The study demonstrated that results depended on explicity of the method; it emphasized the importance of clear and extensive method specification.
ANTIMONY, ARSENIC, SELENIUM, AND TELLURIUM Trace amounts of antimony in natural waters were determined by Piccardi and Udisti (21F) by alternating current stripping voltammetry with a hanging mercury drop electrode. By use of 1 M hydrochloric acid electrolyte, there was sufficient separation of thie antimony peak from the bismuth peak. A preliminary oxidation step was necessary to obain reproducible results. Odanaka, Matano, and Got0 (2OF) discussed the determination of inorganic and methylated arsenicals in water and other environmental rnaterials by graphite furnace atomic absorption spectrometry Enhancement and depression effeckq of various coexisting chemical substances are also discussed. Dimethylarsinic acid, iniethylarsonic acid disodium salt, arsenite, and arsenate eachL gave different sensitivities. Addition of alkali or alkaline earth salts and bases enhanced the sensitivities. Sodium hydroxide and nickel nitrate are used in the determination of arsenicals in river water. Graphite furnace atomic absorption and chromatographic techniques were used by Iverson et 511. (118')for arsenic speciation in river and pore water and sediments. Matrix modification was accomplished with nickel nitrate. Detection limit is 2 pg/L. Speciation is accomplishled by ion-exchangechromatography using AG 50W-X8 cation resin. The determination of nanogram amounts of total arsenic, as well as its speciation in natural waters by graphite furnace atomic absorption spectrometry, was carried out by Shaikh and Tallman (28F). Various arsenic s ecies were reduced to their hydrides, collected in a l i q u i l nitrqgen cold trap, and then selectively vaporized and swept into the sample port of the graphite furnace. Yanagi (3%') reported on the determination of arsenic in natural water by atomic absorption spectrometry. A peristaltic pump is used to pass sodium borohydride solution through the reaction vessel. The arsine formed is swept by hydrogen, which is also evolved at the same time, into a liquid-nitrogen trap prior to measurement. An atomic fluorescerilce method was developed by Rigin (24F) for the determination of arsenic in natural waters by electrochemical reduction to arsine and atomization of the latter. The limit of detection is 0.015 n Studies are presented by Fry et al. ( 6 8 describing an improved application of tlhe sodium borohydride reduction of soluble arsenite to form arsine, as a preconcentrationapproach for ultratrace level arcjenic determination by inductively coupled plasma optical emission spectrometry. Specialized analyte introduction techniques are described for elimination of hydrogen, water vapor, and carbon dioxide byproducts that would normally extinguish a medium-power plasma discharge. The method is applied to the determination of as little as 0.03 ng mL arsenic. henry, Kirch, and Thorpe ( I O F ) achieved speciation of arsenic(III), arsenic(V), and total inorganic arsenic by differential pulse polarography. Arsenic(II1) is determined directly in 1 M perchloric acid or 1 M hydrochloric acid. Total inorganic arsenic is determined after reduction to arsenic(II1) with a boiling solution of sodium bisulfite. Arsenic(V) is determined by difference. The detection limit for total arsenic using hydrochloric acid is 7 ppb. Interferences are also discussed. Chen and Tsui (2F) used anodic-stripping voltammetry to determine arsenic in natural water. Arsenic is electrolyzed in an approximate 1.1 I\[ nitric acid medium on to a gold anode. The stripping potential is from -0.2 to -0.3 V for dissolution. For water samples containing 20-30 pg/L arsenic, the stripping of arsenic is from 94% to 100% complete. Lu, Hsieh, and Tseng (15F) also described an anodic-stripping voltammetric method which uses a gold anode to determine as little as 0.001 ppb arsenic. Sulfuric acid is used as the electrolyte. Pneumatoamperometry was used by Gifford and Bruckenstein ( 7 0 to determine arsenic in water. Arsine was chemically enerated and flushed from the system and over a hydrophohc gas-porous electrode by nitrogen gas. Arsine was then electrolyzed a t constant potential, which gave a
.
response proportional to the initial concentration of constituent. The detection limit is 3 ppb. Cox and Cheng (4F)and Chen ( 3 0 used Donnan dialysis to transfer arsenate from a water sample into an electrolyte solution for determination of the arsenic by cathodic-stripping voltammetry. The method was tested by using lake water and wastewater samples. Results obtained were statistically equivalentto those obtained by accepted analytical procedures for trace-level determinations. An enzyme-catalyzedmethod for the determination of arsenic in water is described by Goode and Matthews (SF). Glyceraldehyde 3-phosphatedehydrogenase is used to perform an oxidative arsenolysis of D-glyceraldehyde3-phosphate. The rate of reaction, as measured by fluorescence, is first order in arsenic(V). A linear calibration plot is achieved for the range 0.02-2 pg/mL of arsenic. The interference of cobalt(II), chromium(VI), copper(II), mercury(II), molybdenum(VI), nickel(II),and antimony(II1) in the determination of arsenic by the silver-diethyldithiocarbamate method was investigated by Sandhu (26F) and Sandhu and Nelson (27F). To eliminate these interferences and to concentrate arsenic in water, the sampales were digested with potassium permanganate, and eluted through Amberlite IRA-40 IS exchange resin. Arsenic was extracted from the resin with hydrochloric acid and determined colorimetrically. Kaneko (14Fj coprecipitated arsenic with ferric hydroxide to determine ppb levels in well water. Both arsenic(II1) and arsenic(V) are completely coprecipitated at pH 3.5-10.0. Average recovery is 98%. A method is described by Cutter (5F) for the determination of selenite, selenate, dimethyl selenide, and dimethyl diselenide in natural waters. Detection limits are in the ppt range. Volatile methyl species are removed from the sample with a stri ping gas, collected in a liquid nitrogen trap, and separated y gas chromatography. Inorganic species are reduced to their hydrides, stripped from the sample, and then collected in a liquid nitrogen trap. All species are determine by atomic absorption spectrometry using a quartz tube furnace. A fluorimetric procedure is presented by Nazarenko and Kislova (19F)for the determination of selenites, selenates, and organoselenium compounds in waters by using 2,3-diaminonaphthalene. Limit of detection is 0.01 pg/L. The relative standard deviation is 0.23% for 0.05-1.00 pg/L of selenium and 0.048% for 50-500 pg/L. Pyen and Fishman (22F) evaluated an automated method to determine both inorganic and organic forms of selenium in water. Organic selenium-containing compounds are first manually decomposed by hydrochloric acid-potassium persulfate di estion. The selenium liberated from these compounds, a ong with inorganic selenium ori inally present, is reduced to selenite with stannous chlorite and potassium iodide, and then to hydrogen selenide with sodium borohydride. Hydrogen selenide is stripped from the solution with the aid of nitrogen and is then decomposed in a tube furnace heated to 800 "C, which is placed in the optical path of an atomic absorption spectrometer. Thirty samples per hour can be analyzed to levels of 1 pg/L. Robberecht and Van Grieken (25F) reported that selenite and selenate in various environmental waters can be determined by energy-dispersiveX-ray fluorescence after preconcentration of elemental selenium on activated carbon. Selenite is reduced to elemental selenium with L-ascorbic acid. Selenite plus selenate is determined after refluxing the Sam les with thiourea in sulfuric acid medium and subsequent alsorption of the elemental form. Selenate is determined by difference. The limit of detection is 50 ng/L for selenite and 60 ng/L for total selenium. Shchukin and Kozirod (29F) determined trace amounts of selenium in mine waters. The method is based on the extraction of selenium o-phenylenediamine complex into toluene, and direct polarographic analysis of the organic extract with a supporting electrolyte of 0.1 N ammonium hydroxide or ammonium perchlorate. Shimoishi and Toei (30F) described a gas chromato raphic method for the determination of selenite and total segenium in natural waters. Selenite reacts with 1,2-diamino-3,5-dibromobenzene to form 4,6-dibromopiazselenol which is extracted into toluene prior to injection into a gas chromato-
E
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
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WATER ANALYSIS
graph. A reduction step is necessary to determine total selenium; as little as 2 ng/L can be detected. Tzeng and Zeitlin (31F) reported that colloid adsorption and flotation can be applied successfully to the separation of selenite from seawater; separation is achieved in 5 min. Recovery of selenium from spiked seawater samples is 100 f 10%. Selenium is then determined by a catalytic-spectrophotometric method. The stability of inorganic selenium species in water at concentrations of 1 and 10 pg/L was studied by Cheam and Agemian (IF) under various conditions of pH, type of water, and type of container. Polyethylene containers and adjustment of the sample to pH 1.5 provided optimum preservation up to 125 days. Flotation and atomic absorption spectrometric determination of selenium(1V) and arsenic(II1) in natural waters is discussed by Nakashima (17F, 18F). The constituents are coprecipitated with ferric hydroxide at specified pHs and floated with air bubbles, using sodium lauryl sulfate for selenium and sodium oleate for arsenic. The hydrides are then formed with sodium borohydride and measured. The selective extraction of tellurium(1V) or selenium(1V) and differential determination of tellurium(1V) and tellurium(V1) or selenium(1V) and selenium(V1)using sodium diethyldithiocarbamate,ammonium pyrrolidinedithiocarbamate, and dithizone in organic solvents and subsequent flameless atomic absorption spectrometry was studied by Kamada, Shiraishi, and Yamamoto (12F) and Kamada, Sugita, and Yamamoto (13F). The sensitivity for tellurium was 0.3 ng/ mL, with a 2% relative standard deviation for 80 ng/mL. For selenium, the sensitivity was 0.4 ng/mL, with a 3% relative standard deviation. Gifford and Bruckenstein (8F)used gas chromatography to determine arsenic(III),antimony(III), and tin(I1) in water. The hydrides are generated with sodium borohydride and swept from solution onto a Porapak Q column, where they are separated and detected at a gold-porous electrode by measurement of the respective electrooxidation currents. Detection limits for 5-mL samples were: arsenic, 0.2 ppb; antimony, 0.2 ppb; and tin, 0.8 ppb. An automated microprocessor-controlled atomic absorption spectrometer was constructed by Morrow, Futrell, and Adams (16F) from commercially available optical components and an in-house-fabricated programmed microprocessor for the determination of arsenic and selenium in natural waters. Optimization of the determination of arsenic and selenium in water by reduction with sodium borohydride and atomic absorption spectrometry, using a low-cost quartz tube, is discussed b Reichert and Gruber (23F). Preliminary reduction, hy$ide generator geometry, carrier gas flow rate, and temperature of atomization were studied.
BORON, PHOSPHORUS, AND SILICA Cox and Cheng (5G)and Cheng (3G)discussed a procedure in which Donnan dialysis is used to transfer orthophosphate from natural water samples into a controlled electrolyte prior to determination by cathodic stripping voltammetr . The results obtained are statistically equivalent to those ogtained by accepted analytical procedures for concentrations210 ppb. A gas chromatographic rocedure was developed b Hanson (9G)to measure orthop osphate in aqueous samp es with a flame ionization detector. The primary advantage of this technique is the small volume of sample required. An automated procedure for determining low-reactive phosphorus concentrations in natural waters in the presence of arsenic, silica, and mercuric chloride was discussed by Downes (6G). Thiosulfate in acid solution removed interferences from arsenate and mercuric chloride. Lennox (13G) described another method for measuring dissolved orthophosphate and total phosphorus in freshwater and organicwaste streams. Total phosphorus compounds are converted to orthophosphate by persulfate digestion; the detection limit for the automated, colorimetric step is 1 pg/L. T q a k a , Hiiro, and Kawahara (18G) determined orthophosphate in water by reacting it with an anion exchange resin in the molybdate from and reducing the molybdophosphate formed by traditional reactions to a blue color. Different concentration ran es can be measured by varying the amount of sample a d d e l t o the resin. Procedures were studied by Gales and Booth (8G) and
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
Jeffries et al. (10G)for digesting total phosphorus compounds in water. In the former, a block digestor and a K'eldahl digestion mixture were used. After digestion, both total phosphorus and total Kjeldahl nitrogen were measured in the 0.1-20 m /L ran e. In the latter procedure, an autoclavepromotef persulkte digestion was applied to samples containing low concentrations of total phosphorus. Recovery studies showed that this technique is suitable for all samples, except for those containing high levels of suspended solids. The spectrophotometric determination of boron in natural waters after specific adsorption on Sephadex G-25 gel was described by Yoshimura, Kariya, and Tarutani (19G). After desorption, the boron was determined spectrophotometrically by the azomethine H method. Interfering cations were removed by the addition of EDTA. Two automated, azomethine H procedures for determinin boron in water were developed by Spencer and Erdmann &6G) and Edwards (7G). The analytical ranges were 0.01-0.40 mg/L and 0.1-4.0 mg/L, respectively. Recoveries, interfering substances, and rate of analyses were presented. Chang et al. (2G)described a curcumin procedure for determinin boron in natural and wastewaters. The reaction is carriecf out in a sulfuric acid-glacial acetic acid medium containing sodium fluoride to prevent interferences from other ions. An additional curcumin procedure was studied b Choi and Chen (4G)that eliminates interferences from harcieners, fluoride, or nitrate. Korena a, Motomizu, and Toei (1IG) determined boron in naturaf waters by complexation with chromotropicacid in the presence of zephiramine and EDTA. The complex is extracted with 1,2-dichloroethane and the absorbance of the organic phase measured at 351 nm. A selective spectrophotometric method for determining boron in water was developed by Kuwada, Motomizu, and Toei (12G). After evaporation of the sample to dryness, 2,4-dinitro-178-naphthalenediol was added to form a complex anion with boron that was extracted into toluene with Brilliant Green. The absorbance of the resultin ion pair was measured at 637 nm; approximately 0.5 p b of 6oron was determined. Ball, Thompson, and Jenne 8 G ) used a dc argon-plasma emission spectrometerto determine dissolved boron in natural waters. Concentrationrange was 0.02-250 mg/L, with a linear analytical range from 0.02 to 1000 mg/L. The determination of boron in natural waters by atomic absor tion spectrometry with electrothermal atomization is descriled by Szydlowski (17G). Barium is added to increase the sensitivity; the recommended boron concentration range is 0-600 ng L. A method is described by Simmons (15G) for t e determination of particulate silica in water. After preliminary steps, the sample is analyzed by atomic absorption spectrometry using a nitrous oxide-acetylene flame. The reproducibility is *5% with a recovery of 90-95%. A method for determining trace concentrations of silica in industrial process waters by flameless atomic absorption Spectrometry is outlined by Rawa and Henn (14G). Calcium and lanthanum are added to enhance sensitivity and minimize interferences, respectively. The detection limit is 2.5 pg/L silicon dioxide with a relative standard deviation of 6.1% at the 25 pg/L level.
k
SULFATE, SULFITE, SULFIDE, AND OTHER SULFUR COMPOUNDS A spectro hotometric method is described by Utsumi, Oinuma, an8Isozaki (18H) for determining trace amounts of sulfate based on formation of the barium-dimethylsulfonazo com lex. A similar procedure is discussed ,by Rei'nders, Van S t a g n , and Griepink (15H) for determining sulfate. Analytical results of pure sulfate solutions containing 1-60 pmol/L are presented. Chloride, nitrate, and qhosphate do not interfere below concentrations of 2 X 10- , 3 X low2,and 1.5 X mol/L, respectively. Murakami et al. (IOH) increased the sensitivity of the barium chloranilate procedure by the use of Chromazurol S. After removal of barium sulfate by filtration, the chloranilate ion reacts with F e ( ~ h e n ) ~The ~+. chloranilate in the resultin com lex is uantitatively replaced comdex, and its absorbance by CAS to form a CAS-Fe!phen[ is measured at 600 nm. A sulfate method, based on the formation of insoluble 2perimidinylammonium sulfate by reaction of sulfate with 2-perimidinylammonium bromide on a glass fiber substrate, is outlined by Dasgupta, Hanley, and West (6H). The colored complex is monitored in acidic solution at 420 nm or in basic
WATER ANALYSIS
solution at 550 nm. No pretreatment is required, and, for a 1oO-pL aliquot, the sensitivity is 1ppm, and the working range extends to 2500 ppm. Cronan (5H)used ultraviolet irradiation followed by an automated, methythymol blue procedure to determine sulfate in colored natural water samples more accurately. The technique yields a relative precision of 1.6% at a sulfate concentration of 50 pequiv/L. Several articles by 16H) discuss Reijnders, Vanestaden,and Griepink (12H-14H, the determination of sul!fate in water samples by using various flowthrough systems with dimethylsulfonazo(II1) as an indicator. Comparisonsi between segmented flow-injection analysis, flowthroughtitirimetry, and several other procedures are included. Indirect determination of sulfate in brines by atomic absorption spectro hotometry is presented by Couto and Curtius (4H). Two mo1ifications to existing methodology are proosed: one applies to the standard addition method for Earium measurements using a Y-shaped capillary aspirator; the other uses prior separation of sulfate from other ions on aluminum oxide. Howarth (7H) outlined an indirect titration method for determining sulfate in seawater, estuarine waters, and sediment-pore waters. EDTA is used to dissolve barium sulfate, and the excesg EDTA is titrated with magnesium chloride solution. Interferences from chloride, iron, and phosphate are negligible. The determination of dissolved sulfate in seawater and natural brines by precipitation with radioactive 133Ba,and countin of the precipitate on a scintillation counter was studied y Rosenbauer and Bischoff (1723. The analytical rwge for a 1.0-mL sample was 0.5-3000 mqL. akalns and Farrar (21H) investigated the effect of nine surfactants on the turbidimetric and titrimetric determination of sulfate in water. The titrimetric procedure can generally tolerate higher concentrations of surfactants and is reconimended for solutions containing anionic and nonionic detergents, tripolyphospliate, or soap. Bruno et al. (2H) discussed the determination of sulfite in water. Accurate and reproducible results were obtained by titrating sulfite with cerium(1V) solution without catalysts. A method is described by Ingvorsen and Joergensen (9M) for the determination of oxygen and sulfide in the same sample. The sulfide is first separated by precipitation with zinc hydroxide, and the oxygen is determined by the Winkler technique on the supernatant. The sulfide is determined either spectrophotometrically or by iodine titration. Chakraborti and Adams (3H) described a procedure for potentiometric determination of sulfur in waters with a cadmium sulfide membrane electrode. After reduction of sulfur compounds and absorption, tlhe sulfide is titrated with lead nitrate solution and the equivalence point is determined potentiometrically. A microcoulometric procedure for determinin total inorganic and organic sulfur is presented by Brull and Golden ( I H ) . These compounds are converted to sulfur dioxide which is titrated inicrocoulometrically. The limit of detection is approximately 0.1 ppm based on a 25-pL sample. The only interference arises from greater than 100 ppm halogen. Hu (8") used differential pulse olarogra hy for determining carbon disulfide in water at tEe 1pg/L evel. A linear relation was observed far 0.8-3.2 pg/L carbon disulfide.
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HALIDES The determination of chloride and bromide in natural waters and brines by X-ray fluorescence is discussed by Sichere, Casbron, and Zu pi (191). Bromide concentrations of 0.6-120 mg/L can be (Petermineddirectly in liquids, with selenium as an internal !standard, Chloride can be measured directly in the 0.6-120 mg/L range, with barium added to minimize interferences friom carbonate and sulfate. Marshall and Midgley (90 presented a method using a solid-state mercury(1) chloride electirode for determining 0.01-1.0 mg/L levels of chloride in boiler water. Interference from ferric ion is eliminated by the addition of fluoride. Another electrode procedure by Marshall and Midgley (100 was designed to determine chloride at the 0-20 pg L level. The HgCl electrodes were housed in a flow cel with a thermostatically controlled water jacket. A computer-controlled multichannelcontinuous-flowsystem for the spectrophotometric determination of nitrate, chloride, and ammonium ions in s n d samples of rainwater is described
i
by Slanina et al. (201). The analytical range is 0.2-20 ppm for the three ions and the Sam ling rate is 18-35 per hour. A spectrophotometric proce ure for determining trace amounts of chloride in boiler water containing corrosion products (copper or iron) was presented by Mor, Beccarla, and Poggi (111). Released iodate was measured with a precision of i 1 0 % following the reaction between chloride and silver or mercuric iodate. An isotachophoretic technique for determining low concentrations of chloride in water is outlined by Ryslavy et al. (181). This technique is based on simultaneous pumping of the leading electrolyte and the sample into the isotachophoretic column; a diagram of the apparatus is given. Kokubu, Kobayasi, and Yamasaki (61) used zirconiumloaded cation exchange columns to concentrate low-level fluoride ions in natural water samples. After elution, fluoride is determined with an ion-selective electrode. Aluminum interferes, but submillimolarquantities can be masked by the addition of CyDTA or citrates. Fluoride procedures involving the use of sulphonated alizarin fluorine blue, alizarin fluorine blue, and the fluoride electrode were compared by Deane et al. (21). These methods were evaluated with res ect to interfering substances, sensitivity, range, re roduci ility, rate of complex formation, and stability of co ors formed. Hashitani, Yoshida, and Adachi (51) determined fluoride by both a La(II1)-Alizarin Complexone spectrophotometric method and an ion-selective electrode procedure. In both cases, acetyl acetone is added to the sample solution to remove the interference from aluminum. A flotation-photometric procedure is described by Rudenko and Popov (171) for determining fluoride in water. Anionic rare earth metal-Alizarine Complexone-F complexes are separated by flotation with toluene; the organic suspension is dissolved in ethanol; and the absorbance of the resultin solution is measured a t 575 nm. Burguera, Townshend, an Bogdanski (14discussed an indirect procedure for determining fluoride in water. Fluoride is converted to silicon tetrafluoride, and this product is transported to a molecular emission cavity analyzer where the silica is determined. Only arsenic and boron interfere. Pyen, Fishman, and Hedley (161) developed an automated, colorimetric procedure to determine bromide in natural waters, based on the catalytic effect of bromide on the oxidation of iodine to iodate by potassium permanganate in acid solution. In this flowthrough system, 20 samples/h can be analyzed to levels of 0.01 mg of bromide L. A similar automated procedure for determining bromi e was presented by Moxon and Dixon (121). A techni ue is included for compensating for s ectrophotometric procedure was chloride interference. develo ed by Peron and ourtot-Coupez (151) to measure bromi&.in seawater,based upon the reaction of bromide with phenol red. The absorbance is measured at 582 nm. Bromates do not interfere. Nota et al. (141) determined bromide in water by reaction of bromide with chlorine and cyanide to form BrCN, which is separted by gas chromatography and determined by an electron capture detector. At 0.163-1.650 ppm bromide, the absolute deviation is 0.012-0.05 ppm. Small amounts of aromatic compounds interfere, but oxidizing or reducing agents, mercury, and cadmium do not interfere. A solvent extraction-ion selective electrode method for the determination of iodide in environmentalsamples is described by Fukuzaki et al. (31). The solvent extraction technique is used to remove substances,such as sulfide, that interfere with the potentiometric determination. The recoveries were excellent. Nikashina and Krachak (131) determined trace amounts of iodine in natural waters using ion-selective electrodes. Ascorbic acid is used as a reducing agent in the measurement of iodine concentrations in the 1X lo4 to 2 X lo* M range. Pneumatoamperometry was used by Gifford and Bruckenstein (44 to determine iodide or iodate in water. For either constituent, iodine was chemically enerated and flushed from the system and over a hydropho%icgas-porous electrode by nitrogen gas. Iodine was electrolyzed at constant potential, which gives a response proportional to the initial concentration of constituent. The detection limits for iodide and iodate were 6.5 and 0.5 ppb, respective1 Indicator reactions are proposed by Kreingol'd et al. (8dfor the kinetic determination of iodide and iodate ions in mineral waters, by measuring the time-dependent optical absorbance during the oxidation of o-phenylenediamine, diphenylcarbazide, .and Variamine Blue with hydrogen peroxide in acid medium.
cp
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981 I
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WATER ANALYSIS
Concentrations of 0.01-2.0 mg/L iodide or iodate can be determined. A technique for the determination of or anically bound halogens in waters and wastes is presented Ey Kowal, Kowalski, and Krasniewska (71). This method is based on mineralization of samples in the presence of Co(III)/Co(II) catalyst followed by the turbidimetric determination of total chlorine, bromine, and iodine content with silver nitrate.
NITRATE, NITRITE, AMMONIA, ORGANIC NITROGEN, CYANIDE, AND THIOCYANATE Murata, Takemoto, and Ikeda (244 analyzed natural waters for nitrogen compounds by measuring the X-ray photoelectron spectrum of the residue from evaporation on an aluminum plate. Nitrate and ammonia values were comparable to those obtained by traditional techniques; however, the nitrite concentration was overestimated. Modifications to the procedure involving peroxodisulfate oxidation of 10 total nitrogen compounds to nitrate is described by Nydahl (264. The choice of pro er concentrations of peroxodisulfate and sodium hyd r o x i 8 for the digestion, and the choice of proper pH and buffer systems for the reduction of nitrate to nitrite for colorimetric analysis, is discussed. An automated system for the analysis of dissolved organic nitrogen was developed and applied to natural waters by Lowry and Mancy (214. The sample was subjected to UV irradiation, followed by the heterogeneous reduction of the nitrogen-containing roducts to ammonia, which was detected by an ion-selective eyectrode. Quantitative recoveries were obtained after 17 min of irradiation. A block digestor procedure for the simultaneous determination of total phos horus and total Kjeldahl nitrogen was evaluated and modifiefby Gales and Booth (114 for the semiautomated determination of these constituents in surface water and domestic and industrial wastes. The applicable range for both constituents is 0.1-20 mg/L. A computer-controlled multichannel continuous flow analysis system used for the spectrophotometricmeasurement of nitrate and ammonium ions in small samples of rainwater is described by Slanina et al. (324. Calibration analysis of samples and quality control are done automatically. The sampling rate is 18-35 per hour, and the analytical range is 0.2-20 ppm. Spectrophotometricproceduresfor determiningnitrate plus nitrite or nitrate in natural waters that involves cadmium reduction, diazotization, and coupling reactions are discussed by several authors. Okada, Miyata, and Toei ( 2 7 4 used p-aminoacetophenone and m-phenylenediamine as diazotization and coupling agents, respectively. Spectrophotometric measurement is made at 460 nm. An automated procedure involving a convenient wire reductor of Cd-5% Ag alloy inserted in Teflon tubing is used by Willis (374. Reduction efficiency is essentially 100%. Anderson (14presented a flow injection method with detection limits of 0.05 pM for nitrite and 0.1 KM for nitrate at a total sample volume of 200 pL. Thirty samples per hour can be analyzed with a relative precision of 1% , Davison and Woof ( 7 4 studied the efficiency and reproducibility of various forms of cadmium as reducing agents. It was concluded that both the filing and spongy cadmium were efficient reducing agents and gave reproducible results. Further study by Davison and Woof ( 8 4 showed that reduction with spongy cadmium was less prone to interference than reduction with cadmium filings. The preparation of a reactivation solution for a copperized cadmium column is presented by Otsuki (285). The column is reactivated by pumping the solution through the automated system. An automated hydrazine reduction method for the automated determination of low nitrate levels in freshwater is described by Downes ( 9 4 . Interferences are eliminated by the addition of zinc to the cop er catalyst solution. The ultraviolet spectro hotometric &termination of nitrate and nitrite in water is iscussed by Hiiro, Kawahara, and Tanaka (164. Absorbances at 223 and 232 nm are measured, and the difference between the two absorbances is calculated. The influence of several substances in Cater is discussed. Chao and Tin (55) presented an ultraviolet spectrophotometric method for the direct determination of nitrite and nitrate in water, based on the fact that they have identical absorbance a t 219 nm. In a portion of one sample, nitrite is removed by sulfamic acid; in another, both nitrate and nitrite are reduced by Zn-Cu. Thus, by measuring the absorbance of the original 194R
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
sample and these two solutions, both nitrate and nitrite can be determined. The detection limit for both ions is 0.07 ppm. An ultraviolet/resin technique for determining nitrate is proposed by Brown and Bellinger (34. Chloride, phosphate, sulfate, carbonate/bicarbonate,bromide, nitrite, colored metal complexes, humic acids, ammonium, dyes, detergents, phenols, and other ultraviolet absorbing organic compounds do not interfere in this procedure. The analytical range in freshwater is 0.1-3.0 mg/L nitrogen. Trojanowicz (344 used the ion association complex of bis(neocuproine)-Cu(I)and nitrate as an electroactive material for a nitrate ion selective electrode. The detection limit in tap water is approximately 0.2 ppm. Data on sensitivity and selectivity are presented. The microdetermination of nitrate in lake waters by potentiometry with an ion-selectiveelectrode is presented by Simeonov, Andreev, and Stoianov (314. Use of the Grand method, which was one of several potentiometric analytical techniques studied, made it possible to determine small fluctuations in nitrate concentrations very precisely. Brinkhoff ( 2 4 determined nitrate in surface waters and sewage effluents by use of a plastic-membranenitrate-selective electrode; he compared these results with those obtained by a standard colorimetric procedure. Hainberger and Nozaki (144 determined nitrate colorimetrically with 2,7-diaminofluorenein an acid media at 435 nm. Most interfering substances can be masked. A description is given by Li (204 of a colorimetric method for the determination of nitrate in seawater with [N,N’-bis(p-sulfopheny1)benzidinel disodium salt. A detailed description of the procedure is included. The range is 1-100 mg/L with an average error of 4%. Williams (364 studied the literature concerning the need for preserving potable samples prior to determination for nitrate. On the basis of this study, he indicated that substantial changes in nitrate content are unlikely. A spectrophotometric procedure for determining nitrite in water is presented by Nair and Gupta (254. This method is based on the formation of a purple azoxine dye by coupling diazotized p-nitroaniline with 8-quinolinol. Beer’s law is obeyed at 550 nm in the concentration range 80-1120 pg/L. The spectrophotometric determination of trace quantities of nitrite in the presence of nitrate with 2,7-diaminofluoreneis described by Hainberger and Nozaki (154. Beer’s law is obeyed for nitrite concentrations of 0.1-2.3 ppm. Chao, Higuchi, and Sternson (65)applied the rapid esterification of nitrite for its determination in water. Nitrite is converted to decyl nitrite by passin an acidified water sample through a bed of packed beads &AD-2), which are coated with 1decanol under optimized conditions. Sixty-eight percent of the nitrite is retained on the column as decyl nitrite; it is eluted and converted to an azo dye by traditional techniques. Garside, Hull, and Murray (134 discussed a standard addition technique using a gas-sensing electrode with a modified electrode filling solution for field or laboratory measurement of ammonia. A detection limit and precision of 0.2 and f0.1 pM ammonia, respectively, were obtained. An ammonia electrode with immobilized nitrifying bacteria is described by Hikuma et al. (175). The ammonia electrode consists of Nitrosomonas euro aca bacteria and an oxygen electrode. The electrode current &creases until a steady state is reached. A linear relationship exists between current difference and ammonia concentration to 11.3 mg/L. A procedure based on the formation of a substituted indophenol with sodium salicylate as phenolic reagent was developed by Verdouw, Van Echteld, and Dekkers (354 for determiningammonia in fresh- and seawaters. This procedure is specific for ammonia and is generally free from interferences. A colorimetric procedure involving the formation of a colored complex of ammonia with 2,5-dimethoxyoxolaneand (E)-pdimethylaminocinnamaldehyde is outlined by Carson and Gross (44. The method is suitable for automation and has a detection limit of IO4 M. Krug, Ruzicka, and Hansen. (19J) described the turbimetric determination of ammonia in low concentrations (0.5-6 ppm) with Nessler’s reagent by flowinjection analysis, The sampling rate is 100 samples/h and sample volume is 30 pL. Reagent and system variables are discussed at length. Tanaka, Ishizuka, and Sunahara (335) investigated the determination of ammonium ion in sewage and river water by ion-exclusion chromatography on an anion-exchange resin, Chromatographic conditions for the
WATER ANALYSIS
separation of ammonium ion from diverse cations, the separation mechanism, and the flow coulometric and conductometric detector responses are discussed. A polarographic procedure is presented by McLean et al. (235) for the determination of ammonia and primary amines at levels of less than 1ppm. It has been applied to water and brine samples. Gardner (124 measured ammonium ion fluorimetrically after chromatographicseparation from amino acids and reaction withi o-phthalaldehyde. This method requires less than 0.5 mlL of sample and is sensitive to 0.2 pM of ammonium ion in seawater. Riemann and Schierup (304 studied the effects of preserving a water sample with sulfuric acid or mercuric chloride and of filtration of this sample through a glass fiber or 0.2 pm Nucleopore filter for the determination of ammonia. It was concluded that stored or preserved samples filtered through both types of fiiters showed similar, unsystematic changes in concentration of ammonia. Eaton and Grant (1091) found that glass support frits for 47-mm Millipore filters and certain lass fiber filters rapidly absorb ammonia from fresh or bracfish waters. Significant analytical errors can occur if one does not compensate for this effect by rinsing with copious quantities of sample before collection, by addin potassium ion to reduce sorption, or by silanizing frits or fiytem to block sorption. McKee (224 compiled a review of analytical methods €or cyanide. A continuous system for the determination of free and complex cyanide was develo ed b Pihlar and Kosta (295). Hydrogen cyanide was reyeasex in acidic solution, absorbed in dilute sodium hydroxide, and then fed into the amperometric detector with a silver flowthrough electrode. Ultraviolet irradiation was used to decompose the complex cyanides. A mercury cold vapor atomic absorption spectrophotometric determination of cyanide, based on the formation of a stable Hg-CN- complex, is described by Zhu et al. (384. This complex, under certain conditions, cannot be reduced to the atomic state. The method follows Beer's law in the range 0-4 ppb and ha*, a sensitivity of 0.4 ppb. An automated procedure for determining thiocyanate at the ppm level in waters using an ion-selective electrode with a liquid membrane is presented by Korenaga (184. Longchained quaternary ammonium salts are used as the exchan e site in the liquid membrane using 1,2-dichloroethane. T i e liquid membrane exhibits a Nernstian response down to 10" M.
RADIOCHEMICAL AND ISOTOPIC ANALYSIS A liquid chromatographic procedure for determining ra-
dioelements in aqueout3 solutions is resented by Moskvin, Miroshnikov, and Mel'nikov (15K). is based on the use of packings in tablet form for liquid chromatographic preconcentration and successive measurement of their a-activity. The mean square deviation is less than 15% for determining I, Cs, Ba, Sr, Y, Mo, and IMn. An evaluation of counting tubes used for the measurement of radioactivity in drinking water was conducted by Van Hemmen, Van Hoek, and Aten (17K). Contaminationmeters were calibrated with the use of solutions containing 89Sr and 204'lrhand then tested with solutions containing increasing concentrations of the two isoto es. The rapid determination of radionuclides and radionuclife groups for drinkin water monitoring is outlined by Haberer and Stuerzer (7k).This method is based on filtration through anion- and cation-exchange filters and subsequent elution and precipitation reactions. A compilation of the separation steps and their yields shows that the yields are generally greater than 90%. A method for routine monitorin of 11radionus by Kimura ancfHamada (IlIQ. clides in rainwater w ~ studied The rainwater is passed through a mixture of anion- and cation-exchange resins, and both the resin and effluent are analyzed by a-spectrometry after concentration by evaporation. The radionuclidesdetermined we@ 141Ce,l4Ce, 1311,'Be, g5Zr,95Nb,and 140Ld. The deterloSRu,lwRu, I4OBa 137Cs, mination of Ia4Cs,'137Cs,210Ra,and zz8Rain coastal marine sediments and seawater ia discussed by Mackenzie et al. (14K). A detailed account of the methods involved is included. Egorova et al. (3K) described a procedure in which cesium was selectively absorbed from seawater with graxiulated zirconium ferrocyanide ~d then determined by a-spectroscopy. The rare earth elements are also absorbed, but they can be easily separated from cesium. Procedures for determinin 13'Cs in seawater are outlined by Gedeonov, Krylov, an$
I"t
Stepanov (6K). One is based on the use of natural 4oKa8 an internal standard. Another determines 13'Cs without the use of standards by pumping a certain amount of water through several successive identical cells filled with sorbent. Kishima and Sakai (12K) determined l80and deuterium in a sibgle water sample by using a modified carbon dioxide equilibrium procedure for determining lag. Five- and twomilligram samples from two stock waters of different isotopic compositions are first analyzed for their 6l80 values. The water samples were then recovered and anal zed for deuterium. A GC/MS technique for determining zO content in HzO is presented by Sharp and Minard (16K), which does not require the handling of gaseous samples. Small quantities of phosphorus pentachloride and the sample react to form phosphoric acid which is then esterified with diazomethane to yield Me3P04. The I80 content of this compound is determined by GC/MS-selected ion monitoring of the molecular ion region. A coefficient of variation of f0.5% has been routinely obtained. Kellomaki and Jutila (IOK) used proton chemical shifts to measure the deuterium content of water by NMR spectroscopy. Hydrogen from sulfonatedpolystyrene ion exchangers suspended in water exhibit two distinct proton NMR peaks. The separation of these peaks, which is dependent on the deuterium content of the water, can be measured by NMR. The accuracy of the method is approximately 5 % A collaborative study of an anion-exchangemethod for the determination of trace plutonium in water is reported by Bishop, Glosby, and Phillips ( I K ) . The method involves coprecipitation, acid dissolution, anion exchange, electrodeposition, and a-pulse-hei h t analysis. In the collaborative study involving four sampfes, standard deviations were in the range 5-13%. Xiang et al. (19K)presented a procedure in which plutonium in seawater is determined with a recovery of 94% or more. The method includes adsorption, coprecipitation, centrifugation, and electroplatin on a platinum cathode. Preconcentration of plutonium raJonuclides from natural waters was investigated by Wong, Nioshkin, and Jokela (18K).A lar e volume sampler with manganese dioxide impregnated cartricfges for the in situ separation of plutonium was used. A method for the ion-exchange separation of low levels of americium in environmental materials is described by Holm, Ballestra, and Fukai (8K). Up to 200 L of sample can be processed. The a-spectrum of americium separated from a river-suspension sample showed only small quantitied of Ra, Rn, and Po. Brown ( 2 9 stated that poor recovery of radioactivity when determining 4C02respired by microbes can be overcome by substituting 2-ethanolaminefor 2-phenylethylamineto absorb 14C02and by increasing the solubility of 14C02in the scintillation solution with 2-ethoxyethanol. The sorption of %r with BaSiF6 for the determination of Y3r in seawater by a-spectroscopy was studied by Egorova, Krylov, and Stepanov (4K). The recovery was approximate1 90% with a contact time of 144 h; the sorption of 13'Cs, 8Zr, and gSNbwas insignificant. A procedure for the determination of 220Rnin mineral springs by toluene extraction and liquid scintillation is described by Horiuchi and Murakami (9K).After extraction, the activity of the solution is measured by an inte ral counting technique with a li uid scintillation counter. BRa rapidly disappears, but 21zPjand its daughters form a radioactive equilibrium in the toluene solution approximately 3.7 h after extraction. The detection limit of the procedure is 680 f 90 pci. Elmore et al. ( 5 K ) described the determination of %Cl in environmental-water samples using an electrostatic accelerator as an ultrasensitive mass spectrometer. Chloride is precipitated from the samples as silver chloride, and the 36Cl-Cl is determined. The determination of 6oCuin environmental samples by substoichiometric isotope dilution analysis is presented by Kudo and Kobayashi (13K). The procedure involved substoichiometric extraction with dithizone.
.
GASES Winkler's procedure for determining dissolved oxygen was modified by Reddy, Rajan, and Reddy (15L)to cope with large quantities of oxidizing or reducing agents in water samples. Dissolved oxygen is determined in the presence of chlorine nitrite, ferric, ferrous, and dichromate ions with a standard ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
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WATER ANALYSIS
deviation of 0.01-0.04 mg/L. Rahim and Mohamed (14.5) studied the determination of dissolved oxygen in water by its oxidation of manganous ion to manganic ion in an alkaline media, and subsequent colorimetry of the red manganicEDTA complex at H 4. The results agreed with those of the the 14 common ions studied, only sulfide Winkler method. interfered appreciably. A method is presented by Ingvorsen and Joergensen (9L) for the determination of oxygen and sulfide by precipitation with zinc hydroxide; oxygen is determined by the Winkler technique on the clear supernatant. A technique for determining low concentrations of oxygen in power station waters was developed by Goodfellow and Webber (7L). The reaction of dissolved oxygen with leucomethylene blue yields a soluble blue oxidation product with an absorbance proportional to the oxygen concentration. The detection limit is 1pg/L; Fe(I1) and Cu(I1) were the only ions present that interfered; these were removable with a cationexchange column. An automated procedure using the same chemical principle was described by Goodfellow, Libaert, and Webber (6L). The standard deviation at 20 pg/L of oxygen was 0.37 p /L by the automated procedure compared with 1.69 pg/L f ~ the y manual method. A rapid, gas chromatographic procedure for determining dissolved oxygen in water is described by Hall (8L). After injection of 10 pL of sam le onto a column, the oxygen is separated and measured y! an electron capture detector. Leggett (IOL)discussed the determination of dissolved nitrogen and oxygen in water by headspace gas chromatography. These gases are determined by shaking 20-25 mL of water with an equal amount of helium in a 50-mL gastight syringe and injecting 2 mL of the equilibrated headgas into the chromatograph. A hot-wire detector is used. The design and use of an electrochemicalanalyzer for oxygen is presented by Storozhenko et al. (20L). Oxygen in the sample diffuses through a semipermeable lastic membrane to a platinum-coil cathode. The cathode a n i an annular zinc anode are in a cell with 0.1 M sodium acetate. Wei (21L)constructed an automatic analyzer to determine dissolved oxygen in water. Nitrogen or hydrogen is used to displace the oxygen from the water in a spiral device followed by determining the electrical potential of the gas. Bender ( I L )compared 10 different methods, all based on the iodine-iodide reaction, for determining total available residual chlorine. Observations regarding advantages, disadvantages, deviations, problems, and matrix effects are included. Problems that may occur in the determination of residual chlorine in seawater by the amperometric titrimetric method were discussed by Wong (22L). It was concluded that serious analytical error may occur if the order of addition of reagents were reversed; furthermore, for concentrations of residual chlorine less than 1mg/L, iodate may cause serious analytical difficulties. Brooks and Seegert (2L) resented a sensitive, amperometric titration procedure for etermining residual chlorine in water. A three-electrode cell, piston buret, and a recorder are used, The suitability of an amperometric probe for determiningresidual chlorine in saline-coolingwaters was evaluated by Dimmock and Midgley (315).The probe had a linear response to hypochlorous acid over the range 0-5 pg mL but was not s ecific for free residual chlorine since ch oramines also pro uced a response. The main product of the chlorination of seawater is bromine, to which the robe is a proximately 5 times more sensitive than to hypoch orous acicf Dimmock and Mid ley (4L) also mqdified a free available chlorine probe to getermine total residual chlorine in saline cooling waters. The basic modification consisted of changing the internal filling solution of the probe from potassium bromide to potassium iodide. Also, solutions of potassium bromide and potassium iodide were added to the samples before determining free residual chlorine and total residual chlorine, respectively. Palin (12L)used diethyl-p-phenylenediamineto determine free available chlorine in water. Thioacetamide is added to the sample solution to remove the interference from high concentrations of monochloramines. An amperometric titration apparatus was constructured b Payne (13L)to determine chlorine in water at a detectabIye limit of5-10 pg/L. This method can also detect bromine and can differentiate between bromine and chlorine. Roscher et al. (16L)discussed the use of syringaldazine to determine free available chlorine and ozone in aqueous solu-
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196R ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
tions. This method is specific for chlorine in the presence of common interferences found in water. It was also modified to determine ozone in water. Analytical ranges for free available chlorine and ozone are 0-10 and 0-6 mg/L, respectively. The differential pulse polarography of phenylarsine oxide as an indirect determination of ozone and residual chlorine in water was investi ated by Smart, Lowry, and Mancy (18L). The limits of cfetection are 3.3 p b for free chlorine at pH 7, 1.6 ppb for total chlorine at p 4, and 2.5 ppb of ozone at pH 4. An amperometric method s ecific for dissolved ozone in water was discussed by Masscfelein et al. (1IL). The technique is based on the polarization of electrode couple Ni/Ag, which is not sensitive to dissolved chlorine, and has a sensitivity of 0.02 g/m3. Stanley and Johnson (19L)developed an am erometric membrane for the selective measurement of mofkular ozone in water. Little interference was observed from Br, HOBr, CIOz,HzOz,NC13, and HOC1, and a detection limit of 62 pg/L is predicted a t twice the observed residual current. Smart, Dormond-Herrera, and Mancy ( I 7L) developed a voltammetric membrane electrode for determining trace quantities of ozone in waters and wastewaters. Measurements are made by using steady-state and pulse techniques, a three-electrode voltammetric cell, and a gaspermeable electrode. A method for determiningdissolved nitrous oxide in aquatic systems by gas chromatography using electron-ca ture detection and multiple phase equilibrium is discussedy! Elkins (5L). Precision of better than 2% can be achieved on sample sizes of 60 mL or more. Possible sources of error are discussed.
J
MULTICONSTITUENTS The determination of trace metals in water b atomic absorption spectrometry (AAS) with electrotherm atomization was discussed by several authors. Lagas (33M) reported that memo effects and reproducibility problems can be avoided when xtermining Be, Ba, and V in water by using tubes coated with pyrolytic graphite and carbide. Improved results were also found for the determination of other carbide forming and/or high-melting elements. The use of electrodeless discharge lamps in conjuction with a graphite furnace for determinin As, Cr, Cd, Pb, and Se in drinking water was outlinedty Sefzik (48M). The use of W-Re wire loops as atomizers for flameless atomic absorption spectrometry was resented by West et al. (59M). A line voltage ramp, proyided g y a variable transformer driven by a motor, was applied to the wire loop for atomization of the analyte. Davis (IOV also successfully used the wire loop as an atomizer. Bozsai and Csanady (7M) obtained good agreement between electrothermal and chelation-extraction atomic absorption s ectrophotometric procedures when determinin Cd, Pb, u, Zn, Cr, and Ba in drinking waters. A chektion-extraction, flameless AAS procedure was discussed by Subramanian and Meranger (53M) for determining Ag, Cd, Co, Cr, Cu, Fe, Mn, and Ni in drinking water. Conditions affecting the chelation-extraction efficiency were studied. Flameless AAS procedures involving a back-extraction step were studied by Jan and Young (24M) and Danielsson, Magnusson, and Westerlund (9q.In the first rocedure, a nitric acid backextraction step is used to stabitze the metal complexes, following a traditional chelation-extraction step. The detection limits listed ranged from 0.003 to 0.20 pg L for a variety of metals. In the latter procedure, metal-car amate complexes are extracted from seawater into Freon TF and stabilized by back-extraction into nitric acid. Separation of eight transition elements from alkali and alkaline earth elements in estuarine and seawater with Chelex 100 and their determination with graphite furnace AAS is described by Kin ston et al. (28M). By careful selection of instrumental con itions, it is possible to determine subnanogram quantities of these metals. Stur eon et al. (52M) determined nine transition metals by grap ite furance AAS after either chelation-extraction and back-extraction with HN03 or preconcentration by ion exchange. The former technique is preferred when only small volumes of sample are available. Bone and Hibbert (6M) described a simultaneous solvent extraction technique using ammonium pyrrolidinedithiofor the carbamate (APDC) and 2,6-dimethyl-4-heptanone determination of 10 trace metals by flame AAS. Calibration
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WATER ANALYSIS
curves are usually linear over the range 0-50 pg/L, and effects of interfering substances are shown. A similar procedure using APDC and 3:l mixture of methyl isobutyl ketone-xylene as chelating and extraction agents, respectively, was presented by El-Enany, Mahmoud, and Varma (22M). With the exception of As, detection limits ranged from 2 to 20 pg/L. Flame AAS was used by Marchin and Collins (37M) to determine Cd, Cs, Cr, CCI,Pb, Ni, Rb, and V in oil field brines and synthetic oil field brines. The method of standard additions, a deuterium arc lamp for background correction, and sodium ion additions were employed to eliminateinterferences. The use of inductively coupled plasma, optical emission spectrometry (ICP-AES) is becoming increasingly popular for multielement determinations in water. Garbarino and Taylor (16M) described an ICJ?-AES procedure that simultaneously determines 17 elements. Comparability studies with singleelement methods of analysis are included. An evaluation of the degree of compensation produced by a commercial background system is discussed by Larson, Goodpasture, and Morrow (34M) and problems encountered in the automated analysis of natural water samples is discussed. A commercial ICP-AES system was automated by Peck, Langhorst, and O'Brien (43M) to provide unattended operation and data collection following initializing commands and loading of the sample changer. Application of the system to the analysis of water samples is described. Ape1 et al. ( I M ) used an ICP-AES procedure to determine nine elements in water. A comparison of several nebulizer designs is included. Simultaneous determination of Fe, MI?, Cu, Zn, and Ni in seawater by a combination of ion-exclhange preconcentration and ICP-AES is described by Berman, McLaren, and Willie (3M). Ultrasonic nebulization with aerosol desolvation is used to introduce the constituents to the plasma. The prominent lines of the emission spectra of somle 70 elements were recorded by Winge, Peterson, and Fassel(60M) as the f i s t step in the development of a spectral atlas that would serve as a useful tool in the selection of analytical lines for ICP-AES analysis. The acid digestion of environmenkd materials for analysis by ICP-AES is described by McQuaker, Brown, and Kluckner (36M). Procedures using HNQ,/HC104 and HF/HN03/HC104are discussed. Johnson, Taylor, and Skogerboe (26M, 27M) investigated the determination of :L8 elements in water by a dc argon plasma, multielement atomic emission spectrometric technique. It is reported t h n t the system gives acceptable selectivity, sensitivity, accuiracy, speed, and economy for the determination of most elements. A comparison of two-electrode and three-electrode dc argon plasma systems show that the latter has improved stability and lower background. Spectral interferences and compensation for such interferences are characterized in detail. The theory of ion chromatography is discussed by Rich, Tillotson, and Chang (47M). Included are analytical results from various waters. Fishman and Pyen (Y3M) simultaneously determined Br, C1, F, NO3, NO2, PO4, and SO4 by ion chromatography. Detection limits ranged from 0.01 mg/L for F to 0.20 mg/L for C1 and SO4. The results obtAned are in good agreement with those obtained by traditional techniques. The use of ion chromatography for determining F, C1, NO , and SO4 in 30 natural waters; was presented by Smee, Hal!, and Koop ( 5 I M ) . A comparison of results obtained through separator columns of two different lengths is included. The adaptation of an ion chromatograph for computer control and the programs for peak detection are described by Slanina et al. (50M). The selectivity of the system for determining constituents in rainwater was optimized by thermostating the separation columns at 40 "C and by using two eluents. Ion chromatography was used by Bogen and Nagourney (5M) for the determination of Na, NH4, and K in rainwaters. The agreement with results from atomic absorption spectrometry for Na and K was good (above 100 pg/L; however, at lower concentrations, significant variations were observed. Some problems encountered with ion chromatographic columns are discussed. Tyree, Stouffer, and Bollinger (54M) analyzed simulated rainwater for F, C1, NO3, SO4,*Na, K, NH4, and Mg in the range from 0.05 t o 20 ppm by ion chromatography. Experimental results of ion chromatographic determination of F, C1, Br, NO3, and SO4 in seawater was reported by Itoh and Shinbori (23M). The relative standard deviations ranged from 0.4 to 7.6%. Rawa (46M) stated that ion chromatography
is an effective technique for monitoring F, C1, NO3, NO2, PO , SO3, and SO4content of industrial waters at the pm and ppk levels. Good agreement was obtained with tra itional automated and manual methods. An ion chromatographic procedure for the determination of Na, K, C1, and SO4 at ppb levels was developed b Fulmer et al, (15M). The constituenta were preconcentrate on a concentrator column. Nordmeyer et al. (42M) determined alkaline earth and divalent transition-metal cations by ion chromatography with Ba(N03)2,BaC12,or Pb(NO& eluents. Alkaline earths were separated from one another; however, the present separator system does not effectively separate transition-metal ions from each other or from calcium. Back round conductivity is suppressed by precipitation of Bas or PbS04 in the sulfate-form anion-exchangesuppressor column. Determination of anions in pore waters from marine cores by ion chromato raphy was discussed by Pyen and Fishman (45M). The sofutions were diluted 50- to 100-foldbecause of high dissolved solid content and then were analyzed for C1, F, NO3, Br, and SO4 Results from this procedure were in good agreement with those obtained by colorimetric methods. Kusaka et al. (32M) determined trace elements in seawater by neutron activation analysis (NAA). Extraction with 1pyrrolidinethiocarbonic acid and freeze drying are used to preconcentrate the metals. After irradiation, the resulting a-spectra are obtained with Ge(Li) detectors. Problems concerning the extractive separation of trace elements in seawater and their determination by NAA are discussed by Heuss and Lieser (19M). Experiments with trioctylphos hine oxide produced a strong interference of the bremsstra lung radiation from 32P.Experiments with oxine at different pHs showed that in each case only a few elements are extracted in greater amounts. The adsorption separation of trace elements and their determination by NAA were investigated by Heuss and Lieser (2OM). Three different adsorption procedures involving activated charcoal were presented, and the adsorption conditions most favorable for each of 23 elements were listed. Kulmatov et al. ( 3 0 described a NAA procedure in which the trace metals in dry residues from natural waters are activated, dissolved in hydrochloric acid, and separated from interferin elements by extraction chromatography. After they are elute3 from the column, they are determined by a-s ectrometry. The recoveries are 98-100% for Cd, Hg, a n f A u and 92-98% for Cu, Zn, Sb, and Mo. Pretreatment techniques combining evaporation and coprecipitation methods for the NAA determination of more than 20 trace elements in river water are discussed by Nagatsuka ( 4 0 . The combination of NAA and electrolysis at a constant controlled potential as a multielement method for determining 28 elements in seawater was presented by Joerstad and Salbu (25M). After freeze-dryingand irradiation, the samples were dissolved and electrolyzed. The radioactive species deposited on the mercury cathode allowed the determinationof 14 elements, and another 14 were determined by measuring their activities in the residual solution. Kulmatov, Kist, and Karimov (31M) used NAA to determine 10 elements in the dissolved and undissolved fractions of various water samples. Lenvik, Steinnes, and Pappas (35W determined As, Cd, Co, Hg, Mo, and Zn in freshwater by a NAA procedure based on anion-exchan e separation in hydrochloric acid media followed by simpfe precipitations. Detection limits for these elements range from 1 X 10-1to 1 x lo4 pg/L. NAA determination of rare earths and heavy metals in river water after preconcentration with Chelex 100 was studied by Hirose (2IM). The rare earths and heavy metals were eluted with sodium carbonate and nitric acid, respectively, and the activities were counted with a Ge(Li) detector. Preparation of multielement standards for use in the NAA determination of trace metals is described by Neitzert and Lieser (41M).Eleven NAA, X-ray fluorescence, and spark source spectrometric procedures for the multielement analysis of geothermal waters were evaluated by Blommaert et al. (4M). The efficiency of each method was discussed. An X-ray method is described by Pik et al. (44M) for the determination of Fe, Co, Ni, Cu, Zn, Cd, and P b in water at pg/L levels, in which the metals are coprecipitated with a molybdenum-pyrrolidinedithiocarbamate carrier complex. The precipitate is collected as a thin film on a membrane filter and analyzed directly by X-ray fluorescence. Vanderborght
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
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WATER ANALYSIS
and Van Grieken (55M) combined a preconcentration technique with energy-dispersive X-ray fluorescence to determine trace metals in water that contains humic substances. The preconcentration step consisted of chelation with oxine, followed b adsorption on activated carbon. Hubert and Chao (22M) &scribed an X-ray fluorescence procedure for determining trace metals in water at the ppb level. The metals are preconcentrated by addition of ammonium pyrrolidine dithiocarbamate and the resulting precipitate is collected for analysis on a 3.0-pm filter. X-ray fluorescence analysis of trace metals in water is presented by Vanderstappen and Van Grieken (57M). Prior to analysis, the metals are concentrated by the addition of l-(Z-pyridylazo)-Z-naphtholto the sample. The recovery for many ions is excellent. X-ray fluorescence and flameless atomic absorption spectrometric procedures for the determination of trace quantities of elements in aqueous solutions were studied by Disam, Tschoepel, and Toelg (1IM). The elements were concentrated by precipitate exchange reactions on thin metal sulfide layers. Detection limits in the ng/L range were obtained. Gillain, Duyckaerts, and Disteche ( 17M) used differential pulse anodic stripping voltammetry with a hanging mercury drop electrode for the direct and simultaneous determinations of Zn, Cd, Pb, Cu, Sb, and Bi in seawater. Detection limits for the various elements ranged from 0.01 to 0.1 ppb. An anodic stripping monitoring system for determining trace metals in natural waters is described by Wang and Ariel (58M). A rotating disk electrode is adapted for flow-through cell voltammetry that resulted in enhanced sensitivity. Simultaneous determination of Cu, Bi, Pb, and Cd at levels down to 1ng/kg by differential pulse anodic stripping voltammetry is outlined by Mart, Nuernberg, and Valenta (38M). Necessary instrumental modifications, the construction and treatment of a rotating glassy carbon mercury film electrode, and the adaptation of this electrode to contamination-free clean bench operation in a multicell system are described in detail. Trace elements were determined by Vanderborght and Van Grieken (56M) in various waters by spark-source mass spectrometry, after preconcentration by chelation of the dissolved elements with oxine, and subsequent adsorption of the oxinates and natural occurring organic and colloidal species onto activated carbon. The activated carbon was then filtered off and ashed at low temperature. It was possible to determine 23 elements simultaneously above the 0.1 pg/L detection limit. Mykytiuk, Russell, and Sturgeon (39M) determined trace quantities (pg/L) of Fe, Cd, Zn, Cu, Ni, Pb, U, and Co in seawater by isotope dilution spark-source mass spectrometry. The samples are concentrated on Chelex-100, eluted, and the eluant evaporated on a graphite or silver electrode. Multielemental analysis of drinking water by proton-induced X-ray emission (PIXE) was investigated by Simms and Riekey (49M). Targets for PIXE analysis were prepared from samples by a vapor filtration technique. Excellent detection limits (0.1-100 ppb) were obtained for most elements heavier than silica. The target preparation for X-ray emission analysis by anodic electrodeposition of cyano metalates from 2propanol-water mixtures is presented by Wundt, Duschner, and Starke (6IM). The sample is passed through an ion-exchange column and eluted with potassium cyanide. After addition of 2-propanol, cyanide complexes of Co, Ni, Cu, Zn, and Cd are electrodeposited on an aluminum electrode and determined by X-ray emission analysis. Spectrographic determination of trace amounts of 14 metal ions in water is described by Florian and Pliesouska (14M). The samples are evaporated to dryness, and the residues are mixed with lithium carbonate and graphite and excited. A chemical-spectrographic procedure was developed by KOval'chuk et al. ( 2 9 m for the determination of 18 trace elements in seawater. The elements were preconcentrated on H,TiO, a t DH8. cohfluence manifold, which reduces the temporary differences in mixing ratios when two streams meet, was developed by Bergamin, Reis, and Zagatto (234)for flow-injection analysis of natural waters. Spectrophotometric and/or turbidimetric detectors were used to determine nitrite, sulfate, and chloride. Trace enrichment and high-performance liquid chromatography were studied by Cassidy and Elchuk (8M) for the determination of trace metals in water. An inert enrichment system gave quantitative recovery at the pg/L and 198R
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
ng/L levels, and, when interfaced to a high-performance chromatograph equipped with a postcolumn reactor, made simultaneous enrichment and analysis possible. Sensitive luminescence reactions between Al, Sc, Zr, and Hf with polyhydroxyflavones were used by Zel'tzer, Morozova, and Talipov (62M) for the determination of these elements in natural and wastewaters. Optimum conditions were chosen for the fluorimetric studies of the complexes in solutions, in the solid state, adsorped on paper, and in frozen solutions. A system was designed by Grasshoff and Hansen (I8M) to measure 12 parameters from a moving ship. A data ac uisition and control system is included. Samples for other jeterminations can be collected by a continuous integrated sampling system.
ORGANICS-GC AND GC/MS METHODS A rapid, semiautomatic and sensitive method for the detection of organohalogen compounds in treated waters was reported by Van Rensburg, Van Huyssteen, and Hassett ( 4 5 M . The method, which involves liquid-liquid extraction and gas chromatographic analysis using an electron capture detector, has a linear detection range of 0.3-300 pg/L, with a lower limit of detection of 0.1 pg/L. Quantitative and qualitative headspace analysis of ppb amounts of hydrocarbons in water was reported by Drozd, Novak, and Rijks (14N). The method employs glass capillary columns and a simple all-glass splitless injection system that permits introduction of headspace gas samples with a negligible decrease in efficiency. The determination of dichloropropionic and trichloroacetic acids in water by gas chromatography was described by Chmil (7"). Reported limits of detection are 20 and 10 ppb, respectively. Piet et al. (32N) developed a procedure for the direct headspace analysis of volatile halogenated organic compounds, which avoids the need for preconcentration or prehandling of the sample, thus minimizing the introduction of systematic errors. The determination of aniline derivatives in water by gas chromato raphy was reported by Kulikova, Kirichenko, and Pashkevica (23N). These compounds are determined by benzene extraction, followed by conversion into trifluoromethoxytetrafluoro ropionanilides, prior to gas chromatographic analysis. A mo ification of the purge-and-trap technique for the determination of acetone and methyl ethyl ketone in water was described by Tai (43N); this method is applicable to concentrations of 20-60 pg/L. The determination of chlorinated hydrocarbons in water by heads ace gas chromatography is discussed by Dietz and Singley 62N). The headspace method is accurate with a standard deviation of 5% for routine analyses of drinking, natural, and industrial waters. Quimby et al. ( 3 4 N described a method for determination of trihalomethanes in drinking water by as chromatography using a microwave plasma emission fetector. The detector monitors the individual halogens selectively and exhibits consistent molar response factors in a variety of chemical environments. Performance of the detector with respect to chlorine, bromine, and iodine containing compounds is presented in terms of selectivity vs. hydrocarbons, response, interhalogen selectivity, linearity, and detection limits. Gas chromatographic determination of P l s a t the ppm level in water using a graphitized carbon lack is described by Di Corcia and Samperi (ION). Klockow, Bayer, and Fai le (22N) described a gas chromatographic procedure for t e determination of traces of low molecular weight carboxylic and sulfonic acids in aqueous solutions. Preconcentration and derivatization of the carboxylic acids is achieved by freeze-dryingtheir tetra-n-butylammonimsal? and converting the latter into benzyl carboxylates. Sulfonlc acids are converted to the corresponding silver salts, freezedried, and esterified by using butylammonium iodide. Webster and Worobey ( 4 8 N reported on the derivatization and GLC determination of the sterically hindered 2,6-difluorobenzoic acid in pond water. Residues are extracted with ethyl acetate and derivatized with pentafluorobenzyl bromide. Analysis is by GC usin the electron capture detector. Advantages of the methot are short reaction time, no need to evaporate to dryness, no column cleanup, low toxicit of the reagents, and no laboratory hazards. In a report by 4uimby et al. (35N) the aqueous chlorination products of humic and fulvic acids are examined by capillary column gas chromatography and helium microwave emission detection. Significant amounts of chlorinated phenolic and/or other acidic
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WATER ANALYSIS
compounds are apparently formed. In addition, the presence of bromine in the chlorinating mixture is shown to produce bromine containing derivatives. Chen (6N) developed a method for the trace analysis of nitrosamine in water. Water samples are distilled from alkali, acidified to remove impurities, and solvent extracted with methylene chloride. Bellar and Lichtenberg (4N)described a semiautomated headspace analysis of drinking waters and industrial waters for purgeable volatile organic compounds. Chemicals analyzed include vinyl chloride, dichlorobenzenes,and toluene. Analysis for 15 organohalides arid 10 aromatic hydrocarbons by gas chromatography/mass spectrometry yielded recoveries of 101% and 92%, respective1 . A simple, sensitive method for quantitative analysis of cargon tetrachloride and chloroform in water at the ppb level is reported by Brozowski et al. (5N). Carbon tetrachloride and chloroform are determine by direct aqueous injection onto a silica column and an electron capture detector is used. A 10-1~Linjection ermitted sensitivities approaching 100 ppt. Freudenthal 85N) described a new method for detection and identification of unknown halogenated compounds in environmental samples. A mass spectrometer is used as an element-specific detector for the gas chromatograph. Efifluent from the gas chromato raph is atomized in a microwave-induced discharge locatef in the interface between the gas chromatograph and the mass spectrometer. Elements investigated include fluorine, bromine, iodine, sulfur, and nitrogen. A method discussing the determination of hydrazine residues in water by derivaitiization and gas chromatography was reported by Selim and Warner (38N). Hydrazine is converted to its acetone azine, which is extracted with methylene chloride, and determined by gas chromatography using a N/P detector. Minimum detectability is 0.1 pb, and recoveries average 92% for water fortified with hygazine a t that level. Murray (29N) describeld the analysis of headspace gases for ppb concentrations of volatile organic contaminants in water samples by gas chromatography. Water is analyzed by placing a small portion in a glass syringe and adding a predetermined volume of nitrogen gas. The mixture is equilibrated by shaking; the gas phase is injected into a magnesium perchlorate drying tube and then into a sampling valve fitted directly to the injection port of the gas chromatograph. A method for the determination of low ng/L levels of polychlorinated biphenyls m drinking water by extraction with macroreticular resin followed by capillary column gas chromatography is presented by LeBel and Williams (25N). Detection limits are limited by interference from other organic compounds in the sample but typically are in the 1-10 range for river water. Prater, Simmons, and Mancy (33 discussed a procedure for the analysis of aqueous samples for phenols and organic acids. Carboxylic acids and phenols at ppb levels are determined by trace enrichment on macroreticular resins followed t1.y pyridine elution. This is followed by subsequent derivatizadion with bis(trimethylsily1)acetamide and analysis by gas chromatography. A delayed injectionpreconcentration gas chromatographic technique for ppb determination of organic compounds in air and water was developed by Melcher and Caldecourt (28N). The technique is particularly valuable for the determination of very low levels of organic compounds and for compounds which are difficult to extract or purge from water. In addition to increased sensitivity, a wider choice of gas chromatographic columns can be used which might otherwise be damaged by direct aqueous injection. The system can employ any of a number of widely used gas chromatographic detectors. Coutts, Hargesheimer, and Pasutto (8N) described the gas chromatographic analysis of trace levels of phenols by direct acetylation in aqueous solution. Acetate esters of six phenolic compounds are formed by the direct addition of acetic anhydride to a volume of a dilute aqueous phenolic solution containing sodium bicarbonate. Following extraction with methylene chloride, the stable acetate esters can be analyzed by standard gas Chromatographic columns and conditions. A method for the determiination of low levels of chlorophenols in drinking water was reported by Soerensen (41"). Chlorophenols are detected in drinking water at below their odor threshold level by gas chromatographic techniques. Electron capture detection sensitivity is increased by bromination of the constituents. Recoveries are reported to be quantitative g/L. Dietz and Traud (1lN) at concentrations above 1 X
discussed a method for the determination of phenols in river water by gas chromatography. Liquid-liquid extraction is used to concentrate phenols by a factor of 1 X lo3 to 1 X lo4. A gas chromatographic method for the determination of trace levels of phenols in water was reported by Lamparski and Nestrick (24N). Phenols, which do not ossess inherent electron capture sensitivity, are convertef to their heptafluorobutyryl derivatives. Recoveries of ten phenolic compounds examined a t the 20-200 ppb level are all 75% or greater. A rapid gas chromatographic profile/computer system for qualitative screenin of organic compounds in water a t the ppb level is describecfby Suffet and Glaser (42N).The system will digitize, store, retrieve, manipulate, and present the data. Data presentations are described as a function of the use of the data, the degree of similarity between two chromatograms, and the degree of chromatographic reproducibility. Methods for gas chromatographic monitoring of EPA Consent Decree Priorit Pollutants in water and wastewater samples are describedl by Keith et al. (21N). Guillemin, Martinez, and Thiault (18N)discuss a technique for organic pollutant survey analysis which involves steam-modified gas-solid chromatography. The technique combines a composite mobile phase of carrier gas plus steam and a physical parameter of the column packing, such as the specific surface area. Direct injections of aqueous samples suppress any pretreatment procedures and permit trace detection within the ppb to ppm level. Wang and Zhao (47N)described a gas chromatographic determination of DDT in industrial wastewater and other surface waters using stationary liquids and supports. Industrial wastewater samples analyzed furnished recovery rates greater than 80% with a relative error of 2%. Concentration, isolation, and determination of acidic material in an aqueous sample are reported by Richard and Fritz (36N). A new anion-exchangeresin prepared from XAD-4 was used to isolate and concentrate acidic organic material. Organic acids are recovered by elution with HC1 saturated with ethyl ether. A new modification of direct aqueous-injection gas chromatography for the determination of trace organics in water was reported by Simmonds and Kerns (40N). The method of direct aqueous-injection gas chromatography is described whereby water is selectively removed by diffusion across a permaselective membrane prior to the sample entering the chromatographic column. Multicomponent methods for the identification and quantitative measurement of polycyclic aromatic hydrocarbons in the aqueous environment is presented by Griest et al. (16N). Their application to aqueous samples taken from an area near a coal coking plant are discussed. A gas chromatographic determination of aromatic hydrocarbons in natural and wastewater by analysis of equilibrium vapor is discussed by Ioffe et al. (20N). Grimmer and Naujack (17N)report on a gas chromatographic procedure for profile analysis of polycyclic aromatic hydrocarbons in water. Analysis involves enrichment on Sephadex, followed by gas chromatographic separation on glass ca illary columns, in which more than 200 completely separatefpeaks between fluoranthrene and coronene are obtained. Routine application of the analysis requires 1-10 ng of each hydrocarbon component. Trihalomethanes (THM) in water samples are the subject of several recent reports dealing with comparison of methods, precision of analysis, quality assurance of controls, specificity of peak identification, and ease of operation. Reports by Varma et al. (46N),Dressman et al. (I3N),and Trussell et al. (44N)deal with aspects of the analysis of THMs in drinking water. An automated system for the determination of organic pollutants in water by gas chromatography mass spectrometry is described by Beggs (3N). Recent deve opments in microcomputer control of GC/MS systems simplifies the analysis by reducing the need for operator attention. This system prepares the sample and processes the analytical data automatically. The sensitivity is in the order of 60 ppt for most organic contaminants. The use of computerized gas chromatography/quadrupole mass spectrometry for the determination of selected volatile organic priority pollutants in water is discussed by Pereira and Hughes (31N). The sparge-and-trap technique is used for the measurement of 19 volatile organic compounds in surface water, round water, and industrial waste water. Analytical range is %etween5 and
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50 pg/L. Reduction in sample foaming in purge-and-trap gas chromatography/mass spectrometry analyses of water is reported by Rose and Colby (37N). Two methods for foam reduction involve the use of a silicone surfactant and application of heat for foam dispersion. Nowicki, Devine, and Kieda (JON) reported on the use of deuterated organics as internal standards in the analysis of drinking water and wastewater for volatile organic compounds by computerized GC/MS. 1,2-Dichlorethane-d is used as internal standard. Positive identification is base% on coincidence of retention time, characteristic peak height, and selective ion current profile. Trace organic components in chlorinated natural waters were investigated by Bean, Ryan, and Riley (2N). Glass-wall-coated open tubular (WCOT) column chromatography is used for separation of the organic components. Capillary GC MS was also employed by using electron impact and chemica ionization techni ues. Concentrations of nonpolar and presumably lipophi ic halogenated components formed by the chlorination of uncontaminated natural waters appear to be very low (in the ng L range) with the exception of the haloforms. Lin et al. (26 reported on the use of glass capillary column GC/MS analysis for organic compounds in drinking water concentrates and advanced waste treatment water concentrates. The analytical scheme includes the use of deuterated internal standards and partition of the concentrate into acidic, basic, and neutral fractions prior to instrumental analysis. The application of computerized gas chromatography/mass spectrometry to the finger rinting of marine-pollutant hydrocarbons is described by A1 aiges and Albrecht ( I N ) . Mass fragmentography for the determination of terphenyls in water and sediment was discussed by Shinohara, Hori, and Koga (39N). Minimum detectability for the three terphenyl isomers in water is between 7 and 25 ppt. Pentachlorophenol determination in water by mass spectrometric isotope dilution techniques is reported b Ingram, McGinnis, and Parikh (19N). A method using ;Y0-labeled pentachlorophenol was developed for the determination of low levels of this material in water. The internal standard is added to a measured volume of water and the combined solution extracted. The methyl ether derivative is prepared by diazomethylation, and the pentachlorophenol determined from the ion intensities in the mass range m / e 278-290. Quantitative gas chromatography/mass spectrometry of trace amounts of glutamic acid in water is presented by Coutts, Jones, and Liu (9N). Glutamic acid is removed from water samples via cation-exchange column chromatography and determined by GC/MS in the single ion monitoring mode following esterification and trifluorocetylation. Nanogram quantities can be determined. The determination of priority pollutants by crossed-beam liquid chromatography/mass spectrometry is discussed by McAdams and Vestal (27N). The technique is suitable for determination of amines, carcinogens, pesticides, and phenols in wastewater and drinking water.
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ORGANICS-HPLC METHODS Crathorne, Watts, and Fielding (1OP)described the determination of nonvolatile organic compounds in drinking water by high-performance liquid chromatography. An analytical scheme is developed for isolation, separation, and identification of low levels of these compounds. Extension of this approach is presented for a wide range of nonvolatile organic compounds. Barcelona, Liljestrand, and Morgan (3P) reported on the determination of low molecular weight volatile fatty acids in aqueous samples. An ion-exchange/derivatization technique is used. The resulting p-bromophenacyl esters are separated by HPLC or GLC depending on desired sensitivity and selectivity. Nanomolar determinations are possible in 1to' 4 L rainwater samples. Hullett and Eisenreich (1") described a technique for the determination of free and bound fatty acids in river water by high-performance liquid chromatography. The method involves sequential liquidliquid extraction followed by isolation of the fatty acid from a Florisil column using an ether/methanol elution. Individual fatt acids are determined following conversion to the phenacy ester derivative. Concentration and fractionation of hydrophobic organic acid constituents from natural waters by liquid chromatography is reported by Thurman and Malcolm (25P). A scheme is presented which is capable of separating and concentrating
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
humic substances into a carboxylic acid fraction, a weaker acid fraction, a water fraction, and a methanol fraction. A quantitative estimation of these fractions through the determination of dissolved organic carbon concentrations can be achieved. Thruston (24P) discussed the potential of highpressure liquid Chromatography for sample cleanu of drinking water extracts for subsequent analysis by gas c romatography/mass spectrometry. Advantages of the HPLC a roach include elimination of background and/or the proiyem of component coelution, thus enabling better identification. Van Vliet et al. (26P) developed a procedure for on-line trace enrichment in mineral and river waters by high-performance liquid chromatography using a precolumn. The technique is demonstrated with phthalate esters as model compounds. They are concentrated onto a short column containing a bonded stationary phase. Analysis is performed on a reverse-phase column using a step gradient with methanol/water as the mobile phase. Detection is by ultraviolet absorption at 233 nm. Ester recoveries are 95100% from sample volumes of 5ocT1000 mL at pumping speeds between 5 and 25 mL/min. Burns (7P)has written a review of automated trace organic analysis. Gas and liquid chromatographic, radioimmunoassay, and enzyme-labeled antibody techniques are discussed along with applications to environmental analysis. Ogan, Katz, and Slavin (18P)discussed the determination of trace amounts of polycyclic aromatic hydrocarbons in drinking water. The compounds are collected on a short column, desorbed, separated in a single step by reversed-phase HPLC, and detected fluorometrically. Application of this method to 400-mL samples of drinking water permitted detection at levels above 0.2 ng/L. In a subsequent paper by the same authors (19P),an analytical method is described for the determination of 16 polycyclic aromatic hydrocarbons in water, 15 of which are on the EPA Priority Pollutant list. They are fully resolved chromatographically with a minimum detectability of less than 10 ng L. Thin-layer and highperformance liquid chromatograp y have been combined into a procedure for the determination of polycyclic aromatic hydrocarbons in drinking water in a report by Crane, Crathorne, and Fielding (9P). Sorrel1and Reding (23P)described the determination of olynuclear aromatic hydrocarbons in environmental waters i y high-pressure liquid chromatography. Their technique utilizes cyclohexane extraction, cleanup and fractionation on alumina, and high-pressure liquid chromatography with UV detection. The method is capable of determining PAHs at 1-3 ng/L levels in raw, finished, and distributed waters. Confiation of identity was accomplished by using fluorescence, emission, and excitation spectra. The use of a fluorescence detector and high-performance liquid chromatographic determination of polycyclic hydrocarbons in environmental pollution and occupational health studies is reported by Das and Thomas (11P).Nine major polycyclic aromatic hydrocarbons are determined by HPLC with fluorescence detection. Fluorometric analysis involves a deuterium light source and excitation wavelengths below 300 nm. The extremely high sensitivity of fluorescence detection reduces minimum detectability to the subpicogram level. This system permits the use of dilute solutions, thus eliminating the usual cleanup procedures associated with trace analysis. Rapid determination of polycyclic aromatic hydrocarbons in water by liquid chromatography with fluorometric detection is reported by Cavelier (8P). A water sample is extracted on column, eluted with tetrahydrofuran, and separated and analyzed by high-pressure liquid chromatography with fluorescence detection. The use of liquid chromatography for the determination of polyc clic aromatic hydrocarbons in the environment is reported gy Dutkiewicz et al. (12P). The compounds are isolated from surface water by extraction with cyclohexane. The extracts are passed through a column of alumina, eluted with a cyclohexane/ethyl ether mixture, and examined photometrically in the 210 to 470 nm region. Hellmann (15P)discussed the fluorometric determination of per lene in the presence of other polycyclic aromatic hydrocartons by high-pressure liquid chromatography. A special chromatographic column is described, which permits isolation of perylene from normally coeluted 3,4-benzofluoranthene. The recommended mobile phase is acetone/water. Trace determination of phenolic compounds in water by reverse-phase liquid chromatography with electrochemical detection was presented by Armentrout, McLean, and Long
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WATER ANALYSIS
(2P).This system is capable of selectively detecting individual phenolic compounds a t the 1 ppb level. A carbon-polyethylene tubular anode is used in the electrochemical detector. Comparisonswith other types of carbon-basedelectrodes with respect to detector sensitivity and applicability to water analysis are also discussed. A direct liquid chromatographic determination of phenol in polluted water was reported by Guillemin and Thiault (13P).Phenol is determined without preconcentration or extraction by using purified water as the mobile phase. Minimuin detectability is approximately 100 p b. Schwartz et al. (22P)described the determination of pgthalate esters in sediments from river water by using high-performance liquid chromatography. Separation is accomplished on a silica column using hexane methylene chloride as mobile phase. Detection is by UV a sorption a t 233 nm. Minimum detectability for bis(2-ethylhexyl) phthalate and dibutyl phthalate is approximately 10 ng. The determination of acrylamide monomer by liquid chromato raphy is reported by Brown and Rhead (6P).Acrylami e determination in river, sea, estuarine, and potable waters m d sewage is effected by bromination, followed by extraction of the a,/3-dibromopropion;ide formed with ethyl acetate, and uantitative measurement by HPLC using UV detection. A jetection limit of 0.20 pg/L is reported. Brown (5P) also described the determination of acrylic acid monomer in natural and polluted waters and in polyacrylates following extraction with methainol/water. A detection limit of 0.05 mg/L and a precision of‘8% at 1-10 mg/L of acrylic acid were obtained. Gurley (14P)discussed the determination of terephthalic acid at low ppb levels by reversed-phase high-performance liquid chromatography. Trace levels of terephthalic acid in water samples are separated on a reverse-phase column and detected by UV absorbance at 240 nm. A rapid method for the trace determination of tetrachloroethylene in natural waters by direct aqueous injection HPLC was reported by Kummert, Molnar-Kulbica, and Giger (17P). Samples are introduced directly into a reverse-phase HPLC system and separated by use of a methanol/water mobile phase. Detection is by ultraviolet absorption a t 208 nm. A detection limit of 0.06 pmol/L of tetrachloroethylene can be achieved. Riggin and Howard (NP)reported on the determination of benzidine, dichlorobenzidine, and diphenylhydrazine in aqueous media b HPLC. These compounds can be determined by either &ect injection, solvent extraction, or resin absorption prior to anah sis by HPLC with a detection limit of greater than 1pg/L. ‘{he linearity, precision, and specificity of the method are reported to be excellent with minimum interferences encountered on wastewater samples. An HPLC procedure for the determination of hytoplankton pigments is reported by Abaychi and Riley (IPf:Pigments are extracted with a mixture of acetone and methanol. Following concentration under reduced pressure, the pigments are separated on a silica column using light petroleum, acetone, dimethylamine, and diethylamine as the mobile phase. Detection is carried out spectrophotometrically at 440 nm. Method sensitivity is reported to be approximately 80 ng for the chlorophylls and 5 ng for the carotenes. Determination of phosphonic acids by ion chromatography is outlined by Schiff, Pbeva, and Sarver (21P).The utility of ion chromatography as a sensitive analytical method is demonstrated for the nerve agent related compounds includin isopropyl methylphosphonate, ethyl methylphosphonate, and methylphosphonic acid. The determination of organophosphoric and organophosphorothioic acids in aqueous solution by ion chromatography is reported by Bouyoucos and Armentrout (4P). Separations are achieved on columns of low capacity ion-exchange resin using sodium carbonate/sodium bicarbonate as eluant. lletection is accomplished by a combination of a conductivity measurement and a UV absorbance measurement at 210 nm. The UV detector furnishes more s ecificity and sensitivity for organophosphorothioates,while 8scriminating against a strong chloride ion interference with the conductometric detection of the dialkylated organophosphorothioic acids.
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METHODS
A method for the determination of three phenolic compounds in water by laser excited resonance Raman spectrometry was reported by Van Haverbeke and Herman (20Q). Phenol, o-cresol, and m.creso1 were determined in aqueous
solution by Raman spectrometry via derivatization with the diazonium salt of 4-nitroaniline. In natural waters, the detection level of phenol was 50-300 ppb, dependin on the characteristics of the water sample. Spectra of t e three henols were recorded to indicate the identification capaEilities of this technique. Spectrometric determination of aniline compounds in water is described by Ci (2Q). These materials are determined at 550 nm following treatment with sodium nitrite and coupling the product with N-(lnaphthy1)ethylenediamine dihydrochloridein acidic medium. Phenols interfere in this determination when present at concentrations above 200 mg/L. However, this interference can be eliminated by pretreatment throu h an anion-exchange resin. A low-level determination of hy razine in boiler feed water using an unsegmented high-speed continuous-flow system is reported by Basson and Van Staden (14). The continuous-flowsystem determines hydrazine spectrophotometrically at a rate of greater than 350 sample/h with a standard deviation below 1%. Kodura and Lada (118)described a spectrophotometric determination of caprolactam in water and wastewater. The method involves extraction with chloroform, hydrolysis to aminohexanoic acid by heating with hydrochloric acid, and color formation with ninhydrin. Absorbance measurements are made at 570 nm. Concentrations between 1and 75 mg/L can be determined. Determination of organofluorine compounds in water is reported by Kussmaul and Hegazi (12Q). Volatile fluorocarbons are stripped by an air stream, while nonvolatile fluorocarbonsare extracted with diisopro yl ether. Pyrolysis in a two-step combustion train, followecf by photometric determination of the hydrogen fluoride formed, furnishes total organofluorinecontent. The detection limit is 0.1 pg of fluorine. Parker (15Q)described an atomic absorption spectrometricmethod for determination of organosiliconcompounds in water. Hydrophobic and hydrophilic methylsiloxane compounds are extracted with a mixture of 1-pentanol and methyl isobutyl ketone. A method for the rapid detection of organic pollutants in water by vapor-phase ultraviolet absorption spectrometr is reported by Thompson and Wagstaff (198). Organic pol utants in water are detected following extraction with hexane. A small portion of the extract is placed in a graphite tube and slowly heated while the absor tion is monitored. Monitoring wavelengths of 190, 210, a n i 253.7 nm are used. A rapid routine method for quantitative determination of benzo[a]pyrene in water by low-temperature s ectrofluorimetry was studied by Monarca, Causey, and Kirkiri ht (14Q). The reproducibility of the method is adequate ancfthe time required for analysis is very brief. Karyakin, Anikina, and Pivovarov (1OQ) described a luminescence determination of simple aromatic compounds in water. Compounds determined include benzene, toluene, indole, phenol, aniline, diphenylamine, and tryptophan. The method permits direct determination of these compounds in water with a detection limit A fluorimetric group detection method for of 1 X polycyclic aromatic hydrocarbons on silica gel was optimized by Hellmann (9Q). Chromatographic determination of these aromatic hydrocarbons in water and wastewater gives detection limits well below 0.1 ng per compound. Analysis of hydrocarbons in the foam from water sluices also was reported b Hellmann (7Q). Analytical techniques suitable for the idrentification of surface water hydrocarbon pollution are discussed. The scope and limitations of techniques such as infrared spectroscopy and gas and thin-layer chromatography are discussed in relation to pollutant source identification. Griffith et al. (5Q)described a rapid and sensitive quantitative method for determining oil in water. Quantitative determination is made by a turbidimetric measurement. The method is sensitive to 0.5 ppm and is rapid and reasonably accurate. It is most useful when many samples must be run to determine when corrective adjustments are required. Hellmann (SQ) reported on the change of the fluorescence intensity of polycyclic aromatic compounds on thin-layer plates. The fluorescence intensity changes during the separation and subsequent holding time. Studies on silica and mixed layers of alumina and cellulose acetate reveal critical oints and potential error limits in analysis of drinking anzindustrial process water for polycyclic aromatic hydrocarbons. Richardson, George, and Ando ( I S Q ) described a sub-ppt detection of organics in aqueous solution by laser induced molecular fluorescence. Pulsed laser irradiation is a superior
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
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WATER ANALYSIS
excitation source for fluorescence analysis and is suitable for trace level organic determinations in water. Three different instrumental configurations are compared experimentallyand detection limits determined for selected organic compounds. Second-derivative ultraviolet absorption spectroscopy was applied as a method of trace organic determination in water and wastewater by Hawthorne et al. (6Q). Various methods for recording a second-derivative spectrum are presented, with examples of improved selectivity between compounds due to the enhanced resolution furnished by the second-derivative technique. Determination of organic substancesin water using structural phosphorescence spectra is reported by Sorokina, Anikina, and Karyakin (18Q). Interactions between organic molecules in an organic matrix at low temperature is observed mass % , This mainly consists a t concentrations of 1 X of energy transmissions from molecules of high-excitation states to those of lower excitation states. Interaction observed at high concentrations of substances does not interfere with luminescence determination of organic solutes in an aqueous solution. For analytical purposes concentration of organic substances to be determined should not exceed 1X mass % Application of Fourier transform infrared spectroscopy to the identification of trace organics in water is re orted by Gomez-Taylor et al. (46). The method describes t i e on-line identification of or anic water pollutants separated by gas chromatographya n t high-performance liquid chromatography followed by quantitative determination by dual-beam Fourier transform infrared spectroscopy. Organic pollutant solutes are concentrated on polystyrene resins, eluted with diethyl ether, and separated by chromatography. For GC-IR measurements, readily identifiable spectra can be obtained at a level of 2 ppb. HPLC-IR measurements are less sensitive and yield a detection limit in the submicrogram range. Two methods for ultraviolet spectrophotometric determination of lignosulfonic acid and humic acid in water were reported by Goetz (3Q). A rapid analytical method for determining asbestos concentrations in water was developed by Melton et al. (13Q). Asbestos was extracted from a water sample into an immiscible organic solvent phase. The two-phase liquid separation was combined with a light microscopic intercept counting technique and with a colorimetric spot detection technique, resulting in two complete rapid analytical methods. Limit of detection for the two-phase separation technique was 1.0 ng and for the spot test detection technique 100 ng. Schwarz, Braun, and Wasik (17Q)described an o!cillating sljt mechanism for the determination of hydrogen isotope ratio in a microwave-induced plasma. The method was used successfully for the determination of naphthalene in water samples.
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ORGANICS-EXTRACTION AND CONCENTRATION TECHNIQUES Chang and Fritz (5R) described a technique for the con-
centration and determination of trace organic pollutants in water. The pollutants are isolated on a mini-sampler tube containing XAD-2, thermally desorbed at 220 "C in a Tenax trap, and transferred to an analytical column, where they are separated and determined by temperature-programmed gas chromato raphy. Limit of detection is 0.1 ppb of organic compouni in a 15-mL water sample using a 1-ng detector sensitivity. Extraction of organic matter in water using Amberlite XAD-2 is reported by Schnare (24R). Sorbed organic compounds are recovered by elution with etherlacetone mixtures. A minicolumn procedure for concentrating organic contaminants from wastewater and contaminated drinking water was used by Tateda and Fritz (26R). The minicolumn containingXAD-4 resin or Spherocarb effectively sorbed many organic contaminants from a 1-L sample. The sorbed materials were eluted with 50-100 pL of organic solvent and subsequently separated by gas chromatography. A simple, portable apparatus for on-site extractions of organic compounds from water using Amberlite XAD or Tenax-GC resins is described by Stepan et al. (25R). Renberg (21R) reported on the determination of volatile halogenated hydrocarbons in water with XAD-4 resin. Determination of trihalomethanes, chloroethanes, and dichloroethane in water is done by adsorption on Amberlite XAD-4 followed by elution with ethanol. The method furnishes an extract concentrated enough for both chemical determination and small-scale biological testing. Ryan and Fritz (22R) determined trace organic im202R
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
purities in water using thermal desorption from XAD resin. A water sample is passed through a tube containing XAD-4. The sorbed organics are thermally transferred to a small Tenax-GC precolumn while the water vapor is vented. The precolumn is heated to 280 "C, and a vaporized sample is passed directly into a gas chromatograph for separation and identification. Five Amberlite XAD macroporous resins for the concentration and isolation of fulvic acid from aqueous solution were evaluated by Aiken et al. (IR). The capacity of each resin was measured by both batch and column techniques. Highest recoveries were obtained with the acrylic ester resins, which proved to be the most efficient for both adsorption and elution of fulvic acid. A Teflon helix continuous liquid-liquid extraction apparatus and its application to the analysis of organic pollutants in drinking water is described by Yohe, Suffet, and Grochowski (29R). The continuous liquid-liquid extraction is more effecient than batch-serial extraction. Variability of the final Kuderna-Danish evaporation step for volatile compounds limits the use of the s stem for quantitative measurement. Olufsen (18R)modifieBa Soxhlet apparatus technique, which permits adsorption of trace organic materials from water samples and their extraction with small solvent volumes, without drying-out of the resin bed. Peterson et al. (20R) reported on the direct insertion of a porous polymer ,trap by an injector attachment plunger into the heated injection port of a gas chromatograph,which results in rapid flash desorption of trapped volatile componentsdirectly onto the column. The technique is applied to trap ing volatile organic compounds from water samples. Enric ment and determination of polycyclic aromatic hydrocarbonsin water is reported by Faltusz (7R). Hydrocarbons in water are enriched rapidly and simply by precipitatin magnesium hydroxide in the sample, centrifuging, dissofving the solids in ammonium chloride, and extracting the organic compounds with a very small volume of cyclohexane. Analysis by electron capture gas chfomatogra hy without further concentration or purification is possiile. Sasaki (23R) described a spectrophotometric determination of strong chelating agents in water by the li and exchange extraction of the copper(I1) chelate with so&um diethyldithiocarbamate. The co per chelate obtained is extracted with carbon tetrachlori e and the absorbance measured. The use of Amberlite XAD-2 resin for the extraction of benzene hexachloride (BHC) isomers from water samples Four was reported by Yamato, Suzuki, and Watanabe (2%). BHC isomers added to distilled water at levels of 1.0,0.1, and 0.01 ppb were recovered at greater than 94% by using Amberlite XAD-2 resins. BHC residues were also detected in tap water and river water samples. Minimum detectability for total BHC in a 3-L water sample is 0.001 ppb. Korenman (12R)used macroporous ion exchangers for the extraction of small amounts of nitrophenols from water. The three nitrophenol isomers were determined in water by ion exchange chromatography and photometry. The detection limits reported were in the range of 0.02-0.06 mg/L. A comprison of headspace gas and liquid extraction determinations of hydrocarbons in water by the standard addition method is reported by Khazal, Vejrosta, and Novak ( I I R ) . The liquid-extraction method is more accurate but yields chromatograms with an interfering background resulting from the solvent itself. Sensitivity for volatile hydrocarbons in water is approximately the same for each method. Optimization of a gas stripping concentration technique for trace organic pollutants in water was studied by Colenutt and Thorburn (6R). Solutes were stripped from aqueous solution by a stream of inert gas and subsequently adsorbed onto activated carbon, from which they were extracted into a solvent for analysis, The method is applicable to a wide variety of pollutants including pesticides and polychlorinated biphenyls. Otson, Williams, and Bothwell (19R) conducted a comparison of dynamic and static headspace and solvent extraction techniques for the determination of trihalomethanes in water. Potable water samples containing trichloromethane and dibromochloromethane were analyzed in triplicate. Although the headspace technique was more sensitive, the solvent-extractiontechnique furnished comparable precision, while the headspace technique showed relatively poor precision and sensitivity. Friant and Suffet (8R)studied the interactive effects of temperature, salt concentration, and pH on headspace analysis for the isolation of volatile trace organics
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WATER ANALYSIS
in aqueous environmental samples. Effects between parameters are quantitatively shown by the use of the thermodynamic equilibrium partition coefficient. Optimum headspace analytical sampling conditions of pH 7.1 and 3.36% sodium sulfate were determined from a statistical design. Under optimum conditions, river and drinking water can be routinely profiled for volatile components. In a report by Lee et al. (14R)purging methods for the determination of organics in water are evaluated. Discussion centers around detector linearity, reproducibility of standards, and detection limits. Murray (17R) compared rapid microextraction procedures with macroextraction methods for the determination of trace amounts of organic corn ounds in water by gas chromato raphy. Burgasser and Co!kotolo (4R) extracted semivolati e and nonvolatile chlorinated organic compounds from water. The method utilizes a commercial homogenizer to completely emulsify a nonaqueous extraction solvent with the water to be analyzed, followed by centrifugation to separate the aqueous and organic phases, Recoveries in the 0.1-10 ppb range are greater than 85%. A continuous liquid-liquid extractor is described by Goldberg and Weiner (9R)for the concentration of phenols at the pg/L level from water into dichloromethane. Subsequent evaporation ermits concentration factors of 1 X 10" to he achieved. Soyvent extraction of phenol from water using salting-out a ents and organic reagents is discussed by Korenman and hortnikova (13R). The extraction of phenol from water with benzene or butyl acetate is enhanced when sodium chloride or sodium sulfate is added to the water. The most efficient extraction of henol from water is obtained when tributyl phosphate is a d e d to the benzene extractant. Adsorption of phenol from water and subsequent thermal desorption for gas chromatographic analysis is re orted by Voznakova and Pop1 (27R). Phenols are adsorbe8 from the aqueous phase onto macroporous olymer materials. Thermal desorption by heating was folrowed by direct introduction into a gas chromatograph. The method is suitable for the determination of phenols in water in the 1-1000 p b range. Mikhailov an! Oradolvskii (16R)studied methods for sampling seawater from the ocean's surface microlayer, and the reported results of determination of oil in various regions of the Atlantic Ocean. Nylon screen samplers are used for sampling the surface seawater. Hoffman (IOR)described a compact, variable volume, liquid-liquid extractor. Cancentric fixed tubes are arranged so that an extracting solvent percolates through a solvent of lower density and higher boiling point to be extracted. Typically, this solvent is water. The extractin solvent is then boiled and condensed to repetitively perco ate through the water. The apparatus permits the use of a variable volume of water and a small volume of extracting solvent. The use of ultrafiltration for the separation and fractionation of organic ligands in freshwater is reported by Buffle, Deladoey, and Haerdi (3R). Effects of experimental conditions on the use of membrane filters for the separation and fractionation of fulvic and humic substances in freshwater are discussed. A procedure for the concentration of nanogram amounts of hexachlorocyclohexaneisomers in water samples is described by Malaiyandi (15R). A Kuderna-Danish evaporator is modifed to include a built-in distillation trap below the condensing portion of the Snyder column. Mean recoveries for hexane solutions of hexachlorocyclohexaneisomers are substantially improved by this technique. The use of polyurethane foams for the extraction and recovery of aromatic hydrocarbons from water is reported by Basu and Saxena (2R). Flexible foam plugs effectively concentrate trace quantities of aromatic hydrocarbons from large volumes of finished and raw water when the water is heated to 62 "C and pumped at a flow rate of 250 mL/rrtin. Purification of the concentrate is achieved by solvent partitioning and column chromatography on Florisil. Limit of detection for each of the six hydrocarbons examined is 0.1 ng/L.
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ELEMENTAL ANALYSIS
An electrochemical determination of organic carbon in natural water was reported by Levina et al. (38). The method is based on the difference in hydrogen adsorption on platinum in the absence and presence of organic compounds. Optimum potential was chosen for the adsorption of organic materials on a platinum electrode. 'The dependence between the surface
characteristics and concentrationof the latter was established, and rules for the adsorption of characteristic organic compound classes were studied in detail. A gas chromatographic method for the determination of total organic carbon in water was investigated by Rezchikov, Kuznetsova, and Zorin (7s). Organic carbon is converted into methane by using an electrical discharge, followed by gas chromatographic determination of this material using a flame ionization detector. Limit of detection is 1 ng. An automated method for the determination of micro ram levels of or anic carbon in potable waters is discusse by Van Steen eren, Basson, and Van Duuren (11s). For practical applications, the lower limit of detection is of the order of 50 pg dm-3. Rigdon et al. (8s) described a computer-automatedtotal organic carbon analyzer. Organic carbon in a water sample is determined by injection through a septum into a combustion furnace, where oxygen carrier gas is used to convert all the carbon to carbon dioxide which is determined b infrared absor tion measurements. Gloor and Leidner (1Syinvestigated a etector based on the principle of measurement of organic carbon as carbon dioxide which is ap licable to liquid chromatographic monitoring of organic carion in water. Minimum detectability for organic carbon by this technique is 3 X lo4 g/mL. Chromatographic applications are discussed which involve the use of both reversed-phasecolumn materials as well as Sephadex gels. The detector is restricted to use of nonorganic mobile-phase solvents. Seto (9s) described a method for determination of total organic carbon by wet oxidation-nondispersive infrared gas analysis in natural waters, wastewaters, and sewage. Water samples are treated with phosphoric acid and subsequently converted to carbon dioxide by using potassium persulfate with silver nitrate catalyst. The calibration curve is linear over the range of 0.5-5000 pg of carbon. An automatic instrument for simultaneousdetermination of total nitrogen and total or anic carbon in water is reported by Miyagi et al. (5s). An acicftreated sample is introduced into a deaeration tube where dissolved nitrogen and inorganic carbon are removed by extraction into the carrier gas. The deaerated sample is then injected into a combustion tube. Following removal of steam, a portion of the gas is introduced into the reaction tube which is packed with copper filin s. Nitrogen and carbon dioxide are subsequently analyzef by gas chromatography. Lower limits of detection are 0.6 and 0.2 ppm for total nitrogen and total organic carbon, respectively. Another gas chromatographic procedure for the determination of total nitrogen and total organic carbon in water is discussed by Oi et al. (6s). Total nitrogen and total carbon are converted into nitrogen and carbon dioxide in a stream of carrier gas in a reaction tube packed with aluminum oxide coated with palladium. Following removal of steam, oxygen, and h drogen from the gas stream, nitrogen and carbon dioxide are &ermined. Inorganic carbon is converted intocarbon dioxide by ion-exchange resins containing sulfonic acid groups and analyzed by as chromatography. Total organic carbon is determined by Cfzference. When using a 20-pL sample, detection limits are 0.5 mg/L for both total nitrogen and total carbon. McCahill, Conro and Maier (4s)described the determination of organicalg combined chlorine in high molecular weight aquatic organics by preconcentratin the sample, yrohydrolyzing the organics to liberate organic cklorine as hycl!&Aoric acid, and measuring inorganic chloride. An improved automatic liquid-in'ection apparatus for use on a carbon analyzer was developed by Van Steenderen (10s). This report describes the interfacing of a fully automatic sample injection apparatus to a commercial carbon analyzer. The automatic analyzer is nonspecific but suitable for basic monitoring or screening of water samples. An analytical method for dissolved organic carbon fractionation is presented by Leenheer and Huffman (2s).Macroreticular resins are used to fractionate the organic carbon in a water sample into acid, base, and neutral hydrophobic and hydrophilic organic solute fractions. Applications of dissolved organic carbon fractionation analysis range from field studies of changes in water quality to fundamental studies on the nature of sorption processes.
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ORGANICS-OXYGEN
DEMAND
S e e r et al. (5r) discussed methods for the determination of ultimate carbonaceous BOD. Measurements of dissolved oxygen concentration made at 12 to 15 h intervals during a ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
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WATER ANALYSIS
5 to 7 day incubation period provide adequate definition of the rate of carbonaceous oxygen demand. The use of a nitrification inhibitor is recommended for effluent samples which are partially nitrified. Korenaga (47') described an apparatus for measuring COD based on flow injection analysis. A solution of potassium permanganate in sulfuric acid is pumped into a manifold to which 20 pL of water sample is introduced. Following reaction, the absorbance is measured in a spectrophotometer at 525 nm. A sampling rate of 120 samples h is achieved by this technique. Hime augh and Smith (27') determined COD in water by titrimetry following digestion in semimicro Pyrex glass tubes. The tube method is reported to compare favorably to other standard methods with respect to precision, accuracy, simplicity, and safety. The determination of BOD by a coulometric method in which the consumption of oxygen is measured was studied by Gantner (17'). A water sample is added to a closed system maintained at 20 "C, which includes the anodic compartment of a water electrolysis cell. The coulometer is controlled by a mercury switch which responds to change in pressure of the system. Switching times of the coulometer are transmitted to a recorder, so that the plot shows the intensity of the biological growth in relation to time. Klein and Gibbs (37') described a graphical method for calculating BOD by plotting a graph of dissolved oxyFen remaining after incubation in a series of raduated dilutions vs. volume of sample added. The metho offers several advantages: it corrects for blank and seed automatically and does not require separate tests to determine values. It allows use of diluted water with a demand of less than 0.5 mg/L, and it also reduces the number of dissolved oxygen determinations because initial DO values are not required for calculation. In a report by Wa ner (657, practical aspects of the determination of BODgbased on the results of a broad survey are discussed.
i:
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ORGANICS-MISCELLANEOUS An overview of the determination of trace or anics in water is presented by Trussell and Umphres ( 1 1 d Keith (5U)
furnished a list of organic compounds which can be used as models for organic trace pollutant determinations in water. Garrison et al. (2U) described an automatic sampler, a master analytical scheme, and a registry system for organics in water. The sampler can concentrate as many as 14 samples simultaneously for organic determination. The developmentby the EPA of a comprehensive data collation and retrieval system for organics in water is also discussed. The determination of chlorinated long-chain araffins in water, sediment, and biological sam les is reporte by Hollies, Pinnington, and HandIey (4U). Alysamples are prepared by liquid-solid adsorption and thin-layer chromatography. The methods distinguish between chloro-n-paraffins based on length of carbon chains. Sensitivities range from 500 ng/L to 8 pg/L for water samples. Recoveries average about 90% for water. A method for the detection of algogenic substances (polysaccharides) in eutrophic dam waters is described by Lochtman, Reichert, and Bernhardt (8U). Polysaccharides are identified by colorimetric procedures using glucose and gluconic acid standards. Molecular weight determinations are done by gel chromatography using dextran as a comparison standard. Sharma et al. (9U) compared the determination of cobalamins in ocean waters by radioisotopic dilution and bioassay techniques. Isotopic dilution techniques furnish results which are approximately4-10 times higher than results obtained by microbiological assays. The authors suggested that the former technique measures both biologically active and inactive cobalamins indiscriminately. Sensitivity of the isotopic method is in the range of 0.5-400 pg of vitamin B1 mL. dreservation of seawater samples for the determination of carbohydrate content is discussed by Hirayama (3U). The use of new polyethylene vessels for preservation and storage of water samples for carbohydrate determination is recommended, Uchiyama and Yamaguchi (14U) described a method for the determination of formaldehyde in water. Formaldehyde is distilled, extracted with chloroform, and determined fluorometrically. An improved method for the determination of adenosine triphosphate (ATP) in environmental samples is reported by Tobin, Ryan, and Af han (IOU). ATP is determined by enzymatic reaction using uciferin as
cp
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
the substrate and luciferase as the enzyme. Optimization of parameters for the enzyme chemistry is discussed. Leonova, Belen'kii, and Klyachko (6U) described a titrimetric determination of ascorbic acid in the presence of iron in mineralized waters. Ascorbic acid is determined by iodometric titration in the presence of sulfuric acid at pH 0.06-0.08. The method is reported to be suitable for natural waters containing less than 36 mg/L of ferrous iron. Burkhard and Armstrong ( I U ) described a modified perchlorination procedure for the determination of polychlorinated biphenyls (PCB). The technique permits quantitative recovery of PCBs containing low or high numbers of chlorine atoms substituted on the biphenyl structure. Determination of nitrobenzene in ground water by pulse polarography is reported by T u (12U). Optimized polarographic conditions for this analysis are discussed. Minimum detectability is reported to be 5 ppb. The se aration and determination of mineral, animal, and ve etab e oils in water using molecular sieve 5A is discussed \y Uchiyama (13U). Oils are separated and determined by infrared spectroscopy. Following extraction with carbon tetrachloride, the sample is treated with molecular sieve 5A. Mineral oils are not adsorbed onto the sieve, but animal and vegetable oils are. Infrared examination of the carbon tetrachloride extract by measurement of the absorption peak at 2950 cm-' is used for quantitative measurement. Lium and Shoaf (7U) discussed the use of magnesium carbonate as a preservative in chlorophyll determinations.
f
PESTICIDES Rogovskiy, Minenko, and Pastushenko (40V) described a colorimetric procedure for the determination of 3-methyl-4methylmercaptophenol,an intermediate in fenthion synthesis, in water. Silicomolybdicacid is added to a water sample which is mixed with ammonium hydroxide solution, and the absorbance of the resulting blue solution measured. Beer's law is obeyed between 2.5 and 35 mg/L with a relative error of f3.7%. Methods of analysis of natural water samples containin trace levels of chlorpyrifos-methylwere developed by Blancget (6V). Instrumental analysis em loyed flame photometric gas chromatography, to yield a gtection limit of 1 ppb. The efficiency of extraction approached 100% for the water samples examined. Blanchet (5V) also described a general method for the extraction, preservation, and analysis of aqueous solutions of 16 organophosphate insecticides. Extraction involved high-speed stirring following addition of a small volume of hexane. Loeberin ,Weil, and Quentin (29V) used a as chromatographic rocefure for the determination of resifue levels of eight car amate pesticides in water. Extraction is accomplished with methylene chloride, ethyl acetate, or a mixture of toluene and ethyl acetate. The dried extract is subjected to trifluoroacetylation followed by electron capture gas chromatography. The method is applicable to concentrations between 5 and 50 ng/L in drinking or nonpolluted ground water. Fritschi, Fritschi, and Kussmaul (21V) presented a microcoulometricmethod for the determination of total organochlorine compounds in water. Nonvolatile materials are extracted with diisopropyl ether and volatile materials directly transferred by a nitrogen stream from the water sam le into the combustion oven. Total nonvolatile and volatiPe organochlorine compounds are determined by microcoulometric detection of the chloride ion formed by combustion. The utility of Amberlite XAD-2 as the extractant for carbamate insecticides from natural water was studied by Sundaram, Szeto, and Hindle (51V). The carbamates were extracted by percolation through a column of XAD-2 followed by elution with ethyl acetate. Residues were directly analyzed by GLC using a nitrogen/phosphorus selective detector. Recoveries for several carbamates spiked at the 1and .01 ppm levels ranged from 86 to 108%. Only 41-58% of the methomyl was recovered. A liquid chromatographic procedure for the determination of fenitrothion in water was reported by Takaku, Otsuki, and Takahashi (52V). A glass bead coated with diphenylsilane was used for adsorption of the pesticide from water. Fenitrothion was eluted out as a sharp band by a linear gradient of &-loo%acetonitrile in water. The UV detector response, measured at 280 nm, was proportional to the amount injected in the range from 0 to 800 ng. Recoveries from fortified distilled and pond water samples were 97% and 96%, respectively. Mallet, Francoeur, and Volpe (32V) evaluated the
%
WATER ANALYSIS
use of XAD-4 resin for the recovery of fenitrothion from distilled water. Variables studied include GC flow rates, column lengths, extraction methods, sample volumes, concentrations, and elution solvent flow rates. The advantages of XAD-4 over XAD-2 include accelerated flow rate, greater retention capacity, and ability to be regenerated and reused. The use of membrane Blters for the residue analysis of water for chlorinated pesticidies and PCBs was reported by Kurtz (27V). Pesticide residues were separated by chemisorptipn on cellulose triacetate membrane filters and were eluted wlth ether. Capacity-load factors and recovery data, along with pH dependence, were also discussed. Infrared spectroscopic determination of dichlorvos in water is described by Ershova, Komarova, and Shitukhina (19V). Dichlorvos is extracted with carbon tetrachloride, saturated with sodium chloride, and determined by infrared absorbance measurement between 1000 and 1200 cm-'. The relative error is *5% at a sensitivity of 1mg/L. Rees and Au (39V)report recovery data for several classes of esticides recovered from water samples using small XAD-2 coyumns. Concentrations range from 0.001 to 50 ppb. In a re ort by Schulten and Stoeber (44V) carbamate and thiocar!amate pesticides isolated from water are separated by HPLC and identified by low- and high-resolution field desorption mass spectrometry. Reliable identificatioa is achieved on purified river water extracts at levels down to 10-20 ppb. Yamato, Sumuki, and Watanabe (55V) reported on the extraction of BHC isomers from water samples usin a macroreticular resin. Four BHC isomers were recovere from distilled water spiked at levels between 1.0 and 0.01 ppb usin an Amberlite XAD-2 resin at greater than 94% recovery. GLtwith an electron capture detector was used for separation and identification. Minimum detectability for total BHC in a 3-L river water sample was 0,001 ppb. LaBel et al. (28V) developed a screening method for the determination of oranophosphorus pesticides in drinking water at ng/L levels. &he compounds are extracted by Amberlite XAD-2 resin from 100 to 200 L of drinking water and recovered by elution with acetone-hexane. Separation is achieved by GLC using a nitrogen/phosphorus selective detector. Recoveries exceeded 90% for samples spiked at the 10-100 ng/L level. Modification of batch extraction methods and the use of capillary columns for routine analyses of low levels of chlorinated insecticides was reported by Brodtmann and Koffskey (8V). Wall-coated open tubular columns coated with SE-30, having no less than 150000 effective plates, were used. Recoveries of insecticides ranged from 67% to 95% with minimum detectability on the order of 0.5 pg. Progress in the automation of pesticide residue analysis is described by Getz, Hanes, and Hill (22V). Their system automatically indexes, blends, extracts, pumps, partitions, concentrates, and chromatographically refines the sample. Analyses are described on samples of vegetable, animal, and mineral materials fortified with selected insecticides at the 1 pg/g level. A gas chromatographic method for the determination of chlorphoxim in water is presented by Zakitis (57V). In a report by Solomon (49V)an improved method for cleanup of small sample extracts is described for use in the determination of chlorinated pesticides. The method is more rapid and requires smaller quantities of chromatographic materials and solvents than other procedures. Percent recoveries from spiked water samples raqged from 69 to 98%. An application of lyophilization to analytical preconcentration of organophosphate insecticides in water is described by Bargnoux et al. (2V). Samples containing mixtures of insecticides with and without bicarbonates added are analyzed by thin-layer and gas chromatography before and after freeze-drying and the results compared. Samples containing bicarbonate exhibited analytical losses substantially greater than without bicarbonate. Kucher, Ralkov, and Sapegin (26V) described a modified assay for the determination of organochlorine pesticides in the brines of saline lakes and estuaries. The technique consists of repeated extraction of brine samples with hexane followed by thin-layer chromato raphic separation in and below the the presence of standards at a level suspect sample. Analysis of soil and sediment to determine potential pesticide contamination of a water-supply impoundment was reported by Amore ( I V). Insecticides, miticides, and fungicides were determined in soil, sediment, and water by gas chromatography with electron capture detection. Devenish
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stove
and Harling-Bowen (16V)have examined and estimated the performance characteristics of a standard method for organochlorine insecticides and PCBs in water. A water sample is extracted with hexane and the extract concentrated to a small volume. Coextracted materials are removed by passing the concentrate through columns of alumina and alumina impregnated with silver nitrate. The purified extracts are further concentrated and examined by gas or liquid chromatography, New column technology for the determination of or anics in water by gas chromatography is described by Minfrup (34V). Details of the gas chromatographic parameters for the separation of selected organic compounds which are included under the Safe Drinking Water Act are discussed. Applications to chlorinated insecticides and polychlorinated biphenyls are included. Chmil' (9V)has reported on the combined use of thin-layer chromatography and infrared s ectroscopy for identification of organochlorine pesticides ancftheir determination in water. The ap licability of the procedure to DDT and to several chloroptenoxy acid herbicides is demonstrated. Zhu et al. (58V) have re orted on a preliminary investigation of the analytical metgods for organochlorine pesticides in water a t the ppt level. A water sample is extracted with hexane and treated ultrasonically, and the hases are se arated. The dried extract is concentrated, ande!t compound)s are separated by gas chromatography. Preconcentration techniques employing lyophilization and their applicability to determination of or anothiophosphate esticides in water have been evaluated y Bargnoux et al. 3V). Water solutions of parathion, malathion, dichlorvos, and diazinon were lyophilized prior to quantitative analysis. While lyophilization stabilizes the samples and permits extended storage, it also yields concentration suitable for quantitative analysis. A procedure for thin-layer chromatographic determination of pirimicarb and pirimiphos-methyl was reported by Krasnykh (WV). Water samples are extracted with chloroform, followed by cleanup on a chromatographic column. TLC visualization is accom lished in UV light or with bismuth nitrate and potassium i o i d e in sulfuric acid. Sensitivity is of the order of 2-3 pg sample, with recoveries between 83 and 97%. Otsuki and akaku (37V) have reported on the determination of the organophosphate insecticide, abate, in water at the ppb level by reversed-phase adsorption liquid chromatography. Abate is trace-enriched from a water sample on a bonded-bead column and eluted as a sharp peak by a linear gradient. Recovery from distilled water and fiitered pond water was between 97 and 101% at the 0-150 ng level. Handa (23V) has described a spectrophotometric determination of carbofuran residues in water. The method is based on the reaction of carbofuran phenol with nitric acid to form a colored compound with an absorption maximum at 345 nm. The method is applicable to residues in water extracts in the range of 10-150 pg/mL. DiPrima et al. (17V) reported on a method for the determination of diflubenzuron residues in water. The procedure involves liquid-liquid partition, florisil/alumina/silica gel cholumn chromatograph , and high-pressure liquid chromatographic separation andrdetection. Minimum detectability for diflubenzuron residues in water is 0.01 ppm. The determination of residues of benzyl and polyethyleneglycolesters of 2,4-D in water was investigated by Chmil' et al. ( I I V ) . Following extraction with diethyl ether, the esters were hydrolyzed to the free acid and methylated with diazomethane following addition of 2,4,5-T as internal standard. Hexane extracts were then obtained for gas chromatographic analysis with electron capture detection. Limit of detection is 2 and 5 pg L for the benzyl and polyethyleneglycolesters, respective y. Thin-layer and gas chromatography, ultraviolet spectrophotometry, and bioassay techniques were used by Bowmer and Adeney (7V) to investigate the pathway of degradation of diuron to hytotoxic derivatives. Results and 1suggested that 1-(3,4-dich~ropheny1)-3-methylurea (3,4-dichloropheny1)ureamade a contribution to total residues equivalent to a maximum of about 40% and 55%, respectively, of diuron concentrations. The authors also concluded that measurement of diuron alone would underestimate the total phytotoxicity of residues by a maximum of about 7%. Stoeber and Reupert (50V) report an analysis of phenylurea herbicides involving two extractions of the water sample with chloroform, followed by selective separation by gradient elu-
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
205R
WATER ANALYSIS
tion chromatography on silica gel columns. Further purification is required in order to remove less polar components from the sample. Fractions are then analyzed by HPLC usin two different columns. Individual components are identifie1 by field desor tion mass spectrometry with a minimum detectability of &out l ng. Matisova, Krupcik, and Liska (33V) described the quantitative analysis of triazine herbicides by glass capillary column gas chromatography. Separations are achieved on a Carbowax 20M column using flame ionization and alkali flame ionization detection. Limits of detection are 5-10 ng of triazine, with an inlet-splitting ratio of 1:90 for the FID, and 50-70 pg for the AFID, at an inlet-splitting ratio of 1:20. A simplified hydrolysis rocedure for the determination of residues of urea herbicigs was reported by Sholten e t al. (42V). Advantages of the catalytic hydrolysis technique are simplicity, avoidance of the use of hazardous chemicals, and excellent reproducibility. Analysis of water samples containing 20 ppb herbicide presented no problem. Schulten (43V) investigated the field desorption mass spectrometric properties of selected phenylurea herbicides. The spectra show high molecular ion intensities and characteristic fragmentation patterns. The optimal methodological parameters for trace analyses of these compounds by low- and high-resolution field desorption mass spectrometry are described. Application of field desorption mass spectrometry to the identification of selected herbicides in river water was examined by Yamato, Suzuki, and Watanabe (56V). Sackmauerova and Kovac (41V) described a thin-layer chromatographic method using the Hill-reaction inhibition detection technique for the determination of triazine and urea herbicides in water. The most efficient solvent system is toluene-acetone, in which all herbicides with the exception of propazine and monolinuron are ade uately separated. Recoveries reater than 95% are achieve% for the 11 triazine and urea kerbicides tested. An analytical procedure for the determination of residues of oryzalin in water-sediment mixtures a t the 1 ppb level is described by Smith and Willis (46V). Following derivatization, no cleanup by column chromatography is required prior to gas chromatographic separation and analysis. In a report by Lott, Lott, and Doms (31V),various methods for the determination of paraquat residues are reviewed. For paraquat determinations on food-stuffs, crop residues, soil, and water, and in body fluids, colorimetric methods are sug ested. Paraquat has also been determined by HPLC, GL8, and TLC rocedures. The determination of paraquat residues in water y! a gas chromatographic procedure is described in detail. A one-dimensional thin-layer chromatogra hic method is described for the analysis of glyphosate an its major soil metabolite, aminomethylphosphonic acid, by Ragab ( 3 8 9 . A methanol-water solvent system is used for the development of the thin-layer chromatogram. Visualization agents include ninhydrin-copper nitrate or ninhydrin-Rhodamine B. The procedure is applicable to agricultural run-off water at a minimum detectability of 100 ng glyphosate and 50 ng of its metabolite. A gas chromatographic method for the simultaneous determination of nitrofen and neburon in natural water samples was described by Deleu and Copin (15V). The samples were extracted with chloroform and evaporated just to dryness and the residue taken up in 5 pL of benzene. Nitrofen was detected down to a level of 2.5 f 0.25 pg and neburon at levels of 100 f 5 pg. The use of gas chromatography for the determination of suffix residues in water is reported by Chmil' et al. (12V). The limit of detection for suffix is 1ng, with a method sensitivity of 0.002 ng L. Copin et al. (13V) have investigated the extraction an gas chromatographic determination of the herbicide neburon and its metabolite, 3,4dichloroaniline, in natural waters. Determination of selected chlorophenoxy acid herbicides in water by gas chromatography is described by Chmil' and Klisenko ( 1 O V ) . Both acids were analyzed as methyl esters on each of two columns of different polarities. Moseman et al. (35V) described a rapid and simple procedure for the confirmation of nanogram quantities of kepone in environmental samples at ppb levels. Electron capture gas chromatography of the perchlorinated derivative permits identification which often is not possible by gas chromatography/mass spectrometry. Conversion of kepone is accomplished by a high-temperature closed-tube reaction. Mirex that might be present in the original sample extract is removed
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
from kepone by a micro-Florisil column cleanup step. The conversion of kepone to mirex is quantitative, thus allowing for estimation of ke one residues by a separate technique. Soderquist and Crosgy (48V)discussed an analytical method for the simultaneous determination of triphenyltin hydroxide and its possible degradation products tetraphenyltin, diphenyltin oxide, benzenestannoic acid, and inorganic tin in water. The method is rapid, sensitive to less than 0.01 fig/mL for most of the tin species, exhibits no cross-interferences between the phenyltins, and requires no elaborate equipment. Phenyltins are detected by electron capture gas chromato raphy following conversion to their hydride derivatives, whifi inorganic tin is determined by a procedure which responds to tin(1V) oxide as well as aqueous tin(1V). The determination of halogenated anilines and related compounds by HPLC with electrochemical and UV detection is reported by Lores, Bristol, and Moseman (30V). The procedure employs solvent programming. A more sensitive but more complex method based on the use of an electrochemical detector is also described. Compounds examined include aniline, 2-amino-4-ch1oropheno1,p-chloroaniline, bromoaniline, m-chloroaniline, o-chloroaniline, and 3,4-&: chloroaniline. Dawson et al. (14V) described a method for the determination of the lampricide diclosamide in stream water. The pesticide is extracted from acidified water samples with chloroform and hydrolyzed to 2-chloro-4-nitroaniline. This material is diazotized with sodium nitrite, and an azo dye formed with N-(1-naphthy1)ethylenediaminedihydrochloride. There is no observed interference from the lamStandard curves are pricide 3-trifluoromethyl-4-nitrophenol. prepared with untreated water to compensate for interferin substances that occur naturally in some streams. The metho8 is sensitive to about 0.005 mg/L. Smyth and Smyth (47V) prepared a review of the applications of polarographic and other voltammetric methods of analysis for foreign organic compounds in environmental samples. Materials discussed include disulfides, dithiocarbamates, sulfur oxides, nitrogen oxides, amines, amides, heterocyclic N compounds, aldehydes, ketones, phenolic compounds, organic acids, alcohols, su ars, halogenated compounds, organophosphorus compounfs, and organometallic compounds. A new instrumental technique for the determination of pesticide residues in water was described by Kadaba et al. (24V). A nuclear double-resonance spectrograph was designed and constructed with emphasis on quadrupolar nuclei of half-integral spins. The use of data acquisition and processing systems featuring the analog/digital converter and signal averager with built-in fast Fourier transform hardware greatly improved the signal to noise ratio. The spectrograph was used to detect organochlorine, carbamate, and triazine pesticides at the 15-100 fig/L level. Measurements are carried out below ice temperature, so heat-labile compounds can be detected without conversion to more suitable derivatives, as required in gas chromatography. Further improvement in sensitivity is possible by using a liquid-nitrogen cooled electromagnet, by increasing the polarizing field, and by reducin receiver recovery time. Singh, Cochrane, and Scott ( 4 5 8 reported on a procedure for extractive acylation of ethylenethiourea (ETU) residues from water. ETU is partitioned into an organic phase a t room temperature and dissolved in acetonitrile, derivatizing agent in methylene chloride is added, and the layers are allowed to separate. The methylene chloride layer is passed through sodium sulfate and evaporated to dryness and the residue taken up in benzene and analyzed by electron capture gas chromatography. The method is suitable as a rapid screening technique for ETU residues a t the 0.01-0.05 ppm level. Dressler (18V) discussed the extraction of trace amounts of organic compounds from water with porous organic polymers, He describes a concentration technique based on desorption of or anic compounds from porous polymers. The principles o f t e method, the characteristics and applications of various types of sorbents, and the quality requirements for the materials used are discussed. Applications to pesticides are included. Veith, Austin, and Morris (54V) developed a technique for the estimation of log P of organic chemicals that is both rapid and inexpensive. In a (2-18 reversed-phase HPLC system, the logarithm of the retention time (log R n is linearly related to the logarithm of the n-octanol water partition coefficient (log P). The log P may be estimated with a mean accuracy
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WATER ANALYSIS
of 22.8% of log P levells previously calculated by using a calibration mixture. Furthermore, this technique allows an estimation of log P values in less than 25 min, with a knowledge of the chemiical structure of the compound not re uired for the estimate. method for the determination of trace organic pollutants in water by proton magnetic resonance (lH NMR) spectroscopy of solvent extracts was described by Becconsall (4V). Extraction with carbon tetrachloride, followed by 'H NMR using a pulsed Fourier lxansform spectrometer with external field frequency lock, was investigated as a method for identifying and determining trace organic pollutants in water. The method is useful for all hydrogen-containing com ounds that are efficiently extracted by the solvent, incluiing hydrocarbons, halogenated hydrocarbons, and organochlorine pesticides. Measurements were made over a wide range of concentrations, from heavily polluted effluents to waters containing as little as 15 pg/L of alkanes. A method for the measurement of pentachlorophenol in estuarine environments is described by Faas and Moore (20V). Gas chromatography is used to determine PCP residues as low as 0.01 ppm by formation of the ethyl diazohydrocarbon derivative, followed by Florisil cleanup. Seawater concentrations as low as 0.002 ppb may be detected by formation of the amyl diazohydrocarbon derivative. Formation of the am 1derivatives of PCP and several related compounds give 6 L C separations not possible with the methyl or ethyl derivatives. A microextraction procedure for the determination of trace organic compounds in water is reported by Murray ( 3 6 0 . The extraction flask containing 980 mL of water and 200 pL of hexane is manually shaken for 2 min. The solvent layer is held in the center portion and displaced into a capillary tube. The recovered material is suitable for direct analysis by gas chromatography. The rnicro method offers superior concentration factors, elimination of a concentration step, and speed of analysis which is advantageous in routine quantitative analysis. Thompson and Wagstaff (53V) described a novel method for the rapid detection of organic pollutants in water utilizing vapor-phase ultraviolet absorption spectrometry. Water samples are extracted with hexane or chloroform and a small amount of the extract placed in a graphite tube, which is slowly heated, while the absorption of the sample is monitored. For optimum sensitivity of most substances a wavelength of 190 nm was chosen. Each tirace can be completed within 2 min, and the technique responds to many substances that are difficult to characterize or detect by gas chromatography.
%.
DETERGENTS A method for the determination of alkyl benzenesulfonates in river water by gas chromatography/mass spectrometry techniques has been described by Hon-Nami and Hanya (5Wq. Methylene blue-alkyl benzenesulfonate complexes are extracted into chloroform, the methylene blue removed, and alkyl benzenesulfonates converted to methylsulfonate derivatives by treatment with phosphorus pentachloride and methanol. Individual components are determined by mass fragmentography. Minirnum detectability in river water is less than 3 pg/L. Otsuki and Shiraishi (7W) have reported on the determination of poly(oxyethy1ene)alkylphenylether nonionic surfactants in water at trace levels by reversed-phase adsorption liquid chromatography and field desorption mass spectrometry. Recovery of these materials from spiked water samples was greater than 96% a t the 1mg/L level and 71% a t the 50 pg/L level. Extractional spectrophotometric determination of anionic E#urfactantsin water with Remacryl Blue B and Remacryl Red BL is the subject of a report by Yaneva and Borisova-Pangarova (8W). Using these dyes the detection limit for lauryl eulfate was 14 pg/L with a standard deviation of 1p g / L . Chlebicki and Garncarz (1W) have examined the determination of nonionic detergents in water and sewage by atomic absorption spectrophotometry. The method is based on the formation of insoluble complexes of nonionic detergents with phosphomolybdic acid in the presence of barium chloride. Hellmann ( 4 W ) has reported on the detection and determination of anionic surfactants in waters and wastewaters by infrared spectroscopy. Preliminary separation of impurities by thin-layer chromatography permits infrared spectroscopic determination at concentrations of less than 0.04 mg/L.
Gagnon (3W)has described a rapid and sensitive method for the determination of anionic detergents in natural water a t the ppb level. The method was developed by using atomic absorption spectrophotometry and copper ethylenediammine. It is suitable in the concentration range of 0-50 pg/L, with a minimum detectability of 0.3 pg/L. The reaction mechanism involved in the determination of nonionic surfactants in water as potassium picrate active substances has been studied by Favretto, Stancher, and Tunis (2W). The reactivity of the analytes toward the reagent is discussed qualitatively by considering the equilibrium processes involved in the extraction. A method for correcting additive interferences which occur during a surfactant determination in water is the subject of a report by Le Bihan and Courtot-Coupez (6W). The method can be applied to cases where the procedure involves subtraction of two values of the measured parameter proportional to the concentration of the species to be determined.
MISCELLANEOUS A portable analyzer was developed by Shaw (14X) for the determination of hydrogen peroxide in natural water, using the chemiluminescence reaction of luminol and hydrogen peroxide, with K,Fe(CN) as the catalyst. Interfering compounds were removed by ialysis, and hydrogen peroxide was determined a t concentrations equal to or greater than 0.02 mg/L. The construction and evaluation of a Babington-type pneumatic nebulizer for use in ICP-AES analysis of natural water is described by Garbarino and Taylor (6x1.The performance of the nebulizer is relatively insensitive to suspended particulate matter, and detection limits are equivalent to or better than those achieved with other pneumatic nebulizers. An analysis system was developed by Taylor and Erdmann (15X) to automatically determine specific conductance on samples at the rate of 30 samples/h over a range of 1to 15000 pmho/cm with a precision of 1%or less. The custom-designed electronic circuitry permits automatic range switching of the meter so that measurements are made under optimum conditions. Test and evaluation results are reported by Peterson et al. (13X) for a general purpose, portable, water-quality system designed to measure temperature, electrical conductivity, pH, and dissolved oxygen to depths of 30 m. A system description and performance results are provided. Henriksen (8X) provided a quantitative measure of early freshwater acidification by measuring the excess sulfate concentration, pH-calcium, and calcium-alkalinity relationships. A direct method involving a single iteration is given by Keir ( 9 X )for the calculation of carbonate concentration from total carbon dioxide and titration alkalinity. The simplified calculation should allow wider use of existing total carbon dioxide and alkalinity data. On the basis of statistical evaluation, Funk ( 5 X ) suggests specific sample preservation techniques for COD, BODB,TOC NO;, NOz-, NH4+, total N, organic N, P o l - , total P, S042-: Cl-, detergents (anionic and nonionic), and organic acids. The preservation of stream samples containing NO -,NH4+,organic nitrogen, soluble inorganic and organic PO)-, S2-,CN-, and F- was studied by Chakrabarti et al. (3K). The preservation techniques involved chilling a t 4 "C and (or) the addition of HzS04 or CHC13. It was concluded that NH4+,NO3-, and soluble inorganic and organic PO>- are preferably preserved with H2S04,S2- with zinc acetate, and CN- by any method other than H SO4. General and specific contamination factors affecting accuracy of results in heavy metal determination at the trace level by voltammetric analysis are evaluated by Mart (lox,11X). Precautions to prevent contamination in the laboratory and recommended practices to ensure a satisfactory elimination of contamination are discussed. Sampling procedures for preventing contamination during base line studies of trace metals in waters are also given. A procedure is described by Boutron ( 2 X ) for the preconcentration of very dilute solutions at the g/g level by nonboiling evaporation in Teflon bulbs in the presence of HF and HNOB under clean room conditions. The 14 metals are determined by flameless AAS; calibration curves are developed by variable variance techniques. Hall and Godinho ( 7 X ) investigated the concentration of trace metals from natural waters by freeze-drying prior to flame atomic absorption spectrophotometry. They concluded that it is as effective as solvent extraction or chelating ion exchange for concentration
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ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
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of Fe, Mn, Ni, AI, Cr, Cu, and Cd. Preparation of water samples for asbestos fiber counting by electron microscopy was discussed by Chatfield, Glass, and Dillon (4X). Filtration problems when using polycarbonate filters were solved, and an optimum filtration technique was developed that permits microscopically uniform deposits to be obtained. Pakalns, Batley, and Cameron (12X)investigated the effects of surfactants on the concentration of heavy metals from natural waters on Chelex-100 resin. Heavy metals can be separated on Chelex-100 in the presence of cationic, anionic, and nonionic detergents, washing powder, and sodium tripolyphosphate; however, recoveries are poor in the presence of soap or nitrilatriacetic acid. An inert, dense fluorocarbon solvent, FC 78, was examined by Batley and Giles ( I X ) for the displacement by centrifugation of sediment interstitial waters prior to trace metal analysis. Experiments showed that the solvent did not extract organic compounds or heavy metal species from the interstitial water sample. LITERATURE CITED INTRODUCTION
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(6B) Gine, M. F., Zagatoo, E. A. G., Bergamin Fiiho, H., Analyst (London), 704, 371-5 (1979). (78) Hayashi, K., Sasaki, Y., Tagashira, S.,Harada, K., Okamura, K., Bunseki Kagaku, 27,336-43 (1978); Chem. Abstr., 90,33422a (1979). (8B) Hydes, D. J., Anal. Chem., 52, 959-63 (1980). (9B) Korenaga, T., Motomlzu, S., Toei, K., Anal. Chim. Acta, 104, 369-77 (1979). (1OB) Korenaga, T., Motomizu, S., Toel, K., Talanta, 27,33-8 (1980). ( I l B ) Korenaga, T., Motomlzu, S., Toei, K., Ana/yst(London), 705, 328-32 (1980). (128) Mehra, M. C., Landry. J. C., Talanta, 27, 445-7 (1980). (138) Morisige, K., Hiraki, K., Nishikawa, Y., Shlgematsu, T., Bunseki Kagaku, 27, 109-14 (1978); Chem. Abstr., 89, 152375b (1978). (148) Pakains, P., Farrar, Y. J., Water Res., 13, 987-90 (1979); Chem. Abstr., 92,64402q (1980). (156) Sturgeon, R. E., Berman, S.S.,Desaulniers, A., Russell, D. S., Anal. Chem., 51, 2364-9 (1979). (16B) Takada, T., Nakano, K., Anal. Chim. Acta, 707,129-38 (1979). (17B) Tsuyama, A., Nakashima, S., Bunseki Kagaku, 29, 81-4 (1980); Chem. Abstr., 93,31507v (1980). (18B) Watanabe, K., Yoshizawa, H., Kawagaki, K., Bunseki Kagaku, 29, 233-8 (1980); Chem. Absfr., 93, 18497x (1980). (19B) Weiss, H. V., Kenis, P. R., Korkisch, J., Steffan, I., Anal. Chlm. Acta, 104, 337-43 (1979). (208) Wljkstra, J., Van der Sloot, H. A., J . Radioanal. Chem., 46, 379-88 (1978); Chem. Abstr., 90, 127280e (1979). BERYLLIUM, CADMIUM, CHROMIUM, COBALT, COPPER, LEAD, NICKEL, SILVER, THALLIUM, AND ZINC
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BISMUTH, GOLD, INDIUM, MOL'IIBDENUM, RHENIUM, THORIUM, TIN, TUNGSTEN, URANIUM, VANADIIJM, AND ZIRCONIUM
(ID) Bishop, C. T., Caseila, V. FI., Glosby, A. A., Report, No. PB-299237, Avail. NTIS, 60 pp (1979). (2D) Blunden, S.J., Chapman, A. H., Analyst(London), 103, 1266-9 (1978). (3D) Campen, W., Baechrnann, K., Mikrochim. Acta, 2 , 159-70 (1979); Chem. Absfr., 9 2 , 134971a (1980). (4D) Casella, V. R., Bishop, C. T., Glosby. A. A., ASTM Spec. Tech. Pub/., STP 698, 200-13 (1980). (5D) Chin, H.,Huan Ching K'o Iftrueh, 1978, 64; Chem. Abstr., 91, 270222 (1979). (6D) Cospito, M., Rigali, L., Anal. Chlm. Acta, 106, 385-8 (1979). (7D) Epstein, M. S.,Bradshaw, cJ", Bayer, S.,Bower, J., Voigtman, E., Winefordner, J. D., Appl. Spectrosc., 34, 372-6 (1980). (ED) Ferguson, J. R., Caylor, J. D., Rogers, E. R., Cole, S. H., Report, Y2073, Avail. NTIS, 14 pp (1977).
(9D) Geraldo, L. P., Cesar, M. F., Mafra, 0. Y., Tanaka, E. M., J. Radioanal. Chem,, 49, 115-26 (1979); Chem. Abstr., 9 1 , 62446n (1979). (IOD) Gifford, P. R., Bruckenstein, S., Anal. Chem., 5 2 , 1028-31 (1980). (11D) Giodowski, S., Kublik, Z.,Anal. Chim. Acta, 115, 51-60 (1980). (12D) Hall, G. E. M., Geol. Sum. Pap. (Geol. Sum. Can.), 79-1A, 361-5 (1979). (13D) Hirose, A., Ishii, D., J. Radioanal. Chem., 48, 211-15 (1978); Chem. Abstr., 90, 127279m (1979). (14D) Hodge, V. F., Seidel, S.L., Goldberg, E. D., Anal. Chem., 51, 1268-9 (1979). (15D) Hu, Z.,Gao, J., Hua Hsueh Tung Pao, 1979, 236-9; Chem. Ahstr., 91, 1 4 5 8 0 3 ~(1979). (16D) Iordanov, N., Pavlova, M., Stefanov, S., Rlanfa, 2 5 , 389-93 (1978). (170) Keil, R., Fresenlus' Z. Anal. Chem., 297, 384-7 (1979); Chem. Abstr., 9 1 , 2 0 3 8 0 8 ~(1979). (18D) Kimura, K., Hirao, Y., Ayabe, M., Hlrose, K., Radlolsofopes, 27, 705-8 (1978); Chem. Abstr., 9 0 , 2 0 9 8 3 4 ~(1979). (l9D) Kovai'chuk, L. I., Koryukova, V. P., Andrianov, A. M., Radiokhimlya, 2 1 , 767-8 (1979); Chem. Abstr., 92, 1 6 8 9 1 7 ~(1980). (20D) Kulathllake, A. I., Chatt, A,, Anal. Chem., 5 2 , 828-33 (1980). (21D) Kuleff, I., Kostadinov, K. N., J. Radioanal. Chem., 46, 385-71 (1978); Chem. Abstr., 9 0 , 109683) (1979). (22D) McElhaney, R. J., Caylor, J. D., Cole, S.ti,Futrell, T. L., Giles, V. M., Report, Y-2711, Avail. NTIS, 16 pp (1978). (23D) McHugh, J. B., Geol. Sow.Open-File Rep. (U.S.), 79-429, 14 pp (1979). (24D) Monien, H., Bovenkerk, R., Krlnge, K. P., Rath, D., Frisenlus' Z.Anal. Chem., 300, 363-71 (1980); Chem. Abstr., 9 3 , 79628n (1980). (25D) Nakahara, T., Chakrabarti, C. L., Anal. Chim. Acta, 104, 99-111
,.-. -,.
1107QI
(28D) Nakashima, S., Bull. Chem. SOC. Jpn., 5 2 , 1844-8 (1979); Chem. Absfr., 9 1 , 1 4 5 8 1 0 ~(1979). (27D) NI, Z.,Chln, L., Wu, T., Huan Chlng K O Hsueh, 1979, 25-9; Chem. Abstr., 9 2 , 190664q (1980). (28D) Ohta, N., Fujita. M., Tomura, K., BunsekiKagaku, 2 8 , 277-.80 (1979); Chem. Abstr.. 91. 964050 11979). (29D) Pakalns, P., Lane, H. f.,'Mikrochim. Acta, 1, 259-65 (1979); Cham. Abstr., 91, 44298m (1979). (300) Plyusnin, A. M., Pogrebnyak, Y. F., Tat'yankina, E. M., Zh. Anal. Khim., 34, 402-5 (1979); Chem. Abstr., 9 1 , 27033d (1979). (31D) Pogrebnyak, Y. F., /bid.. 34, 91-3 (1979); Chem Absfr., 9 0 , 1970448 (1979). (32D) Putral, A., Schwochau, K., lbid., 291, 210-12 (1978); Chem. Abstr., 8 9 , 117436a (1978). (33D) Pyen, G., Fishman, M., At. Absorpt. News/., 78, 34-6 (1979). (34D) Rakhmonberdyev, A. D., Nazarov, 8. F., Zavod. Lab., 45, 697-700 (1979); Chem. Abstr., 9 7 , 203726t (1979). (35D) Reinhardt, K. H., Mueller, H. J., Fresenius' Z Anal. Chem., 292, 359-61 (1978); Chem. Abstr., 90, 2879061 (1979). (36D) Rigin, V. I., Rlgina, I.V., Zh. Anal. Khim., 35, 929-34 (1980); Chem. Abstr., 93, 3 6 4 1 4 ~(1980). (37D) Simon, N., Weleblr, A. J., Aldridge, M. H., Report, No. AD-A058568, Avail. NTIS, 54 pp (1978). (38D) Tateno, Y., Ohta, N., Bunseki Kagaku, 28, 666-70 (1979); Chem. Abstr., 92, 64427b (1980). (39D) Tominaga, M., Umezaki, Y., Anal. Chim. Acta, 110, 55-60 (1979). (40D) Toshimitsu, Y., Yoshimura, K., Ohashi, S , Talanta, 2 8 , 273-6 (1979). (41D) Voevutskaya, R. N., Pavlova. V. K., Pilipenko, A. T., Zh. Anal. Khim., 34, 1299-305 (1979); Chem. Abstr., 9 1 , 203713rn (1979). (42D) Wllilams, W. J., Glllam, A. H., Ana&st(London), 103, 1239-43 (1978). MERCURY
(1E) Agemian, H., DaSilva, J. A., Anal. Chim. Acta, 104, 285-91 (1979). (2E) Allseda, J. A., Ankersrnit, R., Ashley, G. W., Barjhoux, J., Bult, R., Carter, W. T., Durr, W., Garbayo, J., Garcia, M., et ai., ibid., 109, 209-28 (1979). (3E) Bouzanne, M., Sire, J., Voinovitch, I. A,, Analusis, 7, 62-8 (1979); Chem. Abstr., 9 1 , 27051h (1979). (4E) Brlcker, J. L., Anal. Chem., 5 2 , 492-6 (1980) (5E) Chan, X., Ni, Z.,Hua Hsueh Hsueh Pao, 37, 261-6 (1978); Chem. Abstr., 9 2 , 2 2 0 4 7 4 ~(1980). (6E) Cragin, J. H.. Anal. Chim. Acta, 110, 313-19 (1979). (7E) Duerr, W., Olivier, M., Winkler, H., Vom Wasser, 53, 69-71 (1979); Chem. Abstr., 9 3 , 12861q (1980). (8E) Egawa, H., Tajima, S., U . S . Envlron. Prot. Agency, Off. Res. Dev., (Rep .) €PA, EPA- 60013- 77- 083 (1977). (9E) Farey, B. J., Nelson, L. A., Anal. Chem., 50, 2147-8 (1978). (10E) Farey, B. J., Nelson, L. A., Roiph, M. G., Analyst (London), 103, 656-60 (1978). (11E) Glfford, P. R., Bruckenstein, S.,Anal. Chem , 52, 1024-8 (1980). (12E) Heiden, R. W., Alkens, D. A,, Anal. Chem., 51, 151-6 (1979). (13E) Howard, A. G., Arbab-Zavar, M. H., Talanta, 26, 895-7 (1979). (14E) Hsu, C., Tsai, C., Huan Chlng K O Hsueh, 1979, 78-9; Chem Abstr., 9 2 , 64400n (1980). (15E) Jensen, K. O., Carlsen, V., J Radioanal. Chem., 47, 121-34 (1978); Chem. Abstr., 9 0 , 127278k (1979). (16E) Khakimov, S.,Kutbedinov, A., Abdullaeva, A. A,, Radiokhimiya, 20, 826-8 (1978); Chem. Abstr., 9 1 , 27025c (1979). (17E) Kritsotakis, K., Laskowski, N., Tobschall, H. J., Int. J . Environ. Anal. Chem., 6, 203-16 (1979); Chem. Abstr., 9 1 , 198516t (1979). (18E) Liu, Z., Huang, T., Huan Ching K O Hsueh, 1979, 52-4; Chem. Abstr., 9 2 , 6 4 4 1 4 ~(1980). (19E) Lutze, R. L., Analyst (London), 104, 979-82 (1979). (20E) MacCrehan, W. A., Durst, R. A., Bellama, J. M., NBS Spec. Pub/. (U.S.), 519, 57-63 (1979). ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL. 1981
209A
WATER ANALYSIS (21E) Madej, A., Parczewski, A., Rokosz, A., Stepak, R., Chem. Anal. (Warsaw), 23,231-9 (1978); Chem. Abstr., 89, 117407s (1978). (22E) Matsunaga, K., Konishi, S.,Nishimura, M., Environ. Sci. Technol., 73, 63-5 (1979). (23E) Matsueda, T., Bunseki Kagaku, 29, 110-15 (1980); Chem. Abstr., 93,31512t (1980). (24E) Millward, G. E,, Le Bihan, A,, Water Res., 72,979-84 (1978); Cbem. Abstr., 90, 127282g (1979). (25E) Minagawa, K., Takizawa, Y., Kifune, I., Anal. Chim. Acta, 775, 103-10 (1980). (26E) Mizunuma, H., Morita, H., Sakurai, H., Shimomura, S.,Bunseki Kagaku, 28,695-9 (1979); Chem. Abstr., 92,689592 (1980). (27E) Nagatsuka. S., Tanizaki, Y., Radloisotopes, 27, 379-83 (1978); Chem. Abstr., 90,76296e (1979). (28E) Nelson, L. A., Anal. Chem., 57, 2289-90 (1979). (29E) Podchainova, V. N., Barbina, T. M., Dubinina, L. F., Zh. Anal. Khlm.. 34, 688-92 (1979); Chem. Abstr., 97,162816b (1979). (30E) Rigin, V. I., ibid., 34, 261-7 (1979); Chem. Abstr., 90, 2 1 4 6 3 1 ~ (1979). (31E) Rodriguez-Vazquez, J. A., Talanta, 25,299-310 (1978). (32E) Rychkova, V. I., Doimanova, I.F., Zh. Anal. Khim., 34, 1414-16 (1979); Chem. Abstr., 97,203717r (1979). (33E) Shlraishi, N., Kuroda, T., Bunsekl Kagaku, 29,TI-T4 (1980); Chem. Abstr., 93,79578w (1980). (34E) Slovak, Z., Docekalova, H., Anal. Chim. Acta, 715, 111-19 (1980). Kobayashi, H., (35E) Ueno, K., Shiraishi, K., Togo, T., Yano, T., Yoshida, I., Anal. Chim. Acta, 705,289-95,(1979). (36E) Wang, E., Li, A., Chang, S.,Huan Ching K ' o Hsueh, 1979, 24-7; Chem. Absfr., 92,82064k (1980). (37E) Wang, S.,/bid.. 1979, 36-41; Chem. Abstr., 92, 82048h (1980). (38E) Wrembel, H. Z., Chem. Anal. (Warsaw), 24,793-800 (1979); Chem. Abstr., 93,53562m (1980). (39E) Yamamoto, Y., Kumamaru. T., Shiraki, A,, Fresenius' Z. Anal. Chem., 292,273-7 (1978); Chem. Abstr., 89,208586r (1978). (40E) Yu, M., Liu, K., Wang, W., Huan Ching K ' o Hsueh, 1979, 46-50; Chem. Abstr., 92,152724b (1980). ANTIMONY, ARSENIC, SELENIUM, AND TELLURIUM
(IF) Cheam, V., Agemian, H., Anal. Chim. Acta, 773, 237-45 (1980). (2F) Chen, X., Tsui, C., Huan Ching K ' o Hsueh, 1979, 50-2; Chem. Abstr., 92,82066n (1980). (3F) Cheng, K., U . S . Natl. Tech. Inform. Serv., Rep., No. PB-290382, Avail. NTIS, 151 pp (1977). (4F) Cox, J. A., Cheng, K., Anal. Lett., A l l , 853-60 (1978); Chem. Abstr., 89, 1 9 0 4 6 5 ~(1978). (5F) Cutter, 0. A,, Anal. Chim. Acfa, 98,59-66 (1978). (6F) Fry, R. C., Denton, M. B., Windsor, D. L., Northway, S.J., Appl. Spectres., 33,399-404 (1979). (7F) Gifford, P. R., Bruckenstein, S.,Anal. Chem., 52, 1024-8 (1980). (8F) Gifford, P. R., Bruckenstein, S., ibid., 52, 1028-31 (1980). (9F) Goode, S.R., Matthews, R. J., ibid., 50, 1608-11 (1978). (IOF) Henry, F. T., Kirch, T. O., Thorpe, T. M., ibid., 57, 215-18 (1979). (11F) ,Iverson, D. G., Anderson, M. A,, Holm, T. R., Stanforth, R. R., Envlron. Sci. Technol., 73,1491-4 (1979). (12F) Kamada, T., Shiraishi, T., Yamamoto, Y., Talanta, 25,15-19 (1978). (13FI Karnada. T.. Suoita. N.. Yamamoto. Y.. ibid.. 26. 337-40 (1979). (l4F) Kaneko, E., Buiseki Kagaku, 27,250-2 (1978); Chem. Abstr., 89, 1 1 7 4 2 6 ~(1978). (15F) Lu, Z.,Hsieh, K., Tseng, T., Huan Ching K'o Hsueh, 1979, 47-9; Chem. Abstr., 92,82065rn (1980). (16F) Morrow, R. W., Futreil, T. L., Adams, T. T., Report, Y-2724,Avail. NTIS, 17 pp (1978). (17F) Nakashima, S.,Anawst (London), 703,1031-8 (1978). (18F) Nakashima, S., Anal. Chem., 57, 854-8 (1979). (19F) Nazarenko, I.I., Kislova, I.V., Zh. Anal. Khim., 33, 157-9 (1978); Chem. Absfr.. 90. 109672e (1979). (20F) Odanaka, Y., Matano, O:, Gotb, S., Bunseki Kagaku, 28, 517-22 (1979); Chem. Abstr., 97. 221843h (1979). (21F) Piccardl, G., Udisti, R., Mikrochim. Acta, 2, 447-54 (1979). (22F) Pyen, G., Fishman, M., At. Absorpt. News/., 17,47-8 (1978). (23F) Reichert, J. K., Gruber, H., Vom Wasser, 57, 191-7 (1978); Chem. Absfr., 91,92849 (1979). (24F) Rigin, V. I.;Zh. Anal. Khim., 33, 1966-71 (1978); Chem. Abstr., 90, 478499 (1979). (25F) Robberecht, H. J., Van Grieken, R. E.,Anal. Chem., 52, 449-53 (1980). (26F) Sandhu, S. S., Report, EPA/600/4-78/038, PB Rep. No. 288753, Avail. NTIS, 38 pp (1978). (27F) Sandhu, S. S., Nelson, P., Environ. Sci. Technol., 73,476-8 (1979). (28F) Shaikh, A. U., Tallman, D. E.,Anal. Chim. Acta, 98,251-9 (1978). (29F) Shchukin, V. D., Kozirod, I.D., Zavod. Lab., 44, 1057-9 (1978); Chem. Abstr., 90,28783q (1979). (30F) Shimoishi, Y., Toei, K., Anal. Chim. Acta, 100, 65-73 (1978). (31F) Tzeng, J., Zeitlin, H., ibid., 101, 71-7 (1978). (32F) Yanagi, K., Bunseki Kagaku, 29, 194-9 (1980); Chem. Absfr., 93, 795882 (1980). BORON, PHOSPHORUS, AND SILICA
(1G) Ball, J. W., Thompson, J. M., Jenne, E. A,, Anal. Chim. Acfa, 98, 67-75 (1978). (2G) Chang, C., Keng, C., Shang, S., Lu, T., Huan Ching K'o Hsueh, 1979, 79-80; Chem. Abstr., 92,64401p (1980). (3G) Cheng, K., Report, No. PB 290382,Avail. NTIS, 151 pp (1977). (4G) Chol, W., Chen, K. Y., J. Am. Water Works Assoc., 71,153-7 (1979).
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(5G) Cox, J. A., Cheng, C., Anal. Lett., 7 7 , 653-60 (1978); Chem. Abstr., 89, 1904651, (1978). (6G) Downes, M. T., Water Res., 72, 743-5 (1978); Chem. Abstr., 90, 6097311 119791. (7G) Edwaids, R: A., Ana/yst(London), 705, 139-46 (1980). (8G) Gales. M. E.. Jr.. Booth.. R. L... U.S. NTIS. P6 Reo. No. 287027.Avail. ' NTIS, 23 pp (ig78). (9G) Hanson, R. H., US'. NTIS, PB Rep. No. 277477,Avail. NTIS, 36 pp 11977)
(100) Jeffrles, D. S.,Dleken, F. P., Jones, D. E., Water Res., 73,275-9 (1979); Chem. Abstr., 90,209846h (1979). (11G) Korenaga, T., Motomizu, S.,Toei, K., Ana/yst(London), 703,745-53 (1978). (12G) Kuwada, K., Motomizu, S.,Toei, K., Anal. Chem., 50, 1788-92 (1978). 113G) Lennox. L. J.. Water Res... 13.. 1329-33 (1979): . , Chem. Abstr.. 92. ' 152751h (1980).' (14G) Rawa, J. A., Henn, E. L., Anal. Chem., 51,452-5 (1979). (15G) Simmons, M. S.,Anal. Lett., 73, 67-74 (1980); Chem. Abstr., 93, 79586x (1980). (16G) Spencer, R. R., Erdmann, D. E., Envlron. Scl. Technol., 73,954-6 (1979). (17G) Szydlowski, F. J., Anal. Chim. Acta, 706, 121-5 (1979). (18G) Tanaka, T., Hliro, K., Kawahara, A., Bunsekl Kagaku, 28, 43-7 (1979); Chem. Abstr., 90,179538q (1979). (19G) Yoshlmura, K., Karlya, R., Tarutanl, T., Anal. Chlm. Acta, 709, 115-21 (1979). SULFATE, SULFITE, SULFIDE, AND SULFUR
(IH) Brull, E. E., Golden, G. S., Anal. Chlm. Acta, 770, 167-70 (1979). (2H) Bruno, P., Caselli, M., Di Fano, A., Traini, A,, ibM., 704, 379-84 (1979). (3H) Chakraborti, D., Adams, F., ibid., 709,307-17 (1979). (4H) Couto, M. I., Curtius, A. J., Appl. Spectrosc., 34, 228-9 (1980). (5H) Cronan, C. S.,Anal. Chem., 57, 1333-5 (1979). (6H) Dasgupta, P. K., Hanley, L. G., Jr., West, P. W., ibid., 50, 1793-5 (1978). (7H) Howarth, R. W., Llmnol. Oceanogr., 23, 1066-9 (1978). (8H) Hu, H., Anal. Chlm. Acta, 707, 387-90 (1979). (9H) Ingvorsen, K., Joergensen, B. B., Llmnol. Oceanogr., 24, 390-3 (1979). (10H) Murakami, T., Kamaya, M., Shinozaki, J., Kanari, Y., Bunseki Kagaku, 28,623-7 (1979); Chem. Abstr., 97,2219201 (1979). (11H) Pakalns, P., Farrar, Y. J., Water Res., 73,991-4 (1979); Chem. Absfr., 92,64403r (1980). (12H) Reijnders, H. F. R., Van Staden, J. J., Griepink, B., Fresenlus' Z. Anal. Chem., 293,413-15 (1978); Chem. Abstr., 90, 12728711 (1979). (13H) Reljnders, H. F. R., Van Staden, J. J., Griepink, B., ibid., 295, 122-4 (1979); Chem. Abstr., 97,44305m (1979). (14H) ReiJnders,H. F. R., Van Staden, J. J., Griepink, B., ibid., 295,410-12 (1979); Chem. Abstr., 97,96410m (1979). (15H) RelJnders. H. F. R., Van Staden, J. J., Griepink, B., ibid., 298, 156-7 (1979); Chem. Abstr., 92,64422w (1980). (16H) Reljnders, H. F. R., Van Staden, J. J., Griepink, B., ibid., 300, 273-6 (1980); Chem. Abstr., 93,53587y (1980). (17H) Rosenbauer, R. J., Bischoff, J. L., Limnol. Oceanogr., 24, 393-6 (1979). (18H) Utsumi, S.,Oinuma, Y., Isozakl, A., Bunseki Kagaku, 27, 276-82 (1978); Chem. Abstr., 89,80036s (1978). HALI DES
(11) BurQuera, M., Townshend, A., Bogdanski, S. L., Anal. Chlm. Acta, 777, 247-55 (1980). (21) Deane, S.F., Leonard, M. A., McKee, V., Svehla, G., Analyst(London), 103. 1134-47 119781. ._ (31) Fukuzaki, N., Suzuki, T., Sugal, R., Oshina, T., Bunseki Kagaku, 28, 60-3 (1979); Chem. Abstr., 90, 16163le (1979). (41) Gifford, P. R., Bruckenstein, S.,Anal. Chem., 52, 1024-8 (1980). (51) Hashitani, H., Yoshida, H., Adachi, T., Bunseki Kagaku, 28, 680-5 (1979); Chem. Abstr., 92,6 4 4 2 8 ~(1980). (61) Kokubu, N., Kobayasi, T., Yamasaki, A,, ibld., 29,106-9 (1980); Chem. Abstr., 93,79577v (1980). (71) Kowal, A. L., Kowalski, T. W., Krasniewska, D., Chem. Anal. (Warsaw), 23,681-5 (1978); Chem. Abstr., 90, 1 0 9 6 7 0 ~(1979). (81) Kreingol'd, S. U., Sosenkova, L. I., Panteieimonova, A. A,, Lavrelashvlll, L. V.. Zh. Anal. Khim.. 33, 2168-73 (1976); Chem. Abstr., 90, 109685m (1979). (91) Marshall, B. B., Mldgley, D., Analyst (London), 703,438-46 (1978). (101) Marshall, B. B.. Midgley, D., ibid., 104, 55-62 (1979). (111) Mor, E. D., Beccaria, A. M., Poggi, G., Anal. Chim. Acta, 99,361-4
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(121) Moxon, R. E. D., Dlxon, E. J., J. Auto. Chem., 2, 139-42 (1980). (131) Nikashina, V. A., Krachak, A. N., Zh. Anal. Khim., 34,2236-8 (1979); Chem. Abstr., 92,152723a (1980). (141) Nota, G., Vernassl, G., Acampora, A., Sannolo, N., J. Chromatogr., 774,228-30 (1979); Chem. Abstr., 91, 12876g (1979). 1151) Peron. A.. Courtot-CouDez, J., Analusis, 6, 389-94 (1978); Chem. ' Absfr., 90,92151) (1979): (161) Pyen, G. S.,Fishman, M. J., Hedley, A. G., Analyst (London), 705. 657-662 (1980). (171) Rudenko, E. I., Popov, V. A,, Zavod. Lab., 45, 388-91 (1979); Chem. Abstr., 97,824948 (1979). (181) Ryslavy, Z.,Bocek, P., Deml, M., Janak, J., Chem. Listy, 72,641-6 (1978); Chem. Abstr., 89,99144x (1978). (191) Sichere, M. C., Cesbron, F., Zuppi, G. M., Anal. Chim. Acta, 98, 299-306 (1978).
WATER ANALYSIS (201) Slanina, J., Bakker, F , Bruyn-Hes, A,. Moels, J J., Bid., 113, 331-42 (1980). NITRATE, NITRITE, AMMONIA, CIRGANIC NITROGEN, CYANIDE, AND THIOCYANATE
(IJ) Anderson, L., Anal. Chim. Acta. 110, 123-8 (1979). (2J) Brlnkhoff. H. C., Envlron. Sci, Technol., 72, 1392-4 (1978). (3J) Brown, L., Beilinger, E. 13,Water Res., 72, 223-9 (1978): Chem. Abstr., 8 9 , 1524001 (1978). (4) Carson, F. W., Gross, R. L., Report, MI-WRRC-11, W79-00503, OWRT-A-OO3-DC( I),PB-288307, Avail. NTIS, 15 pp (1979). (5J) Chao, C.. Ting, Y., Huan Ctilng K O Hsueh, 1978. 43-8; Chem. Abstr., 92, 116118~(1980). (6J) Chao, M. K., Higuchi. T.. Sternson, L. A,, Anal. Chem., 50, 1670-5 (1978). (7J) Davison, W., Woof, C., Analyst (London), 103, 403-6 (1978). (8J) Davison, W.. Woof, C., lbk'., 704, 385-90 (1979) (9J) Downes, M. T.. Water Res., 72, 673-5 (1978); Chem. Abstr., 9 0 , 762989 (1979). (IOJ) Eaton. A. D Grant, V., Llmnol Oceanogr., 24, 397-9 (1979). (11J) Gales, M E., Jr , Booth, R, L., U S. M I S , Pfl-287027, Avail. NTIS, 23 pp (1978). (12J) Gardner, W. S., Llmnol. Oceanogr., 23, 1069-72 (1978). (13J) Garside, C., Hull, G., Niurray, S.,Limnol. Oceanogr., 23?3, 1073-6 (1978). (14J) Hainberger, L.. Nozaki, J., Mikrochlm. Acta, 7 , 75-80 (1979); Chem. Abstr., 9 0 , 1 5 6 8 4 3 ~(1979). (15J) Halnberger, L., Nozakl, J., ibid., 2 , 187-91 (1979); Chem. Abstr., 9 2 , 82078t (1980). (16J) Hiiro, K., Kawahara, A.. Tanaka, T., Bunsekl Kagahu, 2 7 , 283-7 (1978); Chem. Abstr., 8 9 , '1523893 (1978). (17J) Hlkuma, M., Kubo, T., Yacrida, T., Karube, I., Suzuki, S., Anal. Chem., 5 2 , 1020-4 (1980). (18J) Korenaga, T., Mikrochlm. Acta, 2, 455-66 (1979); Chem. Abstr., 93, 12844m (1980). (19J) Krug, F. J., Ruzicka, J., tliaflsen, E. H., Analyst (London), 104, 47-54 (1979). (20J) Li, Y., Hal Yang Yu Hu Chao, 10, 112-18 (1979); Chem. Abstr., 9 7 , 2164181 (1979). (21J) Lowry, J. H., Mancy, K. 1-L Water Res., 12, 471-5 (1978); Chem. Abstr., 8 9 , 185722r (1978). (22J) McKee, G. D., U . S . Envlron. Prot. Agency, Off. Res. Dev., (Rep.) &PA I 6001 8- 791 0 74,13.1-4 ( 1979). (23J) McLean, J. D.. Stenger, 'V. A., Reim, R. E., Long, M. W., Hiller. T. A., Anal. Chem., 50, 1309-14 (1978). (24J) Murata, K., Takemoto, S.,lkeda, S.,Bunseki Kagaku, 27, 348-53 (1978); Chem. Abstr., 8 9 , '162402h (1978). (25J) Nair, J., Gupta, V. K., Anctl. Chim. Acta, f 7 7 . 311-14 (1979). (26J) Nydahl, F., Water Res., 72, 1123-30 (1978); Chem. Abstr., 90, 14198q (1979). (27J) Okada, M., Mlyata, H., Toul, K., Analyst(London), 704, 1195-7 (1979). (28J) Otsuki, A., Anal. Chim. Acta, 9 9 , 375-7 (1978). (29J) Pihlar, B., Kosta, L., ibid., 714, 275-81 (1980). (30J) Riemann, B., Schlerup, H., H., Water Res., 12, 849-53 (1978); Chem. Abstr., 9 0 , 60975q (1979). (31J) Sirneonov, V., Andreev, G . , Stoianov, A,, Fresenius' 2.Anal Chem., 297, 418 (1979); Chem. Abistr., 9 2 , 6 4 4 1 8 ~(1980). (32J) Slanina, J., Bakker, F., Br'wyn-Hes, A., Moels, J. J., Anal. Chlm. Acta, 173, 331-42 (1980). (33J) Tanaka, K., Ishizuka, T., Sunahara, H., J. Chromatogr., 777, 21-7 (1979); Chem. Abstr., 9 2 , €12050~(1980). (34J) Trojanowicz, M., Fresenlus' Z. Anal. Chem., 297, 414-16 (1979); Chem. Abstr., 9 2 , 644171, (1980). (35J) Verdouw, H., Van Echteld, C. J. A., Dekkers, E. M. J., Water Res., 12, 399-402 (1978); Chem. Abelr., 8 9 , 152412m (1978). (36J) Williams, T. J., J . Am. Water Works Assoc., 77, 157-60 (1979). (37J) Wiiiis, R. B., Anal. Chem., 52, 1376-7 (1980). (38J) Zhu, G., Shih, K., Yang, C., Chao, H., Huan Ching K'o Hsueh, 1979, 25-8; Chem. Abstr., 9 1 , 190515s (1979). I
RADIOCHEMICAL AND ISOTOPIC ANALYSIS
(IK) Bishop, C. T., Glosby, A. A , Phillips, C. A., Report, MLM-2425, Avail. NTIS, 72 pp (1978). (2K) Brown, K. A., Limnoi. Occ%?nogr..24, 1141-5 (1979). (3K) Egorova, N. V., Krylov, V. N., Pitalev, V. G., Stepanov. A. V., Radiokhimiya, 2 0 , 737-41 (1978): Chem. Abstr., 9 0 , 43628h (1979). (4K) Egorova, N. V., Krylov, V. 1% Stepanov, A. V., ibid., 20, 742-5 (1978); Chem. Abstr., 9 0 , 436193 ('1979). (5K) Elmore, D., Fulton, 8. R.. Clover, M. R., Marsden, J. R,, Gove, H. E., Naylor. H., Purser, K. H., Kiiius, L. R.. Ueukens, R. P., Litherland, A. E., Nature (London), 277, 22-5 (1979); Chem. Abstr., 9 7 , 44290c (1979). (6K) Gedeonov, L. I., Krylov, V N.,Stepanov, A. V., Report, RI-86, Avail. INIS, 14 pp (1978). (7K) Haberer, K.. Stuerzer, U., Fresenius' 2. Ana!. Chem., 299, 177-86 (1979); Chem. Abstr., 9 2 , 1349814 (1980). (8K) Holm, E., Ballestra, S., Fultai, R., Talanta, 2 6 . 791-4 (1979). (9K) Horluchi, K., Murakami, Y . , HunsekiKagaku, 28, 661-5 (1979); Chem. Abstr., 9 2 , 64426a (1980). (10K) Kellomaki, A., Jutila, M., Anal. Chem., 57. 1335-6 (1979). (11K) Klmura, T., Hamada, T., Radioisotopes, 27, 348-9 (1978); Chem. Abstr., 9 0 , 6096% (1979). (12K) Kishima, N., Sakal, H., A.n,al.Chem.. 5 2 , 356-8 (1980). (13K) Kudo, K., Kobayashl, K., -1. Radioanal. Chem., 5 3 , 163-72 (6979); Chem. Abstf., 9 2 , 157153~(1980). (14K) Mackenzie, A. B., Baxter, M. S . , McKlnely, I. G., Swan, D. S.,Jack, W., ibid., 48, 29-47 (1979); Chem. Abstr., 90, 156875h (1979).
(15K) Moskvin. L N , Mlroshnikov, V. 8..Mel'nlkov, V A., Radblrhlmlya, 21, 311 15 (1979); Chem. Abstr., 97, 4 8 8 6 8 ~(1979). (16K) Sharp. T. R., Minard, R. D., Anal. Chem., 52, 598-600 (1980). (17K) Van Hemmen, J. J., Van Hoek, L. P., Aten, J. B. T., Report TNOMBL- 1976- 70, Avail. INIS, 14 pp (1976). (18K) Wong, K. M , Nioshkin, V. E., Jokela, T. A., Report, UCRL-80686, Avail. NTIS, 12 pp (1978) (i9K) Xiang, Q., Min. W., Gao, X , Zhu. G., LI, W.. Hua Hsueh Tung Pao, 1979, 439-41, Chem. Abstr , 9 2 , 64433a (1980). GASES
(1L) hender, D. F.. Reoort, EPA1600/4-78I079, No. PB-287572, Avail. ' NTIS, 40 pp (1978) ' (2L) Brooks. A. S., Seegert, G. L., J.-Water Pollut. Control Fed., 51. 2636-40 (1979). (3L) Dimmock, N. A.. Miigiey, D., Water Res., 73, 1101-4 (1979); Chem. Abstr., 92, 99323s (1980). (4L) Dimmock, N. A . Mldgiey, D., ibM., 13, 1317-27 (1979); Chem. Abstr., 92. 1527500 119801. .. (5L) Elkins. J. h:,Ant;!. Chem., 5 2 , 263-7 (1980). (6L) Goodfellow. G. I., Llbaert. D. F., Webber, H. M., Analyst(London), 704, 1119-23 (1979). (7L) Goodfellow. G. I , Webber, H. M., ibid., 704, 1105-18 (1979). (EL) Hall. K. C., J. Chromatwr Scl., 16, 311-13 (1978); Chem. Abstr., 89. 152418 (1978). (9L)11979) Ingvorsen, K., Joergensen, B. B., Limnol. Oceanogr., 24, 390-3 ,. - . -,. (101) Leggett, D. C., Report CRREL-SR-79-24 No. AD-A074477, Avail. NTIS, 9 pp (1979). (11L) Masscheleln, W. J., Fransolet, G., Goossens, R., Maes, L., Analusis, 7 , 4 3 2 4 (1979); Chem. Abstr., 9 2 , 152710~(1980). (12L) Palin, A. T., J. Am. Water Works Assoc., 72, 121-2 (1980). (13L)' Payne, J. T., /bid., 51, 2540-4 (1979). (14L) Rahim, S. A., Mohemed. S.H.. Taknta, 2 5 , 519-,21 (1878). (15L) Reddy, G. S.,Rajan, S. C., Reddy, Y . K., ibid., 2 5 , 480-2 (1978). (16L) Roscher, N. M., Liebermann, J., Jr., Cooper, W. J., Meier, E. P., Report, No. AD-A059077, Avail. NTIS, 64 pp (1978). (17L) Smart, R. B., Dormond-Herrera, R., Mancy, K. H., Anal. Chem., 57, 2315-19 (1979). (18L) Smart, R. B., Lowry, J. H., Mancy, K. H., Envlron. Sci. Technol., 73, 89-92 (1979). (19L) Stanley, J. H., Johnson, J. D.. Anal. Chem., 57, 2144-7 (1979). (2OL) Storozhenko, V. N., Dlnkevich, F. E., Orlenko, V. V., Moskovskii, V Z., Zavod. Lab., 45, 596-8 (1979); Chem. Abstr., g7, 167783~(1979). (211) Wei, D., Ta-//en Uung Hsueh Yuan Hsueh Pao, 1979, 174-5; Chem. Abstr., 9 7 , 181177k (1979). (22L) Wong, G. T. F., Water Res., 74,51-60 (1980); Chem Abstr., 93. 12852n (1980). MULTICONSTITUENTS
(IM) Apel, C. T., Bieniewskl, T. M., Cox, L. E., Steinhaus, D. W., ICP Inf. Newsl., 3 , 1-11 (1977). (2M) Bergamin. F. H., Reis, B. F., Zagatto, E. A. G., Anal. Chlm. Acta, 97, 427-31 (1978). (3M) Berman, S.'S., McLaren, J. W., Wlliie, S. N., Anal. Chem., 52, 480-92 (1980). (4M) Blommaert, W., Vandelannoote. R., Van't Dack, L., Oilbeis, R., Van Grieken, R., J . Radioanal. Chem., 5 7 , 383-400 (1980); Chem. Abstr., 9 3 , 79673y (1980). (5M) Bogen, D. C.. Nagourney. S. J.. €on Chromatogr. Anal. Envlron. Pol/ut., 2 , 319-28 (1979): Chem, Abstr., 9 2 , 203217~(1980) (6M) Bone, K. M., Hibbert. W. D., Anal. Chim. Acta, 707, 219-29 (1979). (7M) Bozsai, G.. Csanady, M., Fresenius' 2. Anal. Chem., 297, 370-3 (1979): Chem. Abstr., 9 2 , 64415w (1980). (EM) Cassidy, R. M., Elchuk, S.,J. Chromatogr. Sci., 18, 217-23 (1980); Chem. Abstr., 9 3 , 36400q (1980). (SM) Danielsson, L. G., Magnusson, B., Westerlund, S., Anal. Chlm. Acta, 9 8 , 47-57 (1978). (10M) Davis, D. G., Report No. AD-A058091, Avail. NTIS, 75 pp (1978). (11M) Disam. A., Tschoepel, P., Toelg, G., Fresenlus' 2.Anal. Chem., 295, 97-109 (1979); Chem. Abstr., 9 0 , 2146690 (1979). (12M) El-Enany, F. F., Mahmoud, K. F., Varma, M. M., J.-Wafer Pollut. Control Fed., 57, 2545-7 (1979). (13M) Fishman, M. J., Pyen. G. S., U . S . Geoi. Survey, Water Resources Invest., 79-101, No. PB80-177941, Avail. NTIS,30 pp (1979). (14M) Florian, K., Pliesovska, N., Chem. Anal. (Warsaw), 2 3 , 575-81 (1978); Chem. Abstr., 9 0 , 127270b (1979). (15M) Fulmer, M. A., Penkrot, J., Nadalin, R. J., Ion Chromatogr. Anal. Envlron. Poilut., 2 , 381-400 (1979); Chem. Abstr., 9 2 , 185592k (1980). (16M) Garbarino, J. R., Taylor, H. E.. Appl. Spectrosc., 3 3 , 220-6 (1979). (17M) Giliain, G., Duyckaerts, G., Disteche, A., Anal. Chim. Acta, 708, 23-37 (1979); Chem. Abstr., 97, 44308q (1979). (18M) Grasshoff, K., Hansen, H. P., Vom Wasser, 5 3 , 7 3 4 3 (1979): Chem. Abstr., 9 3 , 31531y (1980). (19M) Heuss, E., Lieser, K. H., J. Redloanal. Chern., 5 0 , 277-87 (1979); Chem. Abstr., 91. 145812e (1979). (20M) Heuss. E., Lieser, K. H.. ibid.. 50. 289-302 (19791: . . Chem. Abstr.. 97. 145813f (1979). (21M) Hirose, A., Kobori, K., Ishil, D., Anal. Chlm. Acta, 9 7 , 303-10 f19781. (22M) Hubert, A. E., Chao. T. T., Econ. Geol., 74, 1669-72 (1979): Chem. Abstr.. 9 2 , 8 2 0 2 4 ~11980). (23M) Itoh, H., Shinboii, Y.,'Bunseki Kagaku, 29, 239-43 (1980); Chem. Abstr., 93, 79609g (1980). (24M) Jan, T. K., Young, D. R., Anal. Chem., 50, 1250-3 (1978). ANALYTJCAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
211 R
WATER ANALYSIS (25M) Joerstad, K., Salbu, B., ;bid., 52, 672-6 (1980). (26M) Johnson, G. W., Taylor, H. E, Skogerboe, R. K., Appl. Spectrosc., 33, 451-56 (1979). (27M) Johnson, G. W., Taylor, H. E., Skogerboe, R. K., Spectrochim. Acta, Part 6 , 348, 197-212 (1979); Chem. Abstr., 9 2 , 82056j (1980). (28M) Kingston, H. M., Barnes, I.L., Brady, T. J., Ralns, T. C., Champ, M. A., Anal. Chem., 50, 2064-70 (1978). (29M) Koval'chuk, L. I., Koryukova, V. P., Smirnova, L. V., Shabanov, E. V., Zh. Anal. Khlm., 3 4 , 1136-9 (1979); Chem. Abstr., 9 7 , 162820~ (1979). (30M) Kulmatov, R. A., Kist, A. A., Gureev, E. S., Zhuk, L. I., Zavod. Lab., 45, 109-10 (1979); Chem. Abstr., 9 0 , 1 9 7 0 6 6 ~(1979). (31M) Kulmatov, R. A., Klst, A. A., Karimov, I.I., Zh. Anal. Khim., 35, 254-9 (1980); Chem. Abstr., 9 3 , 53573r (1980). (32M) Kusaka, Y., Tsuji, H., Imai, S., Ohmorl, S., Radiolsofopes, 28, 139-44 (1979); Chem. Abstr., 9 1 , 76685a (1979). (33M) Lagas, P., Anal. Chim. Acta, 9 8 , 261-7 (1978). (34M) Larson, G. F., Goodpasture, R. T., Morrow, R. W., Report, YIDK204(Rev.), CONF-7810705-2, Avall. INIS; NTIS, 42 pp (1978). (35M) Lenvik, K., Steinnes, E., Pappas, A. C., Anal. Chlm. Acta, 9 7 , 295-301 (1978). (36M) McQuaker, N. R., Brown, D. F., Kluckner, P. D., Anal. Chem., 57, 1082-4 (1979). (37M) Marchin, L. M., Collins, A. G., Report, BETCIRI-7918, Avail. NTIS, 12 pp (1979). (38M) Mart, L., Nuernberg, H. W., Valenta, P., Fresenius' Z . Anal. Chem., 300, 350-62 (1980); Chem. Abstr., 93, 79627m (1980). (39M) Mykytluk, A. P., Russell, D. S., Sturgeon, R. E., Anal. Chem., 52, 1281-3 (1980). (40M) Nagatsuka, S., Radioisotopes, 27, 690-7 (1978); Chem. Abstr., 9 0 , 1566392 (1979). (41M) Neitzert, V., Lleser, K. H., Fresenius' 2. Anal. Chem., 294, 28-35 (1979); Chem. Abstr., 9 0 , 12729011(1979). (42M) Nordmeyer, F. R., Hansen, L. D., Eatough, D. J., Rolllns, D. K., Lamb, J. D., Anal. Chem., 5 2 , 852-6 (1980). (43M) Peck, E. S., Langhorst, A. L., Jr., O'Brien, D. W., Report, UCRL87043, CONF-7810105-7, Avail. INIS; NTIS, 17 pp (1979). (44M) Pik, A. J., Cameron, A. J., Eckert, J. M., SholkovZz, E. R., Williams, K. L., Anal. Chlm. Acta, 110, 61-6 (1979). (45M) Pyen, G. S., Flshman, M. J., Ion Chromatogr. Anal. Environ. Polluf., 2 , 235-44 (1979); Chem. Abstr., 9 2 , 165586~(1980). (46M) Rawa, J. A., ibid., 2 , 245-69 (1979); Chem. Abstr., 92, 1855896 (1980). (47M) Rich, W. E., Tillotson, J. A,, Chang, R. C., /bid., 7, 185-96 (1978); Chem. Abstr., 8 9 , 135285e (1978). (48M) Sefzlk, E., Vom Wasser, 50, 265-99 (1978); Chem. Absfr., 9 0 , 28780m (1979). (49M) Simms, P. C., Rickey, F. A., Report, €PA16001 1-781058, No. PB287832, Avail. NTIS, 60 pp (1976). (50M) Slanina, J., Lingerak, W. A,, Ordelman, J. E., Borst, P., Bakker, F. P., Ion Chromatogr. Anal. Environ. Polluf., 2 , 305-17 (1979); Chem. Abstr., 9 2 , 185591) (1980). (51M) Smee, B. W., Hall, G. E. M., Koop, D. J., J. Geochem. Explor., 10, 245-58 (1978); Chem. Abstr., 9 0 , 1 5 6 8 4 1 ~ (1979). (52M) Sturgeon, R. E., Berman, S. S., Desaulniers, A., Russell, D. S., Talanfa. 2 7 . 85-94 (1980). (53Mj Subramanian, K.'S., Meranger, J. C., Int. J. Environ. Anal. Chem., 7 , 25-40 (1979); Chem. Abstr., 9 2 , 99331t (1960). (54M) Tyree, S. Y., Jr., Stouffer, J. M., Bolllnger, M., Ion Chromafogr. Anal. Environ. Pollut., 2 , 295-304 (1979); Chem. Abstr., 9 2 , 185590h (1960). (55M) Vanderborght, B. M., Van Grieken, R. E., Int. J. Environ. Anal. Chem., 5, 221-37 (1976); Chem. Abstr.. 90, 174392~(1979). (56M) Vanderborght, B. M., Van Grieken, R. E., Talanta, 27, 417-22 (1980). (57M) Vanderstappen, M. G., Van Grleken, R. E., Talanta, 25, 653-8 (1978). (58M) Wang, J., Ariel, M., Anal. Chim. Acta, 9 9 , 89-98 (1978). (59M) West, M. H., Molina, J. F., Yuan, C. L., Davis, D. G., Chauvin, J. V., Anal. Chem., 51, 2370-5 (1979). (60M) Wlnge, R. K., Peterson, V. J., Fassel, V. A., Report, €PA/600/4791017, No. PB-294277, Avail. NTIS, 72 pp (1979). (61M) Wundt, K., Duschner, H., Starke, K., Anal. Chem., 51, 1487-92 (1979). (62M) Zel'tser, L. E., Morozova, L. A,, Talipov, S. T., Zh. Anal. Khim., 35, 97-103 (1980); Chem. Abstr., 9 3 , 12831e (1980). ORGANICS-GC
AND GCIMS METHODS
(1N) Albalges, J., Aibrecht, P., Int. J. Environ. Anal. Chem., 6 , 171-90 (1979); Chem. Abstr., 91, 145800~(1979). (2N) Bean, R. M., Ryan, P. W., Riley, R. G., Report, BNWL-SA-6288, CONF-7708108-1, Avail. NTIS, 23 pp (1977). (3N) Beggs, D., NBS Spec. Publ. (U.S.), 579, 169-73 (1979). (4N) Bellar, T. A., Lichtenberg, J. J., ASTM Spec. Tech. Publ., STP 686, 108-29 (1979); Chem. Abstr., 9 2 , 152707~(1980). (5N) Brozowskl, G., Burkitt, D., Gabriel, M., Hanrahan, J., McCarthy, E., Smith, J., NBS Spec. Pub/. ( U . S . ) ,519, 175-9 (1979). (6N) Chen. C.. Huan Chino - K'o Hsueh, 53-8 (1979); Chem. Abstr., 92, i52725c (1980). (7N) Chmil, V. D., Zh. Anal. Khim., 33, 2232-4 (1978); Chem. Abstr., 90, 127281f 119791. > -, (8N)-C&tts, R. T., Hargesheimer, E. E., Pasutto, F. M., J. Chromatogr., 179, 291-9 (1979); Chem. Abstr., 9 2 , 1 6 8 9 2 1 ~ (1980). (9N) Coutts, R. T., Jones, G. R., Liu, S. F., J. Chromatogr. Sci., 17, 551-4 (1979); Chem. Absfr., 9 2 , 152702t 119801 \.---,(ION) Di Corcla, A,, Samperl, R., Anal. Chem., 51, 776-8, (1979). (11N) Dletz, F., Traud, J., Vom Wasser, 57, 235-57 (1978); Chem. Abstr., 9 7 , 9286) (1979). '
212R
ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
(12N) Dletz, E. A., Jr., Singley, K. F., Anal. Chem., 51, 1609-14 (1979). (13N) Dressman, R. C., Stevens, A. A., Fair, J., Smlth, B., J. Am. Wafer Works Assoc., 71, 392-6 (1979). (14N) Drozd, J., Novak, J., Rijks, J. A., J. Chromatogr., 758, 471-82 (1978); Chem. Abstr., 90, 28764r (1979). (15N) Freudenthal, J., Int. J. Enviran. Anal. Chem., 5 , 311-21 (1978); Chem. Abstr., 9 0 , 161742s (1979). (16N) Grlest, W. H., Maskarlnec, M. P., Herbes, S. E., Southworth, G. R., Report, CONF-790663- 7, Avail. NTIS, 22 pp (1979). (17N) Grimmer, G., Naujack, K. W., Vom Wasser, 53, 1-8 (1979): Chem. Absfr., 9 2 , 220467~(1980). (18N) Guillemln, C. L., Martinez, F., Thiault, S., J. Chromatogr. Scl., 77, 677-81 (1979); Chem. Absfr., 9 3 , 166034 (1980). (19N) Ingram, L. L., Jr., McGlnnls, G. D., Parlkh, S. V., Anal. Chem., 57, 1077-9 (1979). (20N) Ioffe, 8. V., Stolyarov, 8. V., Smirnova, S. A., Zh. Anal. Khlm., 33, 2196-201 (1978); Chem. Abstr., 90, 174396g (1979). (21N) Keith, L. H., Lee, K. W., Provost, L. P. Present, D. L., ASTM Spec. Tech. Publ., STP 666, 85-107 (1979); Chem. Absb., 9 2 , 1 5 2 7 0 6 ~ (1980). (22N) Klockow, D., Bayer, W., Faigle, W., Fresenius' Z . Anal. Chem., 292, 385-90 (1978); Chem. Abstr., 9 0 , 921411 (1979). Zh. Anal. Khlm., (23N) Kulikova, G. S., Kirlchenko, V. E., Pashkevich, K. I., 34, 790-3 (1979); Chem. Abstr., 97, 96383e (1979). (24N) Lamparski, L. L., Nestrick, T. J., J. Chromatogr., 756, 143-51 (1978); Pesticide Abstr., 79-0483 (1979). (25N) LeBel, G. L., Williams, D. T., Bull. Envlron. Contam. Toxicol., 24, 397-403 (1960); Chem. Abstr., 93, 79585w (1980). (26N) Lin, D. C. K., Foltz, R. L., Lucas, S. V., Petersen, B. A., Sllvon, L. E., Melton, R. G., ASTM Spec. Tech. Publ., STP 686, 68-84 (1979); Chem. Abstr., 92, 1 5 2 7 0 5 ~(1980). (27N) McAdams, M. J., Vestal, M. L., J. Chromatogr. Scl., 18, 110-15 (1960); Chem. Abstr., 93, 53616g (1960). (28N) Melcher, R. G., Anal. Chem., 52, 875-81 (1980). (29N) Murray, D. A. J., Environ. Sci. Res., 16, 207-16 (1978, Pub. 1980); Chem. Abstr., 93, 31515w (1980). (30N) Nowicki, H. G., Deulne, R. F., Kleda, C. A., ASTM Spec. Tech. Publ., STP 686, 130-51 (1979); Chem. Abstr., 92, 152706~(1980). (31N) Pereira. W. E... Hughes. . B. A.. J. Am. Water Works Assoc... 72,. ' 220-30 (1980). (32N) Piet, G. J., Slingerland, P., De Grunt, F. E., Vander Heuvel, M. P. M., Zoeteman, B. C. J., Anal. Lett. A 11, 437-46 (1978). (33N) Prater, W. A., Simmons, M. S., Mancy, K. H., ibid., 73, 205-12 119801. (34N) Qulmby, B. D., Delaney, M. F., Men, P. C., Barnes, R. M., Anal. Chem., 51, 875-80 (1979). (35N) Quimby, B. D., Delaney, M. F., Uden, P. C., Barnes, R. M., ibid., 52, 259-63 (1980). (36N) Richard, J. J., Fritz, J. S., J. Chromatogr. Sci., 78, 35-6 (1960); Chem. Abstr., 9 3 , 12854q (1960). (37N) Rose, M. E., Colby, B. N., Anal. Chem., 57, 2176-80 (1979). (38N) Selim, S., Warner, C. R., J. Chromatogr., 186, 507-11 (1978); Chem. Abstr., 9 0 , 109690J(1979). (39N) Shlnohara, R., Hori, T., Koga, M., BunseklKagaku, 27, 400-5 (1978); Chem. Abstr., 9 0 , 120240 (1979). (40N) Slmmonds, P. G., Kerns, E., J. Chromatogr., 186, 765-94 (1979); Chem. Abstr., 93, 12853p (1980). (41N) Soerensen. O.,Vom Wasser, 51, 259-64 (1978); Chem. Abstr., 9 7 , . 9287k (1979). (42N) Suffet, I. H., Glaser, E. R., J. Chromatogr. Sci., 16, 12-18 (1978); Chem. Absfr., 89, 1 8 5 7 1 8 ~(1978). (43N) Tal, D. Y., Report, U . S . Geol. Survey, Water Resources Inves., 79002. No. . PB-291 157. Avail. NTIS. 44 DD (19781. (44N)-Trussell, A. R., Umphres, M. D:, Leoig: L. Y: C., Trussell, R. R., J. Am. Water Works Assoc., 77, 385-9 (1979). (45N) Van Rensburg, J. F. J., Van Huyssteen, J. J., Hassett, A. J., Water Res., 12, 127-31 (1978): Chem. Abstr., 8 9 , 1355144 (1976). (46N) Varma, M. M., Siddlque, M. R., Doty, K. T., Machls, A., J. Am. Water Works Assoc., 71, 389-92 (1979). (47N) Wang, J., Zhao, L., Huan Chlng K'o Hsueh, 7 , 20-5 (1880); Chem. Absfr., 92, 220465b (1980). (48N) Webster, G. R. B., Worobey, B. L., Int. J. Environ. Anal. Chem., 6 , 197-202 (1979); Chem. Abstr., 9 7 , 181168h (1979). I
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~-
ORGANICS-HPLC
METHODS
(1P) Abaychl, J. K., Riley, J. P., Anal. Chim. Acta, 707, 1-11 (1979). (2P) Armentrout, D. N., McLean, J. D., Long, M. W., Anal. Chem., 51, 1039-45 (1979). (3P) Barcelona, M. J., Liljestrand, H. M., Morgan, J. J., ibid., 52,321-5 (1980). (4P) Bouyoucos, S. A., Armentrout, D. N., J. Chromatogr., 789, 61-71 (1980); Chem. Absfr., 9 3 , 79580r (1980). (5P) Brown, L., Analyst(London), 704, 1165-70 (1979). (6P) Brown, L., Rhead, M., ibid., 104, 391-9 (1979). (7P) Burns, D. A., NBS Spec. Publ. ( U . S . ) , 579, 587-600 (1979). (8P) Caveller, C., Analusis, 8, 46-8 (1980); Chem. Abstr., 9 2 , 2204832 (1980). (9P) Crane, R. I., Crathorne, B., Fielding, M., Environ. Scl. Res., 76, 161-72 (1978, Pub. 1980); Chem. Absb., 93, 3 1 5 1 3 ~(1980). (lop) Crathorne, B., Watts, C. D., Fielding, M., J. Chromatogr., 785, 671-90 (1979); Chem. Abstr., 9 2 , 185572d (1980). (11P) Das, B. S., Thomas, G. H., NBS Spec. Pub/. ( U . S . ) , 579, 41-56 (1979). (12P) Dutkiewicz, T., Masny, N., Ryborz, S., Maslowski, J., Grabka, A., Chem. Anal. (Warsaw), 2 4 , 191-3 (1979); Chem. Abstr., 9 7 , 49012y (1979).
WATER ANALYSIS (13P) Guiliemin, C. L., Thiault, S., Analusls, 6, 414-15 (1978); Chem. Abstr., 90,92152k (1979). (14P) Gurley, T. W., J. ChromstGogr.Scl., 78, 39-41 (1980); Chem. Abstr., 92, 17387e (1980). (15P) Hellmann, H., Fresenlus' Z . Anal. Chem., 302, 115-18 (1980); Chem. Abstr., 93,882269 (1980). (16P) Hullett, D. A., Eisenreich, S . J., Anal. Chem., 57, 1953-60 (1979). (17P) Kummert, R., Molnar-Kubica, E., Giger, W., ibid., 50, 1637-9 (1978). (18P) @an, K., Katz, E., Siavin, W., J. Chromatogr. Scl., 16, 517-22 (1978); Chem. Abstr, 90,92145k (1979). (19P) Ogan, K., Katz, E., Slaviin, W., Anal. Chem., 57, 1315-20 (1979). (20P) Riggin, R. M., Howard, C. C., ibid., 57,210-14 (1979). (21P) Schiff, L. J., Pleva, S. G., Sarver, E. W., Ion Chromafogr. Anal. Environ. Pollut., 2,329-44 (1979); Chem. Abstr., 92,2032182 (1980). (22P) Schwartz, H. E., Anzion, C.J. M., Van Vliet, H. P. M., Copius Peerebooms, J. W., Brinkman, Ul. A. T., Int. J. Environ. Anal. Chem., 6 , 133-44 (1979); Chem. Absb., 97, 145799f (1979). (23P) Sorrell, R. K., Reding, f?., J . Chromatogr., 765, 655-70 (1979); Chem. Abstr., 92, 168936h (1980). (24P) Thruston, A. D., Jr., J. Chromatogr. Scl., 16,254-9 (1978); Chem. Abstr., 89, 152405m (1978). (25P) Thurman, E. M., Malcolm, 1% L., U.S.Geol Surv. Water-Supply Paper, 7817-G,16 pp (1979). (26P) Van Vliet, H. P. M., Bootsman, T. C., Frel, R. W., Brlnkman, U. A. T., J. Chromatogr., 765,483-9'5 (1979); Chem. Abstr., 92,87599y (1980). ORGANICS-PHOTOMETRIC
METHODS
( l a ) Basson, W. D., Van Staden, J. F., Analyst (London), 103, 998-1001 (1978). (2Q) Ci, Y., Huan Ching K ' o iYsueh, 29-33 (1979); Chem. Abstr., 92, 1855771 (1980). (3Q) Goetz, R., Fresenius' 2. Anal. Chem., 296, 406-7 (1979); Chem. Abstr., 97, 181164d (1979). (4Q) Gomez-Taylor, M. M., Kuohl, D., Griffiths, P. R., Int. J . Envlron. Anal. Chem., 5 , 103-17 (1978); Cbem. Abstr., 89, 117420r (1978). (54) Griffith, K., Thomas, D., Ferrin, C., Deem, C., ASTMSpec. Tech. Publ., STP 641, 69-78 (1977). (6Q) Hawthorne, A. R., Thorngate, J. H., Gammage, R. B., Vo Dinh, T., NBS Spec. Pub/.( U . S . ) , 519,719-22 (1979). (7Q) Hellmann, H., Vom Wasser, 48, 129-41 (1977); Chem. Abstr., 89, 135504a (1978). (8Q) Hellmann, H., Fresenius' i'. Anal. Chem., 295, 24-9 (1979); Chem. Abstr., 97,9281d (1979). (9Q) Hellmann, H., ibid., 295,388-92 (1979); Chem. Absfr., 91,96408s (1979). (IOQ) Karyakin, A. V., Anikina, L. I., Pivovarov, V. M.. Zh. Anal. Khim., 34, 2428-33 (1979); Chem. Abstr., 92, 168938k (1980). (11Q) Kodura, I., Lada, Z., C h m . Anal. (Warsaw), 24, 945-51 (1979); Chem. Abstr., 93,53555m (1980). (12Q) Kussmaul, H., Hegazi, M , Vom Wasser, 48, 143-54 (1977); Chem. Abstr., 89, 135505b (1978). (13Q) Melton, C. W., Anderson, S. J., Dye, C. F , Chase, W. E., Heffeifinger, R. E., Report, EPAl600/4-78IO66, No. PB-290687,Avail. NTIS, 80 pp (1978). (14Q) Monarca, S., Causey, B. S , Kirkbright, G. F., Water Res., 13,503-8 (1979); Cbem. Abstr., 91,1 6 2 8 1 7 ~(1979). (15Q) Parker, R. D., Fresenius' i'. Anal. Chem., 292,362-4 (1978); Chem. Abstr.. 90. 28791r (1979). (I6Q) Richardson, J. H., George, S. M., Ando, M. E., NBS Spec. Pub/. (U. S.),579,691-6 (1979). (17Q) Schwarz, F. P., Braun, VV., Waslk, S. P., Ana/. Chem., 50, 1903-5 11978) I -I
(18Q) Sorokina, T. S., Anikina, L. I., Karyakin, A. V., Zh. Anal. Khim., 33, 1190-5 (1978); Chem. Abstr., 89, 168800~(1978). (19Q) Thompson, K. C., Wagstaff, K., Analyst (London), 704, 668-79 (1979). (20Q) Van Haverbeke, L., Herman, M. A,, Anal. Chem., 57,932-6 (1979). ORGANICS-EXTRACTION
AND CONCENTRATION TECHNIOUES
(1R) Aiken, G. R., Thurman, E. M., Malcolm, R. L., Walton, H. F., Anal. Chem., 51, 1799-1803 (1979'). (2R) Basu, D. K., Saxena, J., Envlron. Sci. Technol., 12, 791-5 (1978). (3R) Buffie, J., Deladoey, P., Haerdi, W., Anal. Chim. Acta, 701,339-57 (1978). (4R) Burgasser, A. J., Colaruotciio, J. F., Anal. Chem., 51, 1588-9 (1979). (5R) Chang, R. C., Fritz, J. S.,Manta, 25,659-63 (1978). (6R) Coienutt, B. A., Thorburn, S . , Int. J. Environ. Anal. Chem., 7,231-44 (1980); Chem. Abstr., 93,53574s (1980). (7R) Faltusz, E.. Fresenius' Z . Anal. Chem.. 294. 385-90 (1979): .. Chem. Abstr., 97,9280c (1979). (8R) Friant, S.L., Suffet, I. H., Anal. Chem., 57,2167-72 (1979). (9R) Goidberg, M. C., Weiner, E. FI., Anal. Chim. Acta. 715,373-78 (1980). (10R) Hoffman, W. A., Jr., Ana!. Chem., 50. 2158-9 (1978). (11R) Khazal, W. J., Vejrosta, J., Novak, J., J. Chromatogr., 157, 125-31 (1978); Chem. Abstr., 89,203905j (1978). (12R) Korenman, Y. I., Alymova, A. T., Taldvkina, S. N., Nurtdinova. L. D.. Zh. And. Khim., 34,2425-7 (1979); Chem. Abstr., 92,185574f (1980). (13R) Korenman, Y. I., Bortnikcwa, R. N., ibid., 35, i63-6 (1980); Chem. Absfr., 93,31511s (1980). (14R) Lee, K. W., Oidham, R: G., Sellman, G. L., Keith, L. H., Provost, L. P., Lln, P. H., Lewis, D. L., Environ. Sci. Res., 16, 185-200 (1978, Pub. 1980); Chem. Abstr., 93,3 1 5 1 4 ~(1980). (15R) Malaiyandi, M., J. Assoc. Off. Anal. Chem., 61, 1459-64 (1978). (16R) Mikhailov, V. I., Oradovskil, S. G., U . S . Envlron. Prot. Agency, Off. Res. Dev., EPA-600/9-78-098, 92-101 (1977).
.
(17R) Murray, D. A. J., J. Chromatcgr., 777,135-40 (1979); Chem. Abstr., 91,216517a (1979). (18R) Olufsen, B., Anal. Chim. Acta, 713,393-4 (1980). (19R) Otson, R., Williams, D. T., Bothwell, P. D., Envlron. Scl. Technol., 73, 936-9 (1979). (20R) Peterson, H., Eiceman, G. A., Fleld, L. R., Slevers, A. E., Anal. Chem., 50, 2152-4 (1978). (21R) Renberg, L., /bid., 50, 1836-8 (1978). (22R) Ryan, J. P., Fritz, J. S., J. Chromatogr. Scl., 16, 488-92 (1978); Chem. Abstr., 90,76300b (1979). (23R) Sasakl, Y., Bunsekl Kagaku, 27,386-90 (1978); Chem. Abstr., 90, 127267f (1979). (24R) Schnare, D. W., J.-Water Pollut. Control Fed., 57,2467-74 (1979). (25R) Stepan, S. F., Smlth, J. F., Flego, U., Reukers, J., Water Res., 12, 447-9 (1978); Chem. Absfr., 89, 185721q (1978). (26R) Tateda, A., Frltz, J. S., J . Chromatogr., 752,329-40 (1978); Chem. Abstr., 69,117421s (1978). (27R) Voznakova, Z., Popl, M.,J . Chromatogr. Scl., 77,682-6 (1979); Chem. Abstr., 93,31428v (1980). (28R) Yamato, Y., Suzuki, M., Watanabe, T., J. Assoc. Off. Anal. Chem., 61,1135-9 (1978). (29R) Yohe, T. L., Suffet, I. H., Grochowski, R. J., ASTM Spec. Tech. Pub/,, STP 686, 47-67 (1978); Chem. Abstr., 92, 152704~(1980). ORGANICS-TOTAL
ELEMENTAL ANALYSIS
(1s) Gloor, R., Leidner, H., Anal. Chem., 57,645-7 (1979). (2s) Leenheer, J. A., Huffman, E. W. D., Jr., U . S . Geol, Survey Water Resources Inves. 79-4,I 6 pp (1979). (35) Levina, G. D., Kolosova, G. M., Senyavln, M. M., Vasil'ev, Y. B., Hh. Anal. Khim,, 33, 2019-25 (1978); Chem. Abstr., 90, 1272741 (1979). (4s) McCahlll, M. P., Conroy, L. E., Maier, W. J., Environ. Scl. Techno/., 14, 201-3 (1980). (5s) Miyagi, H., Kawazoe, K., Kamo, T., Takata, Y., Nakajima, F., Arikawa, Y., Bunsekl Kagaku, 27, 561-6 (1978); Chem. Abstr., 90, 12042m (1979). (6s) Oi, N., Yamamoto, S.,Itoh, T., Yasumasa, Y., Komiyama, Y., ;bid., 27, 551-5 (1978); Chem. Abstr., 90, 12041k (1979). (7s) Rezchikov, V. G., Kuznetsova, T. S., Zorin, A. D., Zh. Anal. Khim., 34, 188-92 (1979); Chem. Abstr., 90,209823~(1979). (8s) Rigdon, L. P., Barton, G. W., Fisher, E. R., Taber, L , Report, UCRL52407,Avail. NTIS, 98 pp (1978). (9s) Seto, M., Bunseki Kagaku, 27, 860-3 (1978); Chem. Abstr., 90, 92138k (1979). (10s) Van Steenderen, R. A., J. Autom. Chem., 7 , 88-91 (1979). (11s) Van Steenderen, R. A., Basson, W. D., Van Duuren, F. A., Water Res., 13,539-43 (1979); Chem. Abstr., 97, 128777e (1979). ORGANICS-OXYGEN DEMAND
(IT) Gantner, H., Fresenius' 2.Anal. Chem., 299, 42-5 (1979); Chem. Abstr., 92,844322 (1980). (2T) Hlmebaugh, R. R., Smith, M. J., Anal. Chem., 51, 1085-7 (1979). (3T) Klein, R. L., Jr., Gibbs, C. R., J.-Water Pollut. Control Fed., 57, 2257-66 (1979). (4T) Korenaga, T., BunsekiKagaku. 29,222-3 (1980); Chem. Abstr., 93, 12859v (1980). (5T) Stamer, J. K., McKenzle, S.W., Cherry, R. N., Scott, C. T., Stamer, S. L., J.-Water Pollut. ControlFed., 51,918-25 (1979). (6T) Wagner, R., Vom Wasser, 53, 283-5 (1979); Cbem. Abstr., 93, 53589a (1980). ORGANICS-MISCELLANEOUS
(1U) Burkhard, L. P., Armstrong, D. E., U . S . NTIS, PB Rep-279610,Avail. NTIS, 25 pp (1978). (2U) Garrison, A. W., Pope, J. D., Alford, A. L., Doll, C. K., NBS Spec. Pu6l. ( U . S . ) , 519,65-78 (1979). (3U) Hirayama, H., BunsekiKagaku, 27,252-5 (1978): Chem. Abstr., 89, 135513~(1978). (4U) Hollies, J. I . , Pinnlngton, D. F., Handley, A. J., Anal Chim. Acta, 7 1 1, 201-13 (1979). (5U) Keith, L. H., Environ. Sci. Technol., 73,1469-71 (1979). (6U) Leonova, V. G., Belen'kii, S. M., Klyachko, Y. A., Zavod Lab., 45, 112-3 (1979); Chem. Abstr., 90,2098354 (1979). (7U) Lium, 9. W., Shoaf, W. T., Water Resour. Bull., 14, 190-4 (1978). (8U) Lochtman, J., Reichert, J. K., Bernhardt, H., Vom Wasser, 50, 7-19 (1978); Chem. Absfr., 90, 12032h (1979). (9U) Sharma, G. M., DuBois, H. R., Pastore, A. T., Bruno, S. F., Anal. Chem., 51, 198-9 (1979). (1OU) Tobin, R. S.,Ryan, J. F., Afghan, B. K., Water Res., 12, 783-92 (1978); Chem. Abstr., 90,60974p (1979). (11U) Trussell, A. R., Umphres, M. D., J. Am. Water Works Assoc., 70, 595-603 (1978). (1.W Tu, c., Fen Hsl Hua Hsueh, 77,34-8 (1979); Chem. Abstr., 91, 181165e (1979). (13U) Uchlyama, M., Water Res., 72,299-301 (1978), Chem. Abstr., 89, 135526) (1978). (14U) Uchiyama, M., Yamaguchi, M., Bunseki Kagaku, 27, 129-33 (1978); Chem. Abstr., 89, 117408 (1978). PESTICIDES
(1V) Amore, F., NBS Spec. Publ. ( U . S . ) , 579, 191-203 (1979). (2v) Bargnoux, H., Pepin, D., Chabard, J. L., Vedrine, F., Petit, J., Berger, J. A., Analusls, 6, 107-1 12 (1978); Pesticide Abstr., 78-221 1 (1978). (3v) Bargnoux, H., PePln, D., Chabard, J. L., Vedrine, F., Petit, J., Berger, J. A., /bid., 8, 117-8 (1980); Pesticlde Abstr., 80-2078 (1980). (4V) Becconsall, J. K., Analyst (London), 103, 1233-8 (1978). ANALYTICAL CHEMISTRY, VOL. 53, NO. 5, APRIL 1981
213R
Anal. Chem. 1981, 53, 214R-233R (5V) Blanchet, P. F., J . Chromatogr., 779, 123-9 (1979); Pesticide Abstr., 80-0884 (1980). (6V) Blanchet, P. F., J . Agric. Food Chem., 2 7 , 204-6 (1979); Pesticlde Abstr.. 79-0990 (1979). (7V) Bowmer, K. H., Adeney, J. A., Pestic. Sci., 9 , 342-53 (1978); Pesticide Abstr., 79-0747 (1979). (8V) Brodtmann, N. V., Koffskey, W. E., J . Chromatogr. Sci., 77, 97-110 (1979); Pesticide Abstr., 79-1487 (1979). (9V) Chmil', V. D., Zh. Anal. Khim., 34, 2067-70 (1979); Pesticide Absfr., 80-1200 (1980). (IOV) Chmil', V. D., Klisenko, M. A,, ibid., 32, 592-5 (1977); Pesticide Abstr., 78-2248 (1978). (11V) Chmil', V. D., Pilenkova, I. I., Far'yanova, A. D., Zorova, A. I., Gig. Sanit., 43, 56-8 (1978); Pesticide Abstr., 79-0981 (1979). (12V) Chrnll', V. D., Pilenkova, I. I., Fat'ianova, A. D., Zorova, A. I., ibld., 44, 57-8 (1979); Pesticide Abstr., 79-1968 (1979). (13V) Copin, A., Delmarcelle, J., Deleu, R., Renaud, A,, Anal. Chim. Acta, 776, 145-52 (1980). (14V) Dawson, V. K., Harman, P. D , Schultz, D. P., Allen, J. L., J . Fish. Res. Board Can.. 35, 1262-5 (1978); Pesticide Abstr., 79-0239 (1979). (15V) Deleu, R., Copin, A., J . Chromatogr.. 777, 263-8 (1979); Pesticide Ab&., 79-1738 (1979). (16V) Devenish, I. W., Hading-Bowen, L., Environ. Sci. Res., 76, 231-53 (1978, Pub. 1980); Chem. Abstr., 93, 31516x (1980). (17V) DiPrima, S.J., Cannlzzaro, R. D., Roger, J. C., Ferrell, C. D., J . Agrlc. Food Chem., 2 6 , 968-71 (1978); Pesticide Abstr., 78-2486 (1978). (18V) Dressler, M., J. Chromatogr., 765, 167-206 (1979); Pesticide Absfr.. 79-2835 (1979). (19V) Ershova, K. P., Komarova, N. S.,Shitukhina, A. F., Gig. Sanit., 43, 69-70 (1978); Pesticide Abstr., 79-0740 (1979). (2OV) Faas, L. F., Moore, J. C., J . Agric. Food Chem., 2 7 , 554-7 (1979); Pesticide Abstr., 79-1969 (1979). (21V) Fritschi, U., Fritschi, G., Kussmaul, H., Z Wasser Abwasser-Forsch., 1 7 , 165-7 (1978); Pesticide Abstr., 79-1000 (1979). (22V) Getz, M. E., Hanes, G. W., HIII, K. R., NBS Spec. Publ. ( U . S . ) , 579, 345-53 (1979); Pesticide Abstr., 79-3131 (1979). (23V) Handa, S . K., J . Assoc. Off. Anal. Chem., 63, 200-1 (1980). (24V) Kadaba, P. K., Bhagat, P. K., Osredkar, R., Murthy, V. R. K., Report, RR- 776, W79-01987, OWRT-A-065-ky No. PB-289370, Avail. NTIS, 69 pp (1979). (25V) Krasnykh, A. A., Gig. Sanit., 43, 92-4 (1978); Pesticide Abstr., 790982 (1979). (26V) Kucher, A. G , Rakov, A. A., Satmain. D. I., Gia. Sanit., 43, 78-9 (1978); Pesticide Abstr., 78-2481 (1978). (27V) Kurtz, D.A., NBS Spec. Publ. ( U . S . ) ,579, 19-32 (1979). (28V) LaBel, G. L., Wllllams, D. T., Griffith, G., Benoit, F. M., J . Assoc. Off. Anal. Chem., 62, 241-9 (1979). (29V) Loebering, H. G., Weil, L., Quentin, K. E., Vom Wasser, 57, 265-71 (1978); Pesticide Abstr., 79-1748 (1979). (30V) Lores, E. M., Bristol, D. W., Moseman, R. F., J . Chromatogr. Scl., 76, 358-62 (1978); Pesticide Abstr., 79-0234 (1979). (31V) Lott. P. F., Lott. J. W., Doms, D. J., ibid.. 76, 390-5 (1978); Pesticide Abstr., 79-0235 (1979). (32V) Mallet, V. N., Francoeur, J. M., Volpe, G., J . Chromatogr., 772, 388-93 (1979); Pesticide Abstr., 79-1975 (1979). (33V) Matisova, E., Krupcik. J., Liska, O., ibid., 773, 139-46 (1979); Pesticide Abstr., 79-2244 (1979). (34V) Mindrup, R., Jr., NBS Spec. Publ. ( U . S . ) , 579, 225-9 (1979); Pesticide Abstr., 79-3127 (1979). (35V) Moseman, R. F., Ward, M. K., Crist. H. L., Zehr, R. D.. J. Agric. Food Chem., 2 6 , 965-8 (1978); Pesticide Abstr.. 78-2485 (1978). (36V) Murray, D. A. J., J . Chromatogr., 777, 135-40 (1979); Pesticide Abstr., 80-0281 (1980). (37V) Otsuki, A., Takaku, T., Anal. Chem., 57, 833-5 (1979). (38V) Ragab, M. T. H., Chemosphere, 7 , 143-54 (1978); Pesticide Abstr., 79-0226 119791. .. (39V) Rees: G. A. V., Au, L., Bull. Environ. Contam. Toxicoi., 2 2 , 561-6 (1979); Pesticide Abstr., 79-2812 (1979). (40V) Rogovskiy, D. Y., Minenko, A. K., Pastushenko, T. V., Gig. Sanit., 43, 109-10 (1978); Pesticide Abstr., 79-0983 (1979). (41V) Sackmauerova, M., Kovac, J., Fresenius' Z . Anal. Chem., 292, 414-5 (1978); Pesticide Abstr., 79-2544 (1979). (42V) Scholten, A. H. M. T., Van Buuren, C., Lawrence, J. F., Brinkman, U. A. T., Frei, R. W., J . Liquid Chromatogr., 2 , 607-17 (1979); Pesticide Abstr., 79-1980 (1979).
(43V) Schulten, H. R., Fresenius' 2. Anal. Chem., 293, 273-81 (1978); Pesticide Abstr., 79-1225 (1979). (44V) Schulten, H. R., Stoeber, I., h i d . , 293, 370-6 (1978); Chem. Abstr., 90. 1...~. 5 6 8 2 9 ~11979) (45V) Singh, J., Coch&e, W. P., Scott, J., Bull. Environ. Contam. Toxicol., 2 3 , 470-4 (1979); Pesticide Abstr., 80-0268 (1980). (46V) Smith, S . , Willis, G. H., J . Agric. Food Chem., 2 6 , 1473-4 (1978); Pesticide Abstr., 79-0480 (1979). (47V) Smyth, M. R., Smyth, W. F., Analyst (London), 703, 529-67 (1978). (48V) Soderquist, C. J., Crosby, D. G., Anal. Chem., 50, 1435-9 (1978). (49V) Solomon, J., ibid., 57, 1861-3 (1979). (50V) Stoeber, I., Reupert, R., Vom Wasser, 57,273-83 (1978); Pesticide Absb., 79-1749 (1979). (51V) Sundaram, K. M. S.,Szeto, S. Y., Hlndle, R., J . Chromatogr., 777, 29-34 (1979); Pesticide Absfr., 80-0278 (1980). (52V) Takaku, T., Otsukl, A., Takahashi, M., Bunseki Kagaku, 28, 702-4 (1979); Chem. Absfr., 92, 82073n (1980). (53V) Thompson, K. C., Wagstaff. K., Analyst (London), 704, 668-79 (1979). (54V) Veith, G. D., Austin, N. M., Morris, R . T., Water Res., 73, 43-7 (1979); Pesticide Abstr., 79-1249 (1979). (55V) Yamato, Y., Suzuki, M., Watanabe, T., J . Assoc. Off. Anal. Chem., 67, 1135-9 (1978). (58V) Yamato, Y., Suzuki, M., Watanabe, T., Biomed. Mass Spectrom., 6 , 205-7 (1979); Pesficlde Absb., 79-2539 (1979). (57V) Zakitis, L. H., Bull. Environ. Contam. Toxicol., 2 3 , 391-7 (1979); Pesticide Abstr., 79-3105 (1979). (58V) Zhu, A., Chang, L.. Wu, H., Yang, C., Ho, Y., Huan Ching K ' o Hsueh, 1979, 58-63; Chem. Abstr., 9 2 , 185568e (1980).
.
DETERGENTS
(IW) Chleblckl, J., Garncarz, W., Chem. Anal. (Warsaw), 2 4 , 675-81 (1979); Chem. Abstr., 9 2 , 99337w (1980). (2W) Favretto, L., Stancher, B., Tunis, F., Analyst (London), 704, 241-7
.- . -,.
I,I q 7 Q \
(3w) Gagnon, M. J., Water Res., 73, 53-6 (1979); Chem. Abstr., 9 0 ,
158847a 11979). ( 4 W < - H e l k h n , -H., Fresenius's 2. Anal. Chem., 293, 359-63 (1978); Chem. Absb., 90, 127285k (1979). (5W) Hon-Nami, H., Hanya, T., J. Chromatogr., 767,205-12 (1978); Chem. Abstr., 9 0 , 76304f (1979). (6W) Le Bihan, A., Courtot-Coupez, J., Analusis, 6, 346-9 (1978); Chem. Abstr., 9 0 , 15719y (1979). (7W) Otsuki, A., Shiraishi, H., Anal. Chem., 57, 2329-32 (1979). (8W)Yaneva, S., Borisova-Pangarova, R., Taianta, 25, 279-82 (1978). MISCELLANEOUS
(1X) Batley, G. E., Giies, M. S . , Water Res., 73, 879-86 (1979); Chem. Abstr., 92, 820493 (1980). (2X) Boutron, C.,Martln, S., Anal. Chem., 57, 140-5 (1979). (3X) Chakrabarti, C. L., Subramanian, K. S.,Sueiras, J. E., Young, D. J., J. Am. Wafer Works Assoc., 70, 560-5 (1978). (4X) Chatfield, E. J., Glass, R. W., Dillon, M. J., U . S . NTIS, PB Rep. 280783, Avail. NTIS, 132 pp (1978). (5X) Funk, W., Vom Wasser, 4 8 , 75-87 (1977); Chem. Abstr., 8 9 , 117415t (1978). (6X) Garbarino, J . R., Taylor, H. E.,Appi. Specfrosc., 34, 584-90 (1980). (7X) Hall, A., Godlnho, M. C., Anal. Chim. Acta, 773, 369-73 (1980). 18x1 Henriksen. A., Nature(London), 278, 542-5 (1979); Chem. Abstr., 9 7 , 128660m (1979). (9X) Kelr, R. S., Mar. Chem., 8 , 95-7 (1979); Chem. Abstr., 9 2 , 82051d (lox) Mart, L., Fresenius' Z . Anal. Chem., 296, 350-7 (1979); Chem. Absfr., 97, 1628271 (1979). (11X) Mart, L., ibid., 299, 97-102 (1979); Chem. Abstr., 9 2 , 1 5 2 7 2 1 ~ (1980). (12x1 Pakalns. P., Batlev. G. E., Cameron, A. J., Anal. Chim. Acta, 99, ' 333-42 (1978). (13X) Peterson, J. M., Whlte, C. C., Pljanowski, B. S.,Ward, G. K., Report, NOAA- TM-NOS-23, NOAA- 79072307; No. PB- 3007 79, Avall. NTIS, 23 PP (1979). (14X) Shaw, F., Analyst(London), 705, 11-17 (1980). (15X) Taylor, H. E., Erdmann, D. E., Chem., Biomed., and Environ. Instrumentation, 9 , 49-60 (1979).
Clinical Chemistry Merle A. Evenson Department of Medicine and Pathology, University of Wisconsin, 600 Highland Avenue, Madison, Wisconsin 53792
This listin of the literature selects articles from December 1978 througa November 1980. The business of clinical chemistry has become a very large industry in the United States, and the trends in the literature clearly reflect the 214 R
0003-2700/81/0353-214R$06.00/0
commercial interests in this field. In the past 2 years, instrument manufacturers and chemical reagent distributors have started to emphasize the use of the literature as an advertising medium to a much greater extent. The name
0 1981 American Chemical Society
