Anal. Chern. 1985, 57,8 8 ~ - 9 4 ~ (14Y) Whlte, C.; Avery, M.; Blanton, W.; Hilpert, L.; Jackson, L.; Junk, G.; Maskarinec, M.; Paule, R.; Raphaellan, L.; Rlchard, J. Report DO€/ P€TC/TR-84/7; Order No. D€84001332, Avail NTIS, 81 pp (1983). (15Y) Winter, J. Report EPA-60010-84-035; Order No. PB84-149277, Avail. NTIS, 24 pp (1984). SAMPLINQ METHODS
(12) Barcelona, M. J.; Heifrich, J. A.; Garske, E. E.; Glbb, J. P. Ground Water Monk. Rev., 4 , 32-41 (1984). (22) Bolarln, M. C.; Romero, M.; Caro, M. An. €dafo/. Agrobiol. 4 1 , 2045-54 (1982) (32) Brandau, E. L.; Farland, R. J.; Bird, J. D.; Conte, J. A. Adv. Instrum., 3 8 , 143-50 (1983). (42) Bruchst, A.; Cognet, L.; Mallevialle, J. Rev. Fr. Sci. Eau, 2 , 297-309 (1983). (52j Carignan, R. Limnol. Oceanogr ., 29, 667-70 (1984). (62) Chen, X.; Zhu, 2. Huanjing Baohu (Beying), (8), 30 (1983). (72) Curran, C. M.; Tomson, M. E. Ground Water Monit. Rev., 3 , 68-71 (1983).
(82) Gibb, J. P.; Barcelona, M. J. J.-Am. Water Works Assoc., 78, 48-51 (1984). (92) Gudernatsch, H. Vom Wasser, 60, 95-105 (1983). (102) Ho, J. S. Y. J.-Am. Water Works Assoc., 75, 583-6 (1983). (112) Huber. A. L.; Kldby, D. K . Hydroblologia, 777, 13-19 (1984). (122) Keely, J. F.; Kerr, R. S. Proc. Natl. Symp. Aquifer Restor. Ground Water Monit., 133-47 (1982). (132) Mlller, H. H.; Crook, M. V.; Spigarelli, J. L. Report DRXTH-TE-CR82782; Order No. AD-A735365, Avall. NTIS, 231 pp (1984). (142) Neumayr, V. Comm. Eur. Communlties, EUR 8518,Anal. Org. Micropollut, Water, 5-14 pp. (1984). (152) Paasivitta, J.; Vihonen, H.; Salovaara, J.; Tarhanen, J.; Veijanen, A.; Lahtipera, M.; Paukku, R.; Kantolahti, E.; Laitinen, R. FOA Rep. 1983, C 40177-C2,C3, Proc. Int. Symp. Prot. Agalnst Chem. Warf. Agents, 37-44. (162) Pankow, J. F.; Isabelle, L. M.; Asher. W. E. Envlron. Sci. Techno/.. 78,310-18 (1984). (172) Pankow, J. F.; Isabelle, L. M.; Hewetson, J. P.; Cherry, J. A. Ground Water, 2 2 , 330-9 (1984).
Geological and Inorganic Materials Carleton B. Moore* and Julie A. Canepa Department of Chemistry, Arizona State University, Tempe, Arizona 85287
This review discusses publications describing methods for analysis of geological and inorganic materials during the period November 1982 through November 1984. The topical boundaries of the inorganic and geological materials are somewhat diffuse since closely related topics are reviewed in both the fundamental and application reviews. Articles of particular interest may be found in the reviews of air pollution, ferrous analysis, fuels, surface characterization, and water analysis in the application reviews and many of the fundamental reviews especially sampling, emission spectrometry, atomic adsorption and flame emission spectrophotometry, mass spectrometry, X-ray spectrometry, and surface analysis. The citations of this review may well, by necessity, include some of those listed in other reviews, but for the most part they have been selected from the many thousands available to give the reader an overview of recent advances in each specialty reviewed together with mentions of particularly interesting specific or specialized contributions.
GENERAL REVIEW LITERATURE The publication of books and monographs directly related to this review seems to have been made at a rather steady state over the past decade. If we were to pick a ”must be read” publication in the past 2 years it would be “Studies in ”Standard Samples” of Silicate Rocks and Minerals 19691982” by Sydney Abbey (1). This excellent contribution includes not only the data but also discussions of the history of standard samples and data handling and evolution. Among the major publications is the publication of the papers presented at an international symposium a t the Bhabha Atomic Research Centre, Bombay, ublished as an edited volume, “Trace Analysis and Technof)ogicalDevelopment” by M. S. Das (2). This book has contributions on the analysis of high-purity materials as well as samples of interest to environmental, earth, and nuclear scientists. “Analytical Chemistry of Molybdenum” (3) by G. A. Parker and “Physical Methods of Modern Chemical Analysis, Vol. 3.” by T. Kuwana (4), both have materials as well as samples of interest to readers of this review. An analytical technique of particular interest to mineral chemistry is reviewed in “Nuclear Tracks” (5) edited by J. N. Goswami. Another standard geochemical technique “Principles of Quantitative X-Ray Fluorescence Analysis” (6) by R. Tertian and F. Claisse has a particularly good chapter on sampIe preparation. Many items of interest are included in the two volume 1984 “CRC Handbook of Atomic Absorption Analysis” (7) by A. Varma, “Trace Elements in Coal” (8)edited by V. Valkovic and ”Trace Elements
in Soils and Plants” (9)by A. Kabata-Pendias and H. Pendias may also be of interest. M. Thompson and J. N. Walsh have produced “A Handbook of Inductively Coupled Plasma Spectrometry” (10). In the handling of data area, “Pattern Recognition Approach to Data Interpretation” (11)by D. D. Wolff and M. L. Parsons is a good short review. Selected papers from the Tenth International Geochemical Exploration Symposium have been edited by A. Bjorklund in a volume “Geochemical Exploration 1983” (12) and ”ArchaeologicalChemistry-111” (13)by J. B. Lambert. Paul Henderson, editor of ”Rare Earth Element Geochemistry” (14), himself contributed a chapter on their analytical chemistry. The entire book, which is volume 2 of “Developments on Geochemistry”, is of importance to analytical chemists.
ANALYTICAL TECHNIQUES Atomic Absorption Spectroscopy. Atomic absorption spectroscopy, both flame and flameless, continues to be a dominant and preferred method for the elemental analysis of geologic and inorganic materials. Van Loon (15) published a review emphasizing trace analysis titled, “Bridging the gaps in analytical atomic absorption spectrometry”. Many of the trace analytical AA techniques are improved by the pretreatment of the geologic and inorganic sample. Bartha and Fugedi (16) suggest that the cold vapor determination of Hg in rocks and soils is greatly improved if the preanalytical extraction procedures done to remove interfering ions be done under strongly alkaline conditions. The determination of Cd and P b in geological materials by Terashima (17) involved a three-step sample dissolution procedure with a subsequent solvent extraction. Similarly,Viets, Clark, and Campbell (18) use an organic solvent extraction after only a partial leach of geologic materials to determine weakly bound Ag, Bi, Cd, Cu, Mo, Pb, Sb, and Zn. These elements are used as pathfinders in the exploration of ores. Castledine and Robbins (19) describe a portable field atomic absorption analyzer. The analyzer is flameless but not a conventional C furnace, but rather the atomizer is a W ribbon. The thallium abundance in all types of environmental samples such as rocks, soils, and waste material was analyzed by Gorbauch et al. (20). Sample decomposition and pretreatment procedures are discussed. Smith (21) presents a laboratory manual for determining metals in water. This manual details the analysis of 19 metals. A universal method for the analysis of a variety of environmental, geologic, and inorganic materials is presented by Schinkel (22). Schinkel determined Cu, Mg, Sr, K, Na, Li, 0 1985
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Fe, Mn, Cr, Ni, Ca. Co, Zn,and Cd by FAAS,and with the addition of Cs and La, interferences in the flame are eliminated. A new twin spray tlame AAS method was developed by Yu et al. (23)for the determination of Sb, Bi, and Hg of trace without the need for hydride generation. The analmetals in siliceous standards were analyzed after a lithium tetraborate fusion. The method compares favorably with acid dipestion (24). The detection of In after a lithium tetraborate fusion was done by Zhou et al. (25). The precision and sensitivity were improved by impregnating the graphite furnace with Na tungstate. Zhou et al. (26)also determined Sn using the same fusion and W impregnation graphite furnace technique. The determination of trace metals in om is of interest Bye (27)determined Se in Zn ore in the presence of high concentrations of P b and Cu, and Ag and Au in copper intermediates were determined by Budesinsky (28). The determination of selenium was also done by Chan and Baig (29). They developed an automated method to generate Se hydride from the acid digested solution of rock samples. Dulude and Sotera (30) discussed interferences in the furnace atomizer when analyzing for selenium in Ni alloys. Arsenic is of much interest to researchers. The determination of As in rock and soil samples by hydride AAS is detailed by Ilgen et al. (32). Voronkova et al. (32) discusses an iodine extraction process and subsequent GFAAS analysis of As,and Shan, Ni, and Zang (33)use the As resonance line of 197.2nm and palladium as a matrix modifier to determine arsenic in environmental samples. The determination of As, Se, Cr, Co, and Ni in geochemical samples is detailed by Pruszkowska and Barrett (34). A temperature platform furnace technique with a Zeeman background correction was used. An overview of P and Si determination in steel is given by McCarthy, Nunn, and Kinard (35). Antimony in steel by hydride generation, GFAAS, and Zeeman background correction was detailed by Vanloo e t al. (36). The analysis of high-purity gallium and rhenium and doped silicon was done by Yudelevich (37). Graphite furnace AA was also used to determine gallium depth profiles in semiconductor silicon by chemical etching (38)and to determine Cr in gallium arsenide (39).
Inductively Coupled Plasma a n d Emission Spectros-
copy. The use of inductively coupled plasma in atomic
spectrosmpy and ~ S B Bspectroscopy has greatly increased and is now a principal tool in the analytical laboratory. Barnes (40) reviews this use of ICP and discusses the problems with ultratrace analysis and the limitations that exist (41). He also
discusses various methodologies and approaches to extend the use of ICP. WalIace (42) compares the capabilities of atomic absorption and ICP in the trace element analysis of metallurgical samples. Direct d i d introduction to an ICP atomic emission spectrometer was detailed by Nim'ee et al. (43). They analyzed metals retained on glass f i h r dters. Direct solid introduction to an AES system was also used by Van Loon et aL (44).They determined metals and metal compounds in air and marine samples by the direct solid analysis method and ICP-MS, and used GC-AASfor the determination of metal speciation. Edge and Trojch (45)assessed the use of ICP optical emission spectroscopy for the determination of trace elements in igneous rocks. The ICP-AES determination of major and minor elements in silicates bv Uchida. Uchida. and Iida (46)and the ICP fluorescent spectiometry elemend analysis Of sediment by Takahashi et al. (47)both use an acid di estion of the solid samples. Uchida et al. digested the powjered rock sample with HCI and HF in a Teflon vessel. Boric acid was added and Si, AI,Fe, Ti, Mn, Ca, Mg, Na, and K were determined. Takahashi et al. di ested the river sediments with HF and analyzed for As, Cf, Pb, Zn, Mg, Ni, AI, V, and Ti. Many analyses of other geologic material are reported in the literature; specifically, Mosier and Matooka (48)analyzed Cambrian carbonate drill cores for major, minor, and trace elements. Mackey and Murphy (49)analyzed zeolites via direct injection. The zeolites were suspended in xylene and directly injected into the plasma. Thompson and Hale (50) discuss a rapid analysis and identification of heavy minerals using ICP-AFS. Heavy mineral grains from stream sediments were set into a polyethylene base and ablated by a laser. A few micrograms of the mineral was volatilized and the vaporized material was efficiently transferred to the plasma. Calibration and mineral identification are discussed. The determination of rare earth elements in eologic materials is also of interest. Fries, Lamothe. a n f Pesek (51) analyzed Y t and Sc in manganese modules. The samples underwent an acid digestion in a polycarbonate vessel and the wavelength selection was optimized to minimize spectral interferences. Yoshida and Haraguchi (52) avoided spectral interferences by separating the rare earth elements using an HPLC. Fifteen REE were determined by ICP-AES by using a concentration eradient method. Crock. Lichte., and ~~~~~~, Wildeman (53) stidied~twogradient strong acid cation exchange chromatography methods and compared the resulta. The I:.S.G.S. rock standard BCR-1 was digested and used for both procedures. Trace mercury wss anal+ by Han and Ni (54). The solid samole was treated with citric acid in order to lower the v o l a h a t i o n temperature. The sample was then heated in AI and the Hg was determined by microwave induced plasma spectrometry. A semiautomatic flow injection system used for hydride arsenic determination is described by Liversage, Van Loon, and De Andrade (55). Arsenic was also determined in geologic, biologic, and water samples by Ho, Tweedy, and Mahan (56).A distillation method was used to separate As and ICP-AES and GFAAS was used to determine As. A preparation of Fe-free solutions from geologic materials by successive fusions for the determination of boron by ICP-AES is described by Din (57). Kitamura, Sugimae, and Nakamoto (58)determined boron in waters, and determination of trace amounts of B in steel using methyl borate as a distillate is detailed by Ishii et al. (59).Brown and Biggs (60) describe a method to determine Pt and Pd in geologic samples by digesting the samples in acid and carrying out an ion exchange to remove interfering metals. Manganese, Nb,P, S, and Ti in niobium containing pig irons were analyzed by Kujirai et al. (61). The analysis of iron-rich ores by Jones (62)gresents aprocedure to separate trace elements from iron y a liquid liquid extraction with i-BuCOMe. The trace elements were concentrated in the aqueous phase and analyzed using an ICP excitation source. Boron, Cu, Ga. Fe, M , Si, V, and Zn were determined in aluminum alloys using I8P-OES (63). Trace impurities in aluminum oxide were determined by ICP-AES (64). Impurities in Zn, Zn-based alloys, Cu, and crude Cu is detailed by Ide (65). Trace elements in uranium are discussed by Kirkbright and Snook (66). Samples were introduced by a graphite rod sample introduction technique. A carrier distillation procedure utilizing AgCl was used to determine trace metals in uranium ~~
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oxide (67). A method for determinin the impurities in plutonium materials from Rocky Flats is cfescribed by Michel and Brown (68). An extraction and separation procedure is described. Other analyses utilizing emission spectrometry techniques, but not an inductively coupled plasma excitation source, are presented in the following. Arsenic, B, C, P, Se, and Si in natural waters were determined by direct current plasma atomic emission spectrometry (69). Direct current plasma emission spectrometry was also used by Natansohn and Czupryna (70) to determine impurities in industrial products. Calcium and barium were determined in steel by electrothermal atomic emission spectrometry (71). Phosphorus was determined in aluminum and aluminum alloys by Nassiff et al. (72) using optical emission spectroscopy. This method is compared to wet methods of analysis. The determination of boron by an emission spectrographic method is detailed by Baucells et al. (73), and the parts-per-billion determination of platinum metals in rocks and minerals is given by Chowdhury et al. (74). Their method combines a fire assay and emission spectrographic technique. X-ray Fluorescence and Microprobe Techniques. X-ray fluorescence and microprobe techniques continue to be the method of choice for multielement bulk analysis of major and trace elements in geologic and inorganic materials. A review of X-ray fluorescence analysis is given by Jenkins (75). Lee and McConchie (76) present a rapid method of whole rock analysis for major and trace elements. A low dilution fusion technique is described, and corrections for matrix effects are detailed suggesting that low dilution fusion can be used effectively for rocks with wide ranges of compositions. The trace element analysis of small rock samples by XRF is given by Schroeder, Thompson, and Sulanowska (77). Rocks from the ocean floor were analyzed and methods for correction are described. XRF was used to determine trace elements in six British Chemical Standards (BCS) and five European Federation of Refractories Producers (PRE) as discussed by Palmer et al. (78). Specific elemental analyses by XRF of geologic materials are given in the following references. Arsenic was determined in rock, soil, and sediment samples after decomposition and complexation of As by benzene. The solvent extraction was deposited on a filter-paper disk and arsenic was determined after that solvent was evaporated. This procedure is detailed by Hubert (79). Eddy (80) determined, Sn, Nb, and Ta in pegmatite by XRF. He studied the effects of interferences of Y, U, Th, Hf, Cu, and Ni. A fusion method and a pressed pellet technique were also compared. An XRF study of Fe, Mn, Cr, and V in natural silicate crystals was done by Dias and Isotani (81). Trace element analysis of waters by X-ray spectrometry is detailed by Marijanovic et al. (82). A routine XRF analysis of elements in Fe ore concentrates is given by Turmel and Samson (83),and Sn and W in ores, concentrates, and residues is described by Balaes et al. (84). Vassilaros (85) determined trace W in titanium based alloys by selectively dissolving the titanium alloy with HF and analyzing the undissolved W by XRF. An X-ray fluorescence binary ratio method is used to nondestructively measure plutonium and uranium in their mixed oxide samples. This procedure is detailed by Jayadevan et al. (86). XRF was also used to characterize Chinese porcelains from the K’ang Hsi period to the present age. Comparisons of porcelain through the Chinese dynasties to the present and porcelain from other localities are discussed by Yap and Tang (87). Trace element analyses of silicates by energy dispersive X-ray spectrometry are discussed by Johnson (88). Three methods were compared by analyzing three new U.S.G.S. reference samples, DNC-1, W-2, and BIR-1. Two established standards were also analyzed, G-1 and W-1. George (89) compares filter methods and fluorescence-to-backscatter methods of EDXRF in geologic matrices. This work suggests that the measurement of fluorescent-to-scatter ratio suitably meets the requirements for a fast and reliable in situ analysis of geologic materials. XRF with an SEM was used by Schoeler and Hahn (90)to determine heavy metals in river sediments. A STEM was used for the analysis of microcrystalline minerals in the study of the homogeneity of clay microparticles (91). SEM techniques are discussed by Ackerman and Planinsek (92) in their application to the computer industry. 90R
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The problems of alkali metal loss during microprobe analyses are discussed by Strope (93). This problem is important when considering the feasability of a nuclear waste repository in basalt. Microprobe analyses of natural biotite were done by DeBruiyn et al. (94) to determine Fe(I1) oxide, fluorine, and HzO by regression. Microprobe analysis of noble gases encapsulated in zeolites is discussed by Vansant et al. (95).
Auger microprobe studies of stainless steel (96) and bulk materials (97) are reviewed. Dubessy et al. (98) discuss the applicationsof MOLE Raman microprobe to the study of fluid inclusions in minerals. An ion robe analysis of H, Li, B, F, and Ba in micas is presented i y Jones and Smith (99). Various (SIMS) secondary ion mass spectrometry techniques are presented in the following. Metson et al. (100) uses SIMS to analyze REE in accessory minerals. A specimen isolation technique is described. Kny et al. (101) used SIMS to characterize phosphorus in hard metals and raw materials. Grasserbauer et al. (102) discusses the possibilities and limitations of state of the art SIMS in the study of in situ trace analyses of ore, alloys, and thin films. Loxton, Tsong, and Pickering (103) discussed the effect of 02 adsorption on Cu-Ni alloys during irradiation, and Clegg et al. (104)presents a comparative study of depth profiling of boron in silicon by SIMS. SIMS has also been applied to the study of mineral dust grains and their applications to a cometary mission (105). Zinner, Pailer, and Kuczera (106) describe an experiment for the study of chemical and isotopic measurements of micrometeoroids by SIMS. Steele and Smith (107) also describe the use of the ion probe in the study of plagioclase in three howardites and three eucrites (meteorites). PIXE. The use of nuclear particle accelerators has generated a variety of techniques such as proton-induced X-ray emission (PIXE), Rutherford elastic nuclear backscattering (RBS), and nuclear reaction analysis. These techniques are reviewed in the analysis of ceramics by Barfoot et al. (108). Maggiore et al. (109) discuss the use of a nuclear microprobe to get direct information of the chemical state of an element, thus providing a chemical history. The use of the nuclear microprobe in geochemistry is discussed. Rogers et al. (110) present the geochemical applications of nuclear microprobes, particularly the use of PIXE in the analysis of geochemical samples. Peak fitting, the deconvolution of spectra, and an internal calibration scheme are discussed. A review by Garten et al. (111)on PIXE discusses the technique’s prospective use in routine analysis. Garten (112) details PIXE in another review on the possibilities of elemental microanalysis and trace analysis. Trace elements in environmental samples such as snow, groundwater, and river sediment were determined by PIXE. Hall et al. (113)discuss the analytical procedures used in these analyses. Annegarn et al. (114) present a preconcentration method used to analyze the Pt group elements in geologic samples by PME. The preconcentration method is essentially a fire assay procedure. Cabri, Harris, and Nobiling (115) review trace Ag determination by P M E in ore evaluation. The proton probe has been applied to the study of meteorites and lunar samples. Van der Stap et al. (116) determined the magnesium isotope ratios in the chondrules of Allende, and the REE fractionation in the meteoritic minerals of Pena Blanca Spring and St. Severin was studied by Benjamin et al. (117). The PIXE analysis produced evidence of actinide and lanthanide fractionation in Pena Blanca Spring oldhamite (Cas). El Goresy et al. (118) did systematic trace element studies in coexisting minerals of lunar rocks (Apollo 15 basalts). Alloys and stainless steels were analyzed by P E E and RBS (119) and PIXE was used in the elemental analysis of aerosols (120). Carlsson (121) used geologic standards to determine the accuracy and precision in thick target PIXE and X-ray emission methods. Activation Analysis. Activation analysis remains a powerful tool in the analysis of geologic material. Laul and Wogman (122) review the application of neutron activation anal sis to geologic materials. Instrumental thermal NAA was usedto do elemental analyses on a number of U.S.G.S. reference samples. Oddone, Meloni, and Genova (123) discuss the use of INAA for the analysis of rare earth elements in terrestrial materials. They critically review instrumental and
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destructive methods and assess the best working conditions for irradiation and present optimized procedures for REE analysis. They use a radiochemical procedure that separates the REE by fluoride precipitation. De Corte et al. (124) evaluate the ko standard method as it is applied to multielement reactor NAA of geological, environmental, and clay reference materials. May and Pinte (125) detail the NAA of rare earth elements in uranium containing rocks. A method was developed to separate the interfering U and fission produced rare earth elements. Celenk and Ozek (126) simultaneously determined alumina and silica in geological samples using a 5-Ci plutonium-beryllium source. The irradiatetransfer-count sequence was repeated five times in succession. This recycling improved the counting statistics and the reproducibility. Chen and Tsai (127) report an internal standard method for determining allium and other trace elements in bauxite, and Yellin et al. 7128)provide elemental abundances of Th, U, and K in tektites and crater glasses. Rudolph et al. (129) used INAA to study trace elements in semiconductor selenium. This rocedure separates radioactive Se isotopes and y-active ra ionuclides. Fast neutron activation was used by Szegedi and Divos (130) to determine oxygen in rock samples and Votava (131) detected y-rays from the inelastic scattering of fast neutrons as a nondestructive method of determining silicon dioxide in rocks. Lacroix et al. (132) used charged particle activation analysis to determine residual impurities in indium hosphide. Charged particle activation analysis was also use by Nozaki et al. (133) in their analysis of semiconductor material and by Mortier et al. (134) for the determination of boron in aluminum and aluminum-magnesium alloys. Parry (135) evaluated boron as a thermal neutron filter for the epithermal NAA of short-lived radionuclides in geologic material. Barnes and Gorton (136) used a low flux reactor (SLOWPOKE-11)to determine trace elements in international reference samples. This method was then evaluated. Watterson et al. (137) combined multielement NAA with a multivariate statistical pattern recognition technique in order to study geochemical differences and to classify unknown samples. Applications include the mapping of mineralized phases in granites, finding trace element signatures that are characteristic of the sources (diamonds),and the identification of sedimentary units. Many papers on methods development and geologic and inorganic materials analysis by INAA are found in the Russian literature. The titles only are translated and are therefore not included in this review; however they look terribly interesting. Mass Spectrometry. Matteucci et al. (138)discuss a rapid multielement analysis of silicate samples by spark source mass spectrography. Spark source MS is also used in the study of abundant REE in geologic samples. Dietze et al. (139) discuss the problems of analyzing high concentrations of REE. Walters et al. (140) utilized spark source MS in the analysis of trace oxygen and carbon in gallium arsenide, and Kingston, Paulsen, and Lambert (141)determined Se and Fe in stainless steel and other alloys. Procedures for isotope dilution spark source MS were developed. Isotope dilution methods were used to verify certified sulfur values in steel reference materials (142) and to determine Pb, Ag, Cd, and Te in carbonaceous chondrites (143). Accelerator-based mass spectrometry of semiconductor materials is discussed by Anthony and Thomas (144). This same method was used to determine cosmogenic aluminum-26 in terrestrial and extraterrestrial material (14.9, iodine-129 in meteorites and lunar rocks (146),and %Al in iron meteorites
B
a
(147).
The use of laser microprobe mass spectrometric analyses of metals is reviewed by Kurosaki (148).Quantitative microanalysis of solid samples by laser probe MS is discussed by Eloy (149) and Odom and Hitzman (150). The determination of trace elements in solid samples using laser source MS is evaluated by Sanderson, Mapper, and Farren (151). Ion Chromatography. Ion chromatography has seen tremendous use in the analytical laboratory. Recent innovations have included new methods for sample preparation. Reviews are presented by Fritz (152)and Jupille (153). Mosko (154) determined inorganic ions in water using an automated IC method. Sample pretreatment is discussed. Urishiyama
et ai. (155) used IC to analyze the S042-and N032-content of airborne particles. Willison and Clarke (156) also analyzed atmospheric aerosols for C1-, NOZ2-,and S042-using single column or nonsuppressed ion chromatography. Koch (157) improved a method for determining trace cyanide using IC and a electrochemical detector. Lai et al. (158) used multidimensional column IC to separate and detect BF, and PO:-. They use this technique to analyze B and P in borophosphosilicate glass. Rocklin (159) determined Au, Pd, and Pt at the parts-per-billion level by IC. Preconcentration techniques are used. Legrand et al. (160) determined ultratrace ion levels in Antarctic snows and ice. Methods were developed to remove field contamination. The results suggest that contamination is a major problem in determining NH4+ and, therefore, previous published concentration data on nitrogen containing compounds ( N o s , NH4+)are suspect. Spectrophotometric and Electrochemical Methods. Spectrophotometric methods continue to be of value in the elemental analysis of geologic and inorganic materials. Depending on the analytical problem, these methods are quite useful in the laboratory. Sarkar (161) reports a rapid spectrophotometric method for determining phosphorus and silicon in phosphate rocks. The analysis was based upon the absorbances of individual heteropoly molybdates. Phosphorus was also determined in silicate rocks by a flow injection method. Kuroda et al. (162) injected the sample solution directly into the flow system which forms heteropoly acids in Mo and Sb. Sauerer and Troll (163) determined trace amounts of beryllium in silicate materials. They developed an extraction procedure to remove interfering A1 and Fe. Chung (164) simultaneously determined Fe and Ti in silicate rocks with diantipyrinylmethane (DAPM) by dual-wavelength spectrophotometry, and Fey and Dixon (165) developed a method to rapidly estimate the iron oxide content in soils and clay material. Rao and Ramakrihna (166)determined traces of Cd in pure zinc materials and Ohls and Riemer (167,168) used recording spectrophotometry to simultaneously determine Cr (VI) and Cr(II1) in oxidic materials and Cu and Ni in iron and steels. Subrahmaniam and Rao (169) did trace element analyses in some Ni, Ti, and Mg based alloys. Hori et al. (170) determined chlorine using ion selective electrodes after pretreatment with KMn04 of environmental samples. Campbell (171) determined fluoride in seawater after a buffer treatment, by a standard addition method and subsequent fluoride analysis using a fluorine selective electrode. Absorption voltammetry was used to determine Ni in the environment using a Hg film electrode (172),Brumleve (173) detailed a coulometric Karl Fischer titration method to determine traces of water, hydroxide, and oxide in halide salts, and Ye and He (174) discussed a polarographic determination of trace zirconium in ores. Zirconium was complexed and absorbed on the dropping mercury electrode. Other Techniques. Cassinelli (175) has reviewed the analysis of minerals by infrared spectrometry. Terashima (176)developed a direct method of determining carbonate and noncarbonate carbon in geologic materials by IR. Baird (177) used low resolution near infrared reflectance to discriminate granitic rock compositions, and Aines and Rossman (178) discuss the IR spectra of water in minerals. Paulik, Paulik, and Arnold (179) detail a simultaneous thermogravimetric (TG), DTG, DTA, and EGA technique for determining carbonate, sulfate, pyrite, and organic material in minerals, soils, and rocks. Huggins and Huffman (180) developed a rapid Mossbauer-based method for determining iron-bearing phases in coal, steels, and slag.
GENERAL APPLICATIONS Inorganic and geological analyses are similar in that they use common techniques on inorganic materials but they differ in that most laboratory or industrial materials have simple matrices while geological materials most often have complex matrices requiring constant attention with respect to sample preparation for elemental determinations. After an analytical technique has run ita course of development, most of the new applications are related to sampling, sample preparation, or extraction of a constituent of interest so that its concentration may be determined. Y. A. Zolotov of the Vernadsky Institute of Geochemistry and Analytical Chemistry has written a review on microtrace ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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anal sis of geological samples in meteorites and lunar soil (1813: Preconcentration from aqueous solutions onto a solid phase has been reviewed by Murthy et al. (182) while contamination concerns are reviewed by Wanninen (183) and Kosta (184). Accuracy in analytical spectrophotometry is discussed by Burke and Mavrodineanu (185). Accurate analyses by classical methods for silicon in metals and rocks is reviewed by Mueeller and Staats (186). Another related study i6 the determination of soluble silica in ceramic materials by Mitra et al. (187). Sampling by wet decomposition by acids under pressure has been reviewed by the IUPAC Analytical Chemistry Division (188). Its use for the dissolution of refractory alumina for trace elements is considered by Foner (189). The use of radiochemical methods for the analysis of semiconductor and pure materials is discussed by Haas, Beuerle, and Hofmann (190) and for the characterization of semiconductor material by Hung et al. (191). Analytical clustering studies of trace elements in iron meteorites is utilized by Massart et al. (192). Most geochemical articles refer to analytical techniques originally described in analytical chemistry journals, but occasionally creative adaptions are reported in geochemical journals. This is particularly true with respect to the separation of trace elements from sometimes very complex matrices. Readers are directed to the journal Geochirnica et Cosmochimica Acta which often contains such analytical contributions. A key article in 1984 on the "North American Shale Composite" emphmizing rare earth element composition was written by Gromet, Dymek, Haskin, and Korotev (193). Other useful articles include light-stable isotdpes in meteorites by Pillinger (194), sulfate in fluid inclusions by Dubessy et al. (195)and an EPR study of copper on clays by Goodman et al. (196). X-ray photoelectron study of manganese nodules by Dillard et al. (197) has interesting analytical comments as does the mass spectrometric analysis study of meteorites by Loss et al. (198). A study of argon standards by Roddick (199) is a careful piece of work. Other review articles include nuclear methods used in the semiconductor industry by H. Koch (200), the use of the electron microprobe in geochemistry and mineralogy (201), and an extensively referenced paper on the analysis of extraterrestrial materials (202). A review of the principles of avoiding systematic errors was written by G. Toelg (203). Standard Reference Materials. The preparation, study, and use of standards, especially geochemical standards, is essential to analytical chemistry. Readers must be reminded that the journal Geostandards Newsletter is available, important, and interesting. A partial search of library holdings of this important international contribution showed few subscribers among institutional libraries. It is hoped that many individuals support the publishers, editors, and authors effom if not, you should. Its mailing address is: 15 rue Notre Dame des Pauvres, B.P. 20, 54501 Vandoeuvre-les-Nancy, France. This journal may profitably be read from cover to cover. Volumes VI1 and VI11 were published in 1983-1984. References in them will lead analysts to other sources of standard data. The last article in each volume is a geochemical reference sample bibliography for that year. It is indexed by element. Afi extremely valuable special issue of volume VI11 was published in 1984. It is a compilation of working values and sample descriptions for 170 international reference samples of mainly silicate rocks and minerals. A catalog of Certified Canadian reference materials can be obtained from the Canadian Certified materials project listing details on new standards (204). Govindaraju and Melvelle (205) and Delfanti et al. (206) review available standards and their analysis by activation analysis. Activation analyses of standards are reviewed by several authors (207-209) includin an NBS soil reference standard (210). Fluorine in three NB8 reference standards has been determined by proton activation (211). A detailed study of carbon in steels has application to general analysis (212).
ACKWO WLEDGMENT The authors gratefully acknowledge the help and interest of Linda Shackle of the Noble Science Library at Arizona State University in computer searching the literature. Charles F. Lewis helped in checking the manuscript and references. Extra special thanks are given to Joan A. Wrona for her 92R
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Ferrous Analysis W.A. Straub* and J. K. Hurwitz US.Steel Corporation, Technical Center, Monroeville, Pennsylvania This review is produced from a search of the literature as performed with the DIALOG capabilities of Chemical Abstracts Service. The literature covered in this review spans the period from November 1982 to October 1984 and is the sixth review in the series of reviews compiled by us. Noteworthy in this 2 year span is the significant increase in publications from the People's Republic of China as well as what appears to be an increased emphasis on the determination of gases in ferrous alloys in the industry as a whole.
ALKALI METALS The determination of alkali metals in the steel industry relates to the characterization of ores, enamel coatings on steels, slags, and coal. To achieve adequate sensitivity for sodium and potassium (474) and rubidium (209), these elements were preconcentrated by anion exchange or by liquid-liquid extraction and the analysis completed by atomic absorption spectrometry or inductively coupled plasma spectrometry. Atomic absorption spectrometry was also applied to the determination of Na and K in coals, slags, and ores without preconcentration by adding measured amounts of lanthanum and cesium to eliminate chemical and ionization interference (477). To study the corrosion rate of enamels in hydrochloric acid, the corrosate was assayed for its sodium and potassium content by dc arc optical emission spectrometry (409), while a quartz optical fiber was used to convey light from the analytical gap to the monochromator of a vacuum optical emission spectrometer in order to extend the spectral range for the determination of Na and K in ores (337). Neutron activation analysis has also been used for the measurement of Na in ores (148).
ALUMINUM Included in the reagents that have reportedly been used for the spectrophotometric determination of A1 in steels are 94 R
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salicyloylhydrazones of pyridine-2-aldehyde and pyridoxal (129), Chromazol KS (484), and Chromazurol S in the presence of dodecyldimethylammonium acetate (500). Aluminum was also complexed with Chromazurol S after fusing slag samples with a sodium carbonate-tetraborate mixture (601). In another procedure for the determination of A1 in iron ores, the A1 was separated and concentrated by ion exchange before the colorimetric finish with 8-hydroxyquinoline (475). The addition of butanol to a dissolved steel sample immediately before precipitation of the interfering elements by caustic has allowed the colorimetric determination of A1 with aluminon to be completed without vanadium interference (325). A recent Chinese study has established the conditions for the sensitization by various surfactants of the fluorometricreaction of Al with 8-hydroxyquinoline-5-sulfonicacid (81). A method for the determination of A1 in alloy steel was given. A hydrochloric acid dissolution step was employed before the direct atomic absorption spectrometric determination of A1 in steels in a nitrous oxide-acetylene flame (159), while a liquid-liquid extraction (209) or an ion-exchange separation (474)was used to treat a similar acid dissolution of iron ores prior to the atomic absorption determination of the Al. For the rapid determination of soluble A1 in continuously cast steel, an apparatus has been devised for electrolytically sampling the steel and finishing the analysis by atomic absorption spectrometry (323). Total time of analysis is about 125 s.
ANTIMONY This element has been determined spectrophotometrically in steel and cast iron as an ion-association complex with Crystal Violet following extraction (431), and in steels with several of a family of Rhodamine dyes (Rhodamine B, Bu ester of Rhodamine B, and Rhodamine 6G) (298). Pulse-nebulization has been used for the rapid analysis of trace antimony in steels by atomic absorption by allowing the
OOO3-27OO1851O357-94R$O6.5OlO 0 1985 Amerlcan Chemical Society
