Anal. Chem. 1982, 54, 87R-96R
Organic Elernental Analysis T. S. Ma* Department of Chemistry,, City University of New York, Brooklyn, New York 11210
C. Y. Wang Department of Chemistry, Yunnan University, Kunming, Yunnan, China
Milton Gutterson Flavor Application Laboratow, Dragoco Inc., King Road, Totowa, New Jersey 07512
This article is a continuation of the previous review (1)and covers the literature from October 1979 to September 1981. An exceptionally large number of research papers were published during this period. As has been mentioned before, the trend is to develop methods for or anic elemental analysis at all levels (2). Whereas many stuties have been carried out in the determination of the major constituents in organic compounds, reliable automated methods of general applicability are still limited to carbon, hydrogen, and nitrogen. Much attention has been drawn toward trace analysis, particularly for toxic elements present in all kinds of organic materials. The use of ion-selective electrodes has been increasing steadily (3); these electrodes can be employed in manual as well as computerized processes. ]Research activities on multielemental analysis have been very active, and they encompass the determination of the major, minor, and trace constituents.
CARBON, HYDROGEN, NITROGEN Baur and Dirscherl(4) described the use of a microprocesser for CHN analysis; the pirobes for measuring C02, H20, and N2,respectively, are connected through the computer to give direct readout results. Bpurns et al. (5) constructed an automated signal-recording system for the CHN analyzer. The research group under Gelman (6) reported on automated analysis for CHN in organometallics, recommending a mixture of Cr203and AgMn04 as the oxidizing agent. Binkowski et al. described an automated method (7) for the gravimetric determination of C and H and an automatic sampler (8). Oita and Babcock (9) perfected the automated CH procedure for large samples, up to 40 mg of hydrocarbons. Sakla et al. (10) improved the performance and reliability of the automatic nitrogen analyzer. Bondarevskaya et al. (11) determined nitrogen in silazanes by automated coulometric titration of the NH3 produced. CHN analysis via gas chromatography continued to be studied (12-14), indicating that some problems still await solution. Schofield et al. (15) compared the determination of CHN in environmental standard-reference materials such as leaves and coal using combustion analysis and thermalneutron-capture y-ray spectrometry; it is concluded that the combustion method is more economical and less time-consuming and gives better precision and lower detection limits. Rezl and Uhdeova (16)proposed stannic oxide as a combustion aid. Grigoryan and Platonova (17) described the regeneration of Mn0,-based catalysts used in CHN analysis. For the determination of carbon and hydrogen only, special techniques for organometallics (18), polyhalogenated compounds (191, and liquid fuels (20) were reported. Yu et al. (21) described a packing containing Ag2W0?-MgO/Co3O4/ AgzW04-MgO suitable for the rapid combustion of refractive substances. Windsor and Denton (22) determined the atomic ratios of hydrocarbons or halocarbons emerging from a gas chromatograph by passing the gases into an inductively coupled plasma torch, emission from which was viewed by spectrometry. The effects of the presence of nitrogen in QQQ3-27QQf 82/0354-87R$Q6.00/0
carbon and hydrogen analysis by various methods (23) and of balance readings by the gravimetric method (24) were studied. Aoyogi et al. (25) determined carbon and nitrogen only using the gas chromatograph. Determination of carbon alone was performed for certain samples such as agricultural materials (26), marine sediments ( 2 3 , organic matter dissolved in methanol (28), and the 13C/12Cratio in vegetation (29). Determination of hydrogen alone in compounds containing C, H, and 0 can be done by simultaneous application of @-particle transmission and back-scatter auge models (30). As expectecf the individual element which has received most attention is nitrogen, and the Kjeldahl method predominates. Many papers were published on the improvement of digestion conditions (31-40), catalysts (41-44), and automation of the procedure (45,46); the modes of finish include colorimetry using the indophenol blue reaction (47, 48) or the Nessler reagent (49), application of ion-selective electrodes (50-52), titrimetry using NaOBr (53),and enzymic determination (54) of ammonia. Comparative studies were made between different digestion catalysts (55,56), semiautomated and conventional procedures (57), and Kjeidahl and Dumas methods (58). For the Dumas method, modifications of combustion techniques to deal with special samples (59-62), and gas chromatographic procedures for halogenated compounds (63, 64), polymers (65), and plant material (66) were reported. Organic nitrogen was converted to NH3 by hydrogenation (67) or pyrolysis in steam (68). Nitrogen-15 was determined by emission (69) or mass (70) spectrometry.
OXYGEN, SULFUR, HALOGENS Kopycki et al. (71) constructed an automated apparatus for the determination of oxygen; the sample is pyrolyzed in a stream of nitrogen to produce CO which is converted to C 0 2 to be determined coulometrically (72). Duan et al. (73) determined oxygen via gas chromato raphy using molecular sieve 5 4 complete elution of N2 and C peaks requires 8 min. For the determination of oxygen in samples containing fluorine, it is necessary to fix the fluorine in the sample zone (74). Campbell and Chang (75) proposed some new combustion catalysts. Gusinskii et al. (76) described a radioactivation method for determining IsO. Liang et al. (77) described the determination of sulfur by combusting the sample in a platinum basket placed in a heated round-bottomed flask through which oxygen was passed; SO3 was collected and the resulting sulfate solution was titrated with BaC12. Other methods for decomposition include the use of W03 in a silica tube (78, 79), KMn04 in glass vessel (80), and fusion with KOH (81). After closed flask combustion the resulting S O B can be titrated with Pb(N0J2 using a Pb2; ion selective electrode (82), or determined by indirect polarography (83);interference due to phosphorus can be preas Ag3P04(84). Because vented by precipitating the Pod3the closed flask combustion method is unsuitable for certain organometallic compounds, Chen et al. (85)heated the sample
8
0 1982 American Chemical Society
87 R
ORGANIC ELEMENTAL ANALYSIS
with potassium in a sealed tube and, after acidification, determined the HzS coulometrically or iodometrically. Chumachenko et al. (86) employed pyrolysis in the presence of saturated hydrocarbon to obtain HzS which was measured in a gas chromatograph. Paroutaud et al. (87) designed an automated analyzer for sulfur using a vertical combustion tube; the SO3produced is reduced to SOz which is determined in a titration cell. Volynskii et al. (88) described a semiautomated procedure to determine sulfur in organometallics; the combustion products are absorbed in alkaline HzOzand the residual alkali is titrated with HzS04. Since organic materials can be decomposed by the same technique (2) for the determination of sulfur and halogens, Rudnicki and Binkowski (89) described a semiautomated apparatus for determining these elements separately; after combustion in an oxygen stream, SO2- is titrated with Ba(C104)2,while Cl- or Br- is determined mercurimetrically, and I- iodometrically. Van Steenderen (90) constructed a halogen analyzer in which the combustion products are carried by argon into the titration cell. Conditions for complete combustion in the determination of chlorine or bromine were studied (91-93). In the finishin step, ion-selective electrodes (94-96) and coulometry (97,987 were used for C1-, Br-, and I-, respectively. End point detection for determining C1- by argentimetry (99) or mercurimetry (100) was refined. Machida and Utsumi (101) described a colorimetric method for bromine by closed flask combustion, oxidation of Br- to Br2,extraction with CC14,and measurement of 460 nm. Iodine was determined by potentiometry (102) or activation analysis (103). Calusaru et al. (104) compared combustion flask with Parr bomb for determining chlorine. Hilp (105) studied closed flask combustion for iodine in pharmaceuticals. Maciak and Kozlowski (106) described an automated method for determining fluorine. After decomposition in a tube in the presence of humidified oxygen, the combustion products are transferred with HzO to the titration vessel, and the Fis titrated with Th(C104) Other workers reported on the use of La3+ (107, 108) or Ce3$ (109) or the fluoride-ion electrode (110) for the determination of F after mineralization. Joglekar et al. (111) determined fluorine in perfluoro substances by neutron activation.
.
OTHER NONMETALLIC ELEMENTS Carboranes (112) and other organoboron compounds (113) were decomposed with low-temperature oxygen plasma after mixing with NH4N03as an additional oxidant, the residue B203being determined gravimetrically. Semenko et al. (114) described the flame-photometric determination of boron by using an air-acetylene flame; the sample was decomposed by digestion in HC1-HN03 mixture in a silica flask and the resulting solution was made up to volume with HzO for flame photometry. For group 5 elements, Galka and Machoy (115) tested the ascorbic acid analogues as reducing agents in the molybdenum blue method for the determination of phosphorus; only ascorbic and isoascorbic acids are suitable. After closed flask combustion of an organophosphorus compound, Grob and as Pb3(P04)2 McNally (116) attempted to precipitate Po43and titrate the unconsumed Pb2+with EDTA; it was unsuccessful owing to dissolution of the precipitate with formation of the PbEDTA complex. Campbell and Low (117)employed closed flask combustion to decompose organic arsenicals and described two titrimetric and two colorimetric methods to determine the As02- in the presence or absence of halogens. Chatterjee (118) decomposed organoantimony compounds in which antimony is attached to alkylthio groups by dissolving the sample in HC1 and adding I to oxidize Sb3+ to Sb5+; subsequent boiling regenerated S i 3 + which was determined iodometrically. For the determination of bismuth in pharmaceuticals, Krzek and Al-Mutari (119) found that Bi3+forms a 1:4 complex with I- which can be extracted into isobutyl alcohol for absorption measurement at 396 nm. Campiglio (120) decomposed organoselenium compounds by closed flask combustion and determined Se4+by potentiometric titration with Pb(N03)zusing a lead ion selective electrode for end point detection. Tsurkan et al. (121) conducted the combustion in a silica tube after mixing the sample with sucrose; the resulting SeOz was driven out by a stream 88R
ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982
of Oz and determined iodometrically. Koyama et al. (122) described the inductively coupled plasma determination of selenium; after decomposition in HN03, the solution was introduced into the argon plasma and the emission intensity was measured at 196.03 nm.
ORGANOMETALLICS During visits to chemical research laboratories, the senior author has noted that many new organometallic compounds were synthesized from a number of elements. Analytical reports on these compounds, however, are seldom published, because they are related to national defense or the search for catalysts. Hence the papers which appear in the literature are of general nature. For instance, Volodina et al. (123) described the determination of metals in organic compounds using a low-temperature oxygen plasma; the oxides obtained were either weighed or dissolved in HN03 and titrated with EDTA. Utsumi (124) determined organometallics by an indirect method using N-methyl-2-pyrrolidine acid adducts. Abou-Taleb (125) combusted organometallic compounds in closed flask or open tube and determined the metals with 8-hydroxyquinoline. Basceanu et al. (126) analyzed A1C13-hydrocarbon complexes by decomposing the sample with 2 M NaOH and adding EDTA; after acidification and extraction of AI-EDTA with toluene, the unconsumed EDTA in the aqueous phase was titrated with 0.05 M ZnS04. According to Springer et al. (127), the formation of the A1-EDTA complex is not quantitative in the presence of acetate or tartrate, unless the solution is boiled and then cooled, or kept for 4 h, before the back-titration. Mikhailovskaya et al. (128) decomposed organochromium compounds in HzS04-HC104 mixture, added HzO and KMn04 to oxidize Cr3+to Cr6+,and determined Cr6+ with diphenylcarbazide by measuring the absorbance at 546 nm. Shushunova et al. (129) separated dimethylmethoxygallium and -indium by gas chromatography in a molybdenum-glass column, and determined Ga and In by flameless atomic absorption spectrometry using the lines 287.4 nm and 324 nm, respectively. Bazalitskaya et al. (130) analyzed organic compounds containing lanthanoids by pyrolysis at 1000 "C for 1 h in an oxygen stream and determined the residue as metal oxide gravimetrically. Mercury in organic compounds was determined by the use of an Hg2+ion selective electrode after closed flask combustion (131), or by X-ray fluorescence spectrometry (132). Shanina et al. (133) digested organorhodium compounds with HzS04-HN03 or HZSO4-HC1O4,and determined rhodium spectrophotometrically as a complex with 5-sulfoallthiox or with SnClz and KI. Anisimova and Klimova (134) decomposed organotellurium compounds by heating the sample in a silica test tube placed into a tubular silica furnace at 900 "C for 45 min with passage of oxygen and weighed the residue as TeOz. Several groups of workers reported on the analysis of organotin compounds. Coldea and Haiduc (135) digested the sample in HN03-HC104-HzS04, added H,O and evaporated the reaction mixture to dryness, dissolved the residue in HC1, and determined Sn4+by anodic stripping voltammetry. Kapila and Vogt (136) studied the Sn emission at 610 nm by organotin compounds in a flame-photometric detector in the gas chromatograph. Komora et al. (137) found that gas, thin-layer, and gel chromatographic methods were applicable to the determination of organotin compounds used for wood preservation. Vishnyakova et al. (138) described the determination of titanium in organotitanium compounds containing halogens; the sample was decomposed by refluxing with sodium in 2ethoxyethanol, and after dilution with HzO and acidification, titanium was determined spectrophotometrically with HzOp For the determination of uranium in organic complexes, Celon et al. (139) decomposed the sample by closed flask combustion in the presence of benzoyl peroxide, using HNOBas absorbent; the solution was then adjusted to pH 3 and titrated with 0.01 M pyridine-2,6-dicarboxylicacid using Arsenazo I as indicator. Vishnyakova and Malkova (140) gave a spectrophotometric method to determine zirconium in organozirconium compounds.
SIMULTANEOUS MULTIELEMENT DETERMINATION As more and more organic substances submitted for analysis
ORGANIC ELEMENTAL ANALYSIS
Table 1. Simultaneous Determination of Several Elements elements determined
he time
between wning at in NOM Carand consuitlng or kcluring abroad. He has wmen 7 books. 6 chapters in chemical treatisas. and 150 research papers. He has lectvred in m n y C W ~ M dving past 3 decades. He sewed twice as Fulbrght lecturer and wce as American spaclaiist wim the Bureau of Educational and c m a i A I I ~ ~ ~ Dof me state ~epartment. ROfesso( Ma is an editor of MikroEhimics .~ .-Acts , the IntamaNanal .. kwrnil on microchemistry and trace analysis. The cwrent interests of Professor Ma are c o n m e d wim microchemical investkption of medicinal plants, orwnic analysis and Synthesis in the milligram to micragram range, and the use of small-scab, inexpensive equipment to teach chemistry.
P
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Y. waw (Wang Cho"g-YI or wang ChangYi) was barn in 1938 in Kunming. Yunnan Rovhce. Chlna. He s w at me Department 01 Chemlmy of Yunnan UntYersky. Upon graduation in 1959 wim a diploma equivalent to the bachekn's degee. he was assigned to work in me microanalytical b b o r a t q 01 the Research Instilute of Chemistry. Chinese Academy of Scbncns. in Peking. Thirteen years later, he was mansfenedto his nattve town to take charge 01 me microanalytlcai senion of me Yunnan Research Institute 01 Chemical Technology. I n 1979 he was appohted lemrw in analytical chemistry in Yunnan Univeroltv. Presentw Mr. Wang teaches BYW yea; a group d about 40 students who apecblize in wganic analytical chemistry and conducts research in organic mF uoanalysls. Ion-sekctlve electrcdes. and trace analysis. He has published over 50 .DBDB~S. He is a member d the American Microchemical Socbty. .
r,
H,S,or halogen c, H,CI C, H,Cl,or Br c, H,AS C, H,Fe c, H,Hg C, H,In C,
C, H, Si c, H,N, C, H,N, 0, or S c, H,N, c, H. N,
o s s
N, halogen
S, CI, F
s,
se
halogen, Ti
method
ref
gravimetric gravimetric gravimetric gravimetric gravimetric gravimetric gravimetric gravimetric gas chromatographic automated gas chromatographic automated titrimetric titrimetric titrimetric titrimetric. colorimetric
142-143 144 145 146 147
148 149 150-1 51 152 153 154
155 156 157 158 159
"-
MMon QUn.nm received his B.S. &gree ham me cw Of cw Universny Of New Y a k in 1949. After gradman he waked tor papskb indwwies ( i m r l y JLowe Co.) DtYlsion of Consolmated Fmds Cap.. Englewwd, NJ. where he was chief duImbt and then plam manager. He hap since waked for E h h Division of Brmke b n d Fmds. Inc. He is now connected wim Dragom, Inc.. Totowa. NJ. w e he is directa. Flavor Applicalh Laborat-. For s e Y B T d yean ha was a part-time leC" in the graduste divlsbn of Brwklyn College. City UnkersW of New York. where he %peorised me laboratory for q ~ n t i t a t i ve~l e mental and funnionai woup microanatysis. He earned his master's degree horn Brmklyn College in 1956 by anending classes and doing research after waking hours. His special interest is In field of organic microanalysis. He was adlunct professo~01 chemistry at me New York Insthuts of Techn c k g y . Manhattan Campus. evening division. Mr. Outterson recently pub llshed several mnagraphs on lwd processing wim the Noyes Data Corp.. Park Ridge. N J There were tnied "Baked G a d s Production Processes. 1969". "Conlenionary Products Manufacturing Processes. 1969". "Frun J u b T e c h n w . 1 9 7 0 . "Fmn ProceBsing. 1971". and "Vegetable PToces hg. 1971". He k a member Of the ACS. me American Association 01 Cereal Cbmlsts. and the Instlute 01 F w d Technolagists.
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are mixtures (141) containing several elements. much effort has been made to determine simultaneously some or all elements present in one sample. Table I summarizes the papers in which existing combustion methods and conventional a p paratus were employed to perform the experiments. The researchers reported on improvement of techniques and difficulties encountered. Hence this information is useful to other analysts who are faced with the same combination of elements. It should be noted that the simultaneous determination of carbon. hydmgen, and nitrwen has been discusMd in a previous sertion. At the 4th International Sym osium on Capillary Chromatography held in Hindelang, germany, in May 1981, Yu et al. (160) presented a paper which is concerned with the simultaneous determination of I O nonmetallic elements in volatile organic compounds. The method is based on the
complete destruction of a compound into its constituent atoms by using a helium plasma and measurement of each atomic species by means of a spectrometer. The new instrument, designated as Model SG-1 Protype (GC)*-MES Apparatus, was jointly developed by the Lanchow Institute of Chemical Physics, Chinese Academy of Sciences, and the Second Optical Instruments Works, Peking; it was constructed from components entirely made io China. The whole system consists of t h e e parts: gas chromatograph, microwave generator and plasma discharge tube, and polychromator and data recording. The capacity of the spectrometer is up to 20 channels, of which 12 (C, H, D, 0, N, F, CI, Br, I, P, S, Hg) have hsen tested. The signal of the (GC)'-MES Apparatus for the specific element is nearly proportional to the quantity of the element; hence it is possible to calculate the atomic ratio of the parent compound and to deduce the quantity of the compound in a mixture through the elemental analysis. Satisfactory emoirical formulas were obtained for 14 test comnonnds con. . ~ Lining up to 16 carbons and H. 0, S. F, CI. Br, I. and Hg, respectively. For a mixture compristng Hg(C,H,J, and Hg(CH,)(C,H,), the weight percent of each compnund can he obtained with any one of the three elements using pure Hg(CH& as the internal standard. Hughes et al. (262)studied the photodiode array of nearinfrared and red atomic emission of C, H, N, and 0 in the argon inductively coupled plasma (ICP) using pure organic compounds. Contrasting sensitivity and resolution considerations involved in red and near-infrared ICP spectra with ultraviolet ICP spectra, it was found that the unintensified diode array is most sensitive io the 65C-930 nm region. For the analysis of pure organic compounds, the relatively high elemental concentrations and the enhanced red and near-infrared sensitivity of the photodiode array collectively mean that shorter exposure times may be used to achieve the desired array signal level. The simple nature of ICP spectra in the 650-930 nm region and the limited number of nonmetallic elements present in a pure compound provide an unusual situation in analytical plasma spectroscopy where high resolution appears to be unnecessary, and low dispersion spectrometers may be used for the simultslreous determination of C, H, N, and 0. As to the determination of metallic elements occurring at low and trace concentrations in organic materials, many avenues are open for simultaneous multielemental analysis. A number of papers are listed in Table I1 to show the great variety of analytical methods and instruments which are available and the nature of the samples submitted for routine analysis. Some interesting applications of multielemental analysis may he mentioned. For instance, Bayer e t al. (302) used it to determine the geographical origin of orange juice. The concentrations of 28 elements were determined in samples from Brazil and Florida; from these, 5 elements (Ba, B, Ga, Mn, and Rh) were chosen as target elements, and, treated by pattern recognition, proved to be adequate discriminators of geographical origin. Pietilainen et al. (303) performed pollution surveys by multielemental analysis of phytoplankton ~
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ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982
-
8BR
~
ORGANIC ELEMENTAL ANALYSIS
Table 11. Multielemental Analysis method anodic stripping atomic absorption
material analyzed biological food marine biological drug food marine
atomic emission
petroleum plant polymer biological marine petroleum pigment plant
atomic fluorescence colorimetry
mass spectrometry neutron activation
petroleum biological marine organometallic petroleum plant biological biological coal drug food
photon activation polarography radioactivity titrimetry X-ray emission X-ray fluorescence
marine petroleum plant polymer biological biological food plant biological food leather plant biological marine biological petroleum plant
elements determined
ref
Cd, Pb, Cu, Zn, T1 Cd, Pb, Cu Cu, Pb, Cd Fe, Mn, Cd, Cr, Pb, Cu, Zn, Co, Au, Ca, Mg, Li, Na, K, As, Sc, Sr, Al, Ba, La Zn, Fe, Ni, Co Cu, Mn, Fe, Zn, Pb, Rb, Se, As, Hg, Cd, Cr, Co, Ag, Bi, Ca, Mg, Ni, K, Sc, Na, Sn, A1 V, Ni, Zn, Fe, Cu, Cd, Pb, Ni, Mn, Cr, Bi, As, Se, co, Hg Pb, Zn, Fe, Ni, Cu, Ca, Al, Ba Ca, Mg, K, Na, Zn, Fe, Pb, Cu, Al, Mn, Sn As, Ba, Hg, Cu, Fe, K, Na, Mn Si, Al, Na, K, Ca, Fe, Cu, Mg, Zn, P, Sb, Te, Se, Bi, As, Hg, Ni, Pb, U, Mo, W Li, Na, K, Mg, Sr, Ba, B, Al, P, Mn, Fe Ni, V, Li, Ba, Ca, B, P, Al, Fe, Cu, P Na, Ca, Fe P, Mg, Ca, K, B, Zn, Mn, Mo, Al, Fe, Cu, Co, Cr, Sb, V 20 metals Fe. Mn. Co Hg, Cd,' Pb, Zn, Cu, P, N HK Cr VrTi N, P, S, C1 Sb, Ba, T1, Bi, Th Ca, P, Cr, Fe, Zn, Rb, Se, Ce, Sm, F, As, Au, Br, Cd, Mo, Ni, Sb, U, C1, Al, Co, Cu, K, Hg, Cs, Mn, Sc, Tb 51 elements N,p, K, Mg Cd, Hg, Pb, V, Cr, Mn, Co, Ni, Cu, Zn, Se, Br, Mo, Sb, Na, Mg, Al, C1, K, Ca, I Se, Hg, Cs, K 25 elements Si, As, Sb, Br, Hg, Se, Co, 17 elements 1 3 elements F, Ca, P, A1 Sn, Pb, Cu Cu, Pb, Cd, Zn, Sn, Hg, Fe, Sb, Cr, Te, As, T1 Cu, Fe, Mn, Zn, Pb, Cd U, Pu, Th, P, Ca, C, H Sr Fe, Cr, Zr, A1 C1. F. S Cl; K; Ca, Br, Fe, Cu, Zn, S, Mn, Rb, Cr, Si, P, Sr Cu, Zn, Pb Mn, Fe, Zn, Rb, Cu, Se, Mo, C1, Br, Pb, Ca s. c1 cr, c u , As
162,163 164-167 168 169-188
which is capable of concentrating metallic elements in water.
TRACE ANALYSIS OF SINGLE ELEMENT Concerning the determination of traces of a particular element in organic materials, research papers abound. While the methods for determining any element present in organic compounds have been well established ( 2 ) , problems frequently arise when working with small samples (304) in order to obtain reliable quantitative data. In most cases the decomposition step is crucial. Thus, Ruana et al. (305)studied various methods for determining vanadium or nickel in petroleum and found that the quality of the results depends fundamentally on the method of decomposition. In blood analysis by atomic absorption spectrometry, Beaty et al. (306) reported that a signal for chromium was almost wholly suppressed when oxygen was used in ashing the sample. Mineralization of organic substances for the determination of volatile elements such as mercury (307), arsenic (308),and selenium (309)was studied. Yuen and Kelly (310)decomposed vegetable oil for phosphorus determination by heating in a Parr bomb containing 2 mL of H 2 0 and filled with oxygen to 25 atm. Wet digestion in an open vessel remains the most common technique; improvements in the digestion media 90R
ANALYTICAL CHEMISTRY, VOL. 54, NO. 5, APRIL 1982
189 190-202 203-211 212-214 215, 216 217, 218 219-2 27 228 229-231 23 2 233-235 236 237 238, 239 24 0 24 1 242-244 24 5 246-264 26 5 266, 267 268-270 271-273 274 275-278 279 280 281 28 2-2 84 285 286-289 290 291 292 293-297 298 299 300 301
(311-313), automation (314),and use of a glassy-carbon container (315) were described. The effects of heating (316) or microwave drying (317) of biological samples, and defrosting, washing and drying of marine products (318) on trace element determination were reported. In the analysis of coal, the loss of Cr, Be, Cu, or Co increases with the temperature of combustion in the range 500-800 "C (319). When atomic absorption spectrometry is employed, the interference due to major elements (320) and the influence of the complex matrixes such as plants (321)and biological specimens (322,323)should be considered. In the determination of chlorine in petroleum by combustion and coulometry, the interference due to nitrogen, sulfur, and phosphorus can be eliminated by placing a scrubber tube packed with CuO between the combustion furnace and the coulometric cell (324). When mercury is determined by neutron activation, the standard can lose mercury before, during, and after irradiation, while biological specimens like hair or leaves show no loss of mercury after irradiation (325). Coating borosilicate containers prevents contamination in the determination of boron or aluminum in plant material (326). The preparation of organic-free water for total organic carbon determination was reported (327).
ORGANIC ELEMENTAL ANALYSIS
Table 111. Trace Analysis of Single Element element
material analyzed
aluminum biological drug food plant antimony biological food plant polymer arsenic biological food marine petroleum! beryllium biological bismuth biological food boron plant bromine biological marine cadmium biological food cesium biological calcium biological drug food petroleum carbon air biological marine methanol sohti on soil water chlorine marine plant chromium biological food biological cobalt marine plant copper biological food plant fluorine biological plant gallium biological gold biological iodine biological food plant iron biological food plant
mode of finisha
ref
aas, aes ise col, flu col, aas aas aas aas aas aas, col, naa, tlc aas, col aas col aas, flu col aas col nas, xry tit aas, naa aas rad col, tit, aas, flu, ms aas col, aas, flu tit, aes gc rad ir gc
334-338 339 340, 341 342, 343 344-346 347,348 34 9 350 351-358 359-363 364, 365 366 367,368 369 370 371-374 375-377 378 379-390 391 392 393-401 402 403-405 406,407 408 409 41 0 411
col, con gc, con, rad ise tit aas, col, naa, gc, ms aas am, gc aas, naa, rad aas col, aas col asv col, ise, mas, xry pir aas, naa, epm aas col, naa, paa, xry col, naa, rad rad col, IC col, aas, rad aas, asv
element lead
material analyzed
mode of finish
biological food marine petroleum lithium biological magnesium biological biological manganese mercury biological food marine petroleum plant biological molybdenum plant nickel biological food biological nitrogen petroleum biological phosphorus food biological platinum biological plutonium food marine biological polonium biological potassium plant praseodymium biological selenium biological dye food 412,413 plant 414-417 biological sodium 41 8 organic 419 420-43 1 compound strontium 432 biological food 43 3-4 3 7 biological 438,439 sulfur 44 0 food 441-446 petroleum 447 plant tellurium 448 plant 449-453 thallium biological 4 54 plant 455-457 thorium biological 4 5 8 , 4 5 9 tin food 460-467 polymer biological 468-4 7 0 uranium vana diurn biological 471 472-486 marine 487-491 petroleum 492,493 plant zinc biological food
ref
aas, aes, asv, rad, ms
494-507 aaS 508 509 aas 510-515 aas, aes, gc, ms 516, 517 aes, ms 51 8 col, aas 519-523 aas, naa 524-528 aas, afs 529-534 aas, col 535-542 aas, rad aas 543 544, 545 aas 54 6 - 54 9 col, pol, naa 5 50- 5 54 col, aas aas, pol, xry 555, 556 557,558 col, aas 559 lum col, lum, paa 560, 561 562-564 col, naa 565, 566 col, aas 56 7 aas 568-570 rad IC 571 IC 57 2 573 rad 574-576 col, ise 577, 578 aas 579 aas . aas, col, flu, gc, naa, xry 580-593 594 col 595-599 flu, aas, afs 600, 601 csv, naa ise, aes 602 603 aes
rad IC, rad col, xry IC
ise, cou, ic, lum, xry tit, tur aas aas, ms XrY rad aas, asv rad flu, naa, rad, ms col, aas, naa naa col, flu, naa col, aas, naa col, aas aas
604 605 606,607 608 609-613 614-616 61 7 618-620 6 21 622 623, 624 625 626-635 636-639 640, 641 642-644 645-647 64 8-6 55 656
a Abbreviations: aas = atomic absorption spectrometry, aes = atomic emission spectrometry, afs = atomic fluorescence spectrometry, asv = anodic stripping voltammetry, csv = cathodic stripping voltammetry, col = colorimetry (spectrophotometry at the visual region), con = conductivity, cou = coulometry, epm = electron probe microanalysis, flu = fluorimetry, gc = gas chromatography, ic = ion chromatography, ise = ion-selective electrode, IC = high-performance liquid chromatography, lum = luminescence, mas = molecular absorption spectrometry, ms = mass spectrometry, naa = neutron activation analysis, paa = photon activation analysis, pir = proton irradiation, rad = radioactivity, tit = titrimetry, tlc = thin-layer chromatography, tur = turbidimetry, xry = X-ray emission or fluorescence.
Standards for the determination of trace elements in plants and foods were published (328, 329). Comparison of the methods for determining sulfur in plants (330),fluorine in biological material (331),and other trace elements (332,333) were reported. During the 2-year period, over 600 papers on trace element analysis in organic materials have appeared. A representative list is given in Table 111. It shows that a wide range of samples were analyzed and many elements were involved. Papers dealing with the analysis of biological material (e.g., blood, urine, tissue) predominated. Among the myriad modes of finish, atomic absorption spectrometry was most commonly
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