80 Analytical A tomic Spectroscopy 4.1 CHEMICALS 4.1.1 Petroleum and Petroleum Products In a field where the requirement is often for sequential or simultaneous mufti-element analysis it is not surprising to find an increase in papers dealing with ICP-OES. Interest in wear metal analysis continues at a high level with particular attention being paid to particle size effects and the relationship between data produced by different techniques.A series of CRMs, metal decanoates, useful in this field of analysis has appeared and is available from the National Physical Laboratory in the U.K. (772). 4. I . 1.1 Petroleum. Ross and Umland (1483) studied the sample preparation procedures available for petroleum products. Dry ashing, wet ashing, plasma ashing, Schoniger combustion, bomb oxidation, and simple dilution were investigated, with the last two techniques considered best for trace determinations.An investigation into the nature of V compounds in Boscan crudc oil was undertaken by Spencer et at. (1387), using chroma- tography, extraction and ETA-AAS. Porphyrin and non-porphyrin species were separated and characterized. The determination of S in petroleum products down to 100ppb was reported by Alder and Kargosha (W2, 1468).Reductive or oxidative techniques were used to liberate H,S or SO,, which were collected and analysed by monitoring the S , molecular emission in a H,/Ar diffusion flame. 4.1.1.2 Lubricating Oils. It was claimed by Wittmann (506) that the use of a mixed solvent, toluene and glacial acetic acid (1 +4), allowed the determination of the additive elements Ca, Mg and Zn by FAAS, using inorganic salts as standards.Interference from K wns absent. The determination of P, down to OSppm, was described by Tittarelli (1015). The sample was diluted with xylene before injection into a graphite furnace that had been treated with lanthanum nitrate. The Dayton Research Institute has been particularly active in the area of wecr metal analysis.Information has appeared on instrumental comparisons of, e.g., d.c. plasma OES, ICP-OES, rotating-disc electrode OES, ETA-AAS and FAAS (1334, 517, 567, 579), on wear metal particle size effects (600) and on the efficiency of sample introduction systems in AAS and AES (1321). Further work on a particle size independent method has been published by Saba et al. (1695, 598) (see ARAAS, 1978, 8, Ref. 931). Hernandez Mendez et al. (1670) have demonstrated the applicability of the emulsion formation technique to the determination of Pb in lubricating oils. The sample was emulsified using ultrasonic disper- sion in the presence of surfactants and the results obtained by FAAS compared with those from aqueous standards. 4.2.1.3 Gasoline. Bye et af. (1046) investigated the use of both FAAS and ETA-AAS as specific GC detectors for the determination of Pb-alkyls (TML and TEL) in gasoline. The coupling of GC and ICP-OES for a similar purpose was described by Sommer et al. (1610). An emulsion formation procedure for the determination of Pb in petrol was claimed to give acceptable results (1635). Iodine and Aliquat 336 were added as in ASTM D3237, and a gel formed by the addition of an emulsifying agent and water, prior to analysis by FAAS. 4.1.2 Chemicals and Miscellaneous Applications 4.1.2.1 Sample Preparation. General methods for the removal of organic material before the determination of Ni (1683) and Se (1505) by AAS have been produced by the Analy- tical Methods Committee oE the Royal Society of Chemistry.Selenium was determined, after wet oxidation, using hydride generation AAS while Ni was determined by conventional FAAS after wet oxidation and extraction with APDC/MIBK. Alder and Bucklow (1981)Applications 81 produced an interesting method for the determination of Cu, Zn and Cr in carbon cloth, in which the cloth was ground, suspended in a HNO, /sodium hexametaphosphate solution and directly aspirated into a flame.The preparation of refuse material for analysis by FAAS has been discussed by Peck (1609). Complete dissolution was effected by using in turn HNO,/HF, HN03/HC10,, and HCl. The use of tri-n-octylamine in MIBK/toluene (1 : 1) for the extraction of Fe (TIT) from TiI, prior to FAAS analysis was described by Spivakov et al.(716). A novel technique for the determination of As down to 35ppb in TiC1, was presented by Orlova et al. ( 3 3 ) . A molybdoarsenate species was formed and extracted into an MIBKlbutyl acetate mixture in which the Mo was measured by FAAS. Ng and Bhattacharyya (1068) determined Pb in a variety of inorganic materials after extraction into MIBK using NaDDC. A method for the layer-by-layer anulysis of Sb in epitaxial Si was described by Zakharchuk et al.(35). Layers of approximately 0.1 pm thick were removed using HF/HNO,, evaporated to dryness, taken up in H20 and analysed by ETA-AAS. In a similar procedure, Paama and Kuus (742) determined Al, Cu, Fe, Mg, and Mn in silicon semi-conductors. In this case, after removal of a thin layer with HF/HNO,/ethanol etching solution, pure graphite was added and the solution evaporated to dryness.The elements were determined in the residue by using a carbon electrode and a.c. arc OES. An enzyme was used by Ambrosetti et al. (480) to digest photographic-film emulsions for the determina- tion of Pd. The Pd was extracted into toluene with dibutylsulphide for analysis by An indirect method for the determination of Ge in CdS, based on the formation of a molybdogermanate complex, was developed by Pelosi and Attolini (1 174).The Mo was measured, which gave increased sensitivity, Coutinho et al. (927) described an indirect method for the determination of CS, in fuel gases by FAAS. Carbon disulphide was collected in alcoholic KOH containing Cu(I1) and an insoluble Cu xanthate complex was formed; this was filtered, redissolved, and the Cu determined. The method was claimed to be interference free, provided that any H2S was removed using cadmium acetate.Signal instability and drift due to burner salting, often experienced when aspirating aqueous solutions of high salt content, was claimed by Gooch et al. (571) to be considerably reduced by the addition of organic acids such as formic, acetic, propionic and butyric.ETA-AAS. 4.2.2.2 Atomic Ahsorptiori ?Methods. Further work on AsIII BV semi-conductors has been reported by Dittrich et al. (see ARAAS, 1978, 8, 78). The determination of traces of Te and Se in acid solution was investigated using both ETA-AAS and hydride generation with a heated quartz tube (1485). Te was best determined by the former and Se by the latter technique.In another paper ETA-AAS, ETA-AFS and d.c. arc OES were compared for the determination of Te (1484). The best sensitivity was obtained with ETA-AAS. In the analysis of dopant levels in semi-conductors, Demko and Copeland (105) used hydride generation coupled to the Woodriff furnace in order to improve sensitivity and, it was claimed, reducc interferences.The coupling of a lascr microprobe and FAAS for the dctcimination of the thickncss of Ag, Au and Ni layers on a copper substrate was investigated by Kantor et al. (1689). Details of the apparatus were given and depth could be determined to an accuracy of better than 0.1 pm for all three elements. Sukhov and Zolotukhin (1821) have described the determination of Cr, Cu and Mn in silicon/chromium layers on ceramics in which the solid sample was both vaporized and atomized using a Q-switchcd lascr.Spivakov et al. (1 8.10) studied the behaviour of In in both a flarnc and a furnace using aqueous solutions and organic extracts. Molecular absorption spectra were used to study82 A naly tical A tom ic Spectroscopy graphite furnace species such as InCl and I n 0 in order to predict optimum conditions for the determination.After separation by HPLC, vitamin B,, was determined (as Co) by Zeeman AAS in the presence of a large excess of inorganic Co (1272). An extensive discussion on the use of U S for the determination of trace metals in pharmaceutical products has been presented by Rousselet and Thuillier (1989).Interference effects and methods for their elimination along with detailed analytical procedures were given. 4.1.2.3 Atomic Emission Methods. The application of ICP-OES to problems in forensic analysis was discussed by Drenski et d. (1286). The multi-element nature of the technique makes it useful as a fingerprinting device for both proof of origin and ownership. The determination of S in halide salts, using a d.c. plasma, has been reported by Swain and Ellebracht (1780).The S species were reduced to H,S, using HT, and swept into the plasma where S emission was monitored in the V.U.V. region. Lowry and Strube (1736) have applied d.c. arc OES t o the determination of residual C in integrated circuits using Cu electrodes. The presence of Ga was claimed to enhance the emission of Al, As, Be, Ge, Mg, Si, Sn and Zn in the 12A d.c.arc, by facilitating a more uniform distribution of the elements between the electrodes. The determination of trace impurities in silicon by Metastable Transfer Emission Spectrometry has been described by Sutton et al. (194) (see Section 1.3.1). Measurement of the emission downstream of the discharge was fmnd to give a considerable reduction in spectral background.Table 4.1A PETROLEUM AND PETROLEUM PRODUCTS b 2 Element X/nm Matrix Concentralion Sample treatment Atomization Ref.Tech. Analyte 3 Form Al - Lubricating oils Trace levels A Ca 422.7 Lubricating oils 1-6 pg/ml A and additives (in extract) Ca cu c u c u Fe Fe 422-7 Mlneral 011s 1-6 pg/g A - Lubrfcating 011s 324-7 Petroleum products - Gasoline - Lubricating oils - Petroleum products Trace levels A 0-1-2 ,g/ml A 0.03-2.5 pg/mt A ( i n extract) Trace levels A 5 pg/ml level A (in extract) Hg 253.7 Natural gas From 0 . 2 ng/m3 A Mg 285-2 Lubricating oils 0.5-2 ,g/ml A and additives (in extract) L L L L L L L L G L See Fe, ref. 517 Graphite furnace (HGA-2100) Dilute with mixed solvent of toluene+ F Air/C,H, glacial acetic acid (1 : 4).Calibrate with inorganic metal salt standards (Ca, Mg, Zn) Comparison of various treatments for the F Air/C,H, determination of Ca, V, Zn : (A) Dry-ash in Pt at 450 "C (B) Wet-ash with HN03/H,S0,/HCI0, (HGA-72) (C) Combust on filter-paper (Schoeniger (D) Ash in microwave oxygen plasma (E) Digest with HNO, in PTFE bomb (Results obtained via above treatments compared with those from direct solution method using acetic acid/toluol dilution) N,O/C,H, Graphite furnace method) See Fe, ref. 517 Dilute with white spirit Graphite furnace F Air/C,H, (HGA-2100) Comparison of ETA-AAS with photometric method (IP 225/71) Comparison of ETA-AAS with various alternative methods for determining (HGA-2100) Al, Cu, Fe in used engine oils Interference study, related to mineralized F sample solutions (5% H,SO,).For Fe, use oxidizing flame; for V, add K+AI to all solutions. No interferences observed for Ni Collect in cold trap containing Au wool, heat to transfer Hg t o control trap and thence to absorption cell See Ca, ref. 506 F Air/C,H, Graphite furnace Graphite furnace - Cold vapour 517 z 506 1483 51 7 1158 1960 51 7 1639 418 506 wTable 4.1A PETROLEUM AND PETROLEUM PRODUCTS - coiztinued 03 P Element X/nm Matrix Concentration Tech.Analyte Form Sample treatment Atomization Ref. Mo 313-3 Lubricating oils Trace levels A L 315.0 320.9 Na - Fuel oils - E c Na - Fuel oils - E L NI - Petroleum products 5 pg/ml level A L P - Lubricating oils From 0-5 pg/g A L (in extract) Pb Pb 283.3 Gasollne 283.3 Gasollne A L A L Pb 283.3 Lubricatlng oils 1.7-3.0 mg/g A L (1-10 pg/ml in extract) Pb - Fuel oils - E L Treat with HFIHNO,, shake and dilute F N,0/C,H2 with MlBK Application of OES to determination of S - contamination levels of Na, Pb, V. Use polyethylene sampling vessels.Automated on-line method. Mix fuel with F - alcoholic surfactant/H,O diluent See Fe, ref. 1639 F - Dilute ( 1 : 1) with xylem and take 20 aliquots for analysis.Pre-treat (HGA-768) furnace with La(NO,), solution, or, with auto-sampler, add organo-La solution to diluted sample. Dry at 130 "C, ash at 1600 "C and atomize at 2700 "C Combined GC-AAS procedure for F Air/C,H, determination of TML and TEL. (A) For flame AAS, pass GC effluent to burner via heated tube ( B ) For ETA-AAS, dilute ( ~ 5 0 ) and pass sample vapour tangentially to furnace (C) Total lead may be determined by acid-extraction AAS Allow sample (4 ml) to react for 5 min.with 10 drops of 6% solution of I in benzene. Add 1 ml of 5% solution of Aliquat i n Pb-free gasoline+2-5 ml of Emulsogen LBH. Add H,O gradually until gel forms and dilute to 100 ml Prepare emulsion (0.1 g oi1/50 mi) by F Air/C,H, ultrasonic dispersion in surfactant solution (Tween 20 +MSe12/benzene) Sea Na, ref. 1765 s - Graphite furnace Graphite furnace (HGA-70) F Air/C,H, 1695 1765 1811 1639 1015 1046 b 3 s 1635 c' % b s 2. h 1670 2 GI 1765 2S 384 Petroleum products From 6 ng/rnl E (S, band) S 384 Gasoline ( S , band) S 384 Petroleum products (S, band) V - Crude oils V V V Zn Zn Various 318.4 Mineral oils - Petroleum products - Fuel oils 213.8 Lubricating oils 213.8 Mineral oils and additives - Lubricants - Petroleum products Trace levels E (as mercaptan) From 0.1 pg/g E A - 50 pg/ml level A 0-2-0.8 pg/ml A 0.4-1 ' 0 pg/g A (in extract) E - (in extract) A - L, G t G L L L L L L L t (A) Reduce with Na and Devarda's alloy F Air/Ar/H, +HCI, collect H,S in NaOH solution and re-liberate gas into flame (B) Combust, collect liberated SO, in Na teirachloro-mercurate solution and re-liberate into flame - F - Reduce to H,S with Na or Devarda's F Ar/H, alloy, under reflux Isolate and fractionate non-porphyrin V compounds on neutral AI,O,, using IPA/THF mixtures as eluants.Measure individual fractions for V by ETA-AAS. (Procedure involves other separations and other techniques, e.g., NMR, i.r.and MS) See Ca, ref. 1483 F N,O/C,H, Graphite furnace Graphite furnace (HGA-72) See Fe. ref. 1639 F - See Na. ref. 1765 See Ca, ref. 506 s - F Air/C,H, See Ca, ref. 1483 F Air/C,H, Graphite furnace (HGA-72) Comparison of methods for determination F, A - of wear metals. Elements quoted : Ag, At, Co, Cr. Cu, Fe, Mg, Mn, Ni, Pb. Si, Sn (Ti, W, Zn unsatisfactory) (A) Pb in gasoline-Dilute with F - 2-butanone and add I (10-fold excess) to equalize TEL and TML absorbances ( 8 ) Zn, Fe in engine oils-Dilute with 2-butanone and calibrate with metal benzoate solutions (C) Ni, Zn, Fe, Cu, Ca i n asphaltenes- Wet-ash with H,SO, and extract with dilute acid (D) Ca, Mg, Fe in crude oils-as for (C) 942 ,$ % e P ;; -.. 1225 1468 1387 1483 1639 1765 506 1483 393 422 00Table 4.1A PETROLEUM AND PETROLEUM PRODUCTS-continued 00 Element X/nm Matrix Concentration Tech.Analyte Form Sample treatment Atomization Ret. Lubricating oils Various - Trace levels E, A Comparison (on 350 samples) of four methods for wear metals determination : (A) AAS (B) OES - ro-trode method (D) D.c. argon plasma Add mineral acid mixture to oil sample, agitate and dilute with homogenizing reagent.(Comparison of OES and AAS methods for Fe, Ni, Cr, Mg, Cu, Al, Sn, Mo and T i ) Theoretical study of particle size effects Dilute with toluene or MIBK. (Comparison of results with those given by rotrode method) Comparative study of sample transport and particulate size in wear metal determinations by OES (ICP, d.c. arc plasma and rotrode) and AAS Comparative study of sample matrix effects in wear metal determinations by OES (ICP, d.c.arc plasma and rotrode) Elements : Fe, Al, Cr, Cu, Mg, Ni, Ti, Mo (C) ICP F, S - P ICP, D.c. plasma 567 579 598 Various - Lubricating oils (9) pg/g levels E, A F - P D.c. plasma Various - Lubricating oils Lubricating oils Trace levels Trace levels E E A. E P ICP P ICP 600 882 Various - Lubricating oils Trace levels Various 1321 Lubricating oils Trace levels E Various 1334 b oils Various - (7) Various - Used diesel-engine 0.5-50 pg/g A (various elements) E - Results quoted, on 150 samples, for Cu, F - Fe, Pb, Ag, Cr, Zn and Mg Combined GC/ICP system.Applications P ICP include TEL/TML in gasoline, Si in tetra-ethoxysilane and, indirectly, NJargon 1 ethsnol and toluene detection Investigation of use of acid-treated F Air/C,H, suspended metal particle standards, as alternative to organo-rnetallics (argon or N,O/C,H, 1417 1610 Petroleum products Used jet-engine oils p g / g levels A, F 1679Various - Used jet-engine oils Trace levels E L Dilute ( 1 : 9) with xylene.Elements : P ICP 1698 'Q Various - Lubricating oils Trace levels E , F L - - _ 1733 2- ( 8 ) Ag, Al, Cu, Cr, Mg.Ni, Si, Fe % (13) 3 Various - Engine oils (25) Trace levels E , F L - F Air/C,H, 2013 N,0/C2H,Table 4.1B CHEMTCALS AND MTSCELLANEOUS MATERTALS E Element X/nm Matrix Concentration Tech. Analyte Form Sample treatment Atomization Ref. Ag Al As As As AS As Au Ba C C Cd Metal films Organo-Si compounds High-purity t i tani um chloride Colour additive (FD & C Red No. 3) Wood preservatives and timber Antimony compounds Lewisite (in air) Metal films Calcium compounds Organic compounds Integrated circuit residues Plastic utensils From 0.025 pg A (absolute) - A From 35 ng/g A From 1 A - A - A From 0.032 p g A pg/g levels A (absolute) - A 0.1-5.0 mg E (absolute) A - S, G L L L L L, G L, G S, G L L S L Vaporize by laser microprobe and pass F Air/C,H, sample vapour/aerosol to flame See Si, ref. 571 F N,O/C,H, Adjust sample solution to contain 0.2M F - KI and 9M HCI. Form molybdo-arsenate complex and extract into MIBK/ butyl acetate solvent for measurement of Mo by AAS Digest with HNO,, evaporate t o low volume and dilute to 5 ml with H,O. Take 20 aliquots for analysis Extract As, Cr, Cu by leaching with F N,O/C,H, HzSOJH,O, and add Na,SO, solution.(Comparison with colorimetric method) Dissolve in HCI, dilute, add TiCI, solution F and extract with C,H,. Back-extract with H,O. Proceed by arsine generation method, using Zn + HCI Collect in aqueous NaOH bubbler See Ag. ref. 1689 F Air/C2H, Graphite furnace or Ar/H, NJH, + entrained air Graphite furnace Extract Ba ( 2 x 1 6 5 to 5x10-4M) from F N,0/C2H, excess Ca ( 5 x l a 2 M) with 18-crown-6 solvent extraction Ca(OH), and determine Ca in CaCO, formed or in excess Ca(OH), - A D.c.arc Combust in 0,-flask, absorb CO, in F - Extract with HLO; 3% acetic acid: 10% F Air/C,H, ethanol of ethyl ether: 4 % acetic acid. Evaporate extracts t o dryness and redissolve in 1N HNO, 1689 571 33 49 1160 1176 1410 1689 5 374 g 2.k 1230 a, 3 1736 5. 8 760 8 ;* 8 > 0cd Cr Cr Cr c s c u cu c u c u Fe Fe Fe Fe FO Ge Ge 228.8 - 359.3 - - - - 324 * 7 324.7 - 248.3 - - 248.3 313-3 (Mo) 265.1 (doublet) Calcium salts; boric acid; waters Wood preservatives and timber Thin films Carbon cloth Radioactive leachates Rare-earth reagents Wood preservatives and timber Thin films Carbon cloth Rare-earth reagents Ti ta ni um tetra-iod ide Cellulose products Drugs Perchlorate solutions Cadmium sulphide Miscellaneous samples ng/ml levels A A - A A From 0.5 C1g/mf A From 70 ng/g A A - A 7% level A From 50 ng/g A A - - A A 0.1-100 pg/rnl A 40-1 000 pS/O A A + L L S, G L L L L S, G L L L L L L L L Dissolve in H,O and separate Cd on Pt F Air/C,H, electrode (-1 -0 V).Dissolve Cd deposit in hot HNO, (1 : 1) See As, ref. 1160 F Air/C,H, or N,0/C2H, Laser evaporat i on/AAS method - - Grind (< 200 u) and shake with 2% F - HNO, +0.1% Na hexametaphosphate to form suspension - F Air/H, Adjust sample solution to pH 2-3 and F - extract Cu, Fe with oxine, into isobutyl alcohol See As, ref. 1169 F N,O/C,H, See Cr, ref. 1821 - - See Cr, ref. 1981 F Air/C,H, Dissolve 0-5g sample in 50 mi 8M HCI F Air/C,H, and extract ( x 2 ) with lOml of 0.2M tri-n-octylamine in MIBK/toluene (1 : 1).Dilute extract with acetone and (a) measure directly or (b) back-extract Fe with H,O into acetone after HCI washing of original extract See Cu, ref. 27 F - - F - Methods, including AAS, for determination F of F e ( l l ) , Fe(ll1) and total Fe - Graphite furnace Dissolve in conc.HNO,, remove S, add Graphite furnace NH, molybdate and adjust t o pH 1.3-1.5 (HGA-74) with KOH. Shake with pentan-1-ol/diethyl ether (1 : 4). Separate, strip organic phase with NH,OH/NH,CI buffer (pH 9.3) and measure for Mo (Ge/Mo=1/12) Add NaOH to sample solution t o avoid - Graphite furnace Ge loss at ashing stage ( FLA-10) A 1827 2 =1 1160 E* 1821 1981 E? 3 1250 27 1160 1821 1981 27 71 6 1416 1814 1948 1174 1470 00 Wv) Table 4.1 B CHEMICALS AND MlSCELLANEOUS MATERIALS- continued 0 Element X/nm Matrix Concentration Sample treatment Atomkatfon Ref.Tech. Analyte Form Hg In K L i Li Li Mg Mn Mo Na Ni Ni Pb 253.7 Drugs 309.3 Organic extracts: 293.3 aqueous solutions - Hydrochloric acid - Polyamide fibres 670.7 Neutron absorbers (containing boron) - Radiosctive leachates - Drugs 279.4 Thin films - Electrolytes - Hydrochloric acid 232.0 Organic matter - Thin films - Exhaust gas catalysts Trace levels (as LiCI) From 10 ng/ml (in extract) From 70 crg/g (as 6) From 0.05 pg/ml (in extract) 1-2% level - Trace levels From 0.073 pg (absolute) - Pb - Chemicals (FeSO,, ZnO, Trace levels MnSO,, Fe powder) (below 1 p / g ) A A E E A A A A E E A A A A G L L L L L L L L L S, G L L Digest with HNO, and reduce with SnCI, Cold vapour Prepare solutions in 0-1M HNO, w F - H F , Graphite furnace - F - Stir 1 g sample in 100 ml N,O for 1 h F - Digest 1-10 mg sample with HNO, in F - micro-Carius tube at 250 "C.(Indirect method for determination of B "burn-up", producing 7Li species) - F Air/H, - F - - - See Cr, ref. 1821 Adjust to pH 1 - 2 with HCI.Heat graphite A electrode to incandescence, cool and immerse for 20 s in sample solution. Dry in air and use electrodes, in pairs, in a.c. arc discharge A.c. arc - F - Oxidize with H202/H,S0,, destroy excess F H202 with SO, or Na,SO,, dilute and extract with APDC/MIBK Air/C,H, See Ag, ref. 1689 F Air/C,H, - F - Extract Pb from sample solution with NaDDC/MIBK, in the presence of excess NaCN-kNH, citrate Graphite furnace 1168 1840 1804 681 1110 1250 425 1821 14 L 1804 1683 '1, b 1689 3.h 696 2 z 1068 2 0Pd 340.5 Photographic emulsions Pd Pt Rh Ru - Ru (SO,) (S,-band) S 384 S 180.7 Sb - Sb 217.0 Sb 206.8 217.6 231.1 259.8 Exhaust gas catalysts Aqueous solutions Aqueous solutions Nuclear waste materials Aqueous solutions Miscellaneous materials Halide salts Epitaxial silicon layers Explosives residues Phosphoric acid From 9 pg/ml From 0.6 pg/ml ng levels (absolute) From 1-25 CLg/ml 40 ng to 5 pg (absolute, as SO,) From 10 ng (absolute) From 30 pg (absolute) - 0.1-2.5 @/ml A A A A A A E E A A F L L L L L L G G L L 1 4 Extract film (2 drn2) with enzyme solution Graphite furnace 480 8 (Serizyrne) at 37 "C.Remove film, evaporate extract to dryness, treat with HN03/H,02, evaporate t o dryness, treat with HNO3/H,SO4/HCIO,, evaporate to dryness, add KBr/HBr solution+0*2M dibutyl sulphide solution in toluene. Separate toluene phase. - F - 696 (HGA-72) 9, 5. 2 Study of interferences and operating F N,0/C2H:, 1875 conditions. Add L%(SO,), buffer See Pt, ref. 1875 F N,O/C,H, 1875 For most matrices (e.g., condensates, Graphite furnace 361 HCI/CH,OH and NaOH scrubber solutions, Zr/Al waste feeds) treat with HCI and compare with single series of standards in 0.1 N HCI.For solid wastes, fuse with Na,O, and extract Ru with APDC/amyl acetate. Atomize at 2800 'C See Pt, ref. 1875 F N,O/C,H, 1875 Heat sample with reducing agent at F Air/H, 1443 300 "C and pass evolved H,S to MECA system.Prepare reducing agent by heating Sn granules with anhydrous H,PO,, in N, at 290 "C Reduce t o H,S by treatment with HI and P D.c. arc 1780 pass gas t o plasma source Etch with HF/HNO, ( 1 : 70), evaporate Graphite furnace 35 almost to dryness, add 0.2 ml HNO, and evaporate (twice). Dissolve residue in H,O (20-50 420 "C and atomize at 2050 'C Application of Zeeman effect AAS P - 1272 (Sb 217.02 nrn/Pb 217.00 nm) Hydride-evolution method, with F Ar/H, 1556 non-dispersive AFS system (+ MECA cavity) plasma Dry at 100 "C, ash at\o Table 4.1 B CHEMICALS AND MISCELLANEOUS MATERIALS- continued t 4 Element X/nm Matrix Concentration Tech.Analyte Form Sample treatment Atomization Ref. ~~ - ~~~~~~ Se 196.0 Semiconductor fragments - Se - Organic materials 0.1-10 pg/g Si - Organo-Si compounds VO levels Te 214.3 Semiconductor fragments ng levels 238.5 (absolute) Te 214.3 Semiconductor fragments - Ti 365.4 Hydrazine 2-6 ng/ml Ti - Fire-proofed wool - Ti 365.4 Hydrazine Trace levels (0.5-5 pg/rnl in extract) Zn - Carbon cloth - Zr - Fire-proofed woo! - C 324.7 Coke oven gases 0-1-0.5 g/nrn3 ( cs, 1 (CU) (indirect) A L, G A, F G A L E, A, F S, L A L, G A L A L A L A L A t A L Comparison of ETA-AAS and hydride- generation methods.Dissolve sample in H CI/H NO, Digest with HNO,/HCIO, (5 : 1) in Kjeldahl flask, add HN0,/H2S0, (1 : 1) and evaporate to fuming stage. Complete by hydride-evolution method Fuse with Na,O, in pressure bomb and F N,O/C,H, dissolve melt in organic acid, t o improve sensitivity and stability Comparison of ETA-AAS, ETA-AFS and (A) For solution methods, dissolve in A 9 A d.c.(8) For direct method, mix with graphite Graphite furnace (8-1268) Heated SiO, tube Heated SiO, tube Graphite furnace OES methods. (8-1268) HCI/HNO, (1 : 1) powder containing 19'0 Bi,O, See Se. ref. 1485 Graphite furnace Heated SiO, tube (B-1268) Flash-evaporate 100 ml sample to dryness Graphite furnace and dissolve residue in small volume of 0.2% HNO,.Calibrate by standard addition method Add excess F e ( l l l ) solution to overcome F - interferences by SO,, PO,, CIO,, citrate and silicate ions Flash-evaporate and dissolve residue Graphite furnace in acid. Atomize at 2800 "C (HGA-2100) See Cr, ref. 1981 F Air/C,H, Absorb CS, in alcoholic potash and add F - Cu(ll) solution to form cuprous xanthate complex.Filter, convert to soluble Cu salt and measure Cu level See Ti, ref. 1242 F - I 4135 1505 517 1484 1485 521 b 1242 ? 5. b 2057 ' $ 1981 5'4 Vitamin B, 217.0 (indirect) (Pb) Chlorpro- 357.9 (indirect) (indirect) (Ag) Various - (Rare earths) thixene (Cr) Thiols 328.1 Various - (Rare earths) Various - (12) Drugs - Drugs - Isopropanol-water 0.8-20 pmol/ml mixtures Luminescence materials - (M,SiO, type) Inorganic compounds From 1 pg/g (various) (3 elements) From 100 pg/g (8 elements) From 0.1 70 (4 elements) Trace levels High-purity acids and salts High-purity ng/g levels aluminium chloride Various - Trimethylgallium ether Trace levels (9) A %.A L De-sulphurize with K plumbite and F - 1066 A L Add exzess NH, reineckate, filter to F - 1231 3, 0 measure unreacted Pb ( I I ) remove precipitate and determine excess 5‘ Cr in filtrate z A L Add AgNO, solution, filter and dissolve F Air/C,H, 1712 E L Dissolve in HF/H,SO,, precipitate s - 23 precipitated salts in HNO, rare-earth hydroxides with NH,OH and redissolve in HCI. Nebulize solution into spark discharge (as appropriate) +Sc as internal standards E L Decompose with acid and add La or Y S Solution- 1142 spark method E E E Various - Semiconductor materials - A (4) (20) Various - Silicon Trace levels E (61 Various - Hydrochloric acid 0 * 001 -0- 2 c”g/g E L Add H,O-miscible organic solvent, e.g., S - ethanol, acetonitrite, to aqueous sample solution t o improve detection limits rhodanide-diantipyrylmethane, into CHCI,.Evaporate extract onto C powder for analysis. (Elements quoted : Co, Cu, Fe, Mo, Sn, Ti, V, Zn) S Extract sample solution with A - 1145 24 L De-alkylate with HCI, extract Ga as Hollow-cathode 26 butyl acetate, evaporate aqueous phase to dryness and redissolve in HCI/HNO,. Transfei 0.05 ml to graphite hollow cathode. for As, Se, Sb, Te discharge L/G Combined hydride evolution/ETA method Graphite furnace 105 L Comparison of ICP and AAS P ICP 148 G Heat samp!e and carry vapour in flow of P Microwave 194 argon to active nitrogen source.Application of Metastable Transfer discharge Emission Spectrometry (MTES) w wv) Table 4.1 B CHEMICALS AND MISCELLANEOUS MATERIALS- corztiriued L Element X/nm Matrix Concenlration Sample treatment Atomization Ref.Tech. Analyte Form Various ( 4 ) (8) Various Various Various Various ( 5 ) Various (13) Various Various (8) Various (5) - Silicon polymers Trace levels - High-purity Trace levels tungsten compounds - Coating materials - (paint, resin, pigments) - Polyimide resins pg/g levels - Silicon semiconductors Trace levels - Metal decanoates Major levels - Ammonium hydrogen Trace levels fluoride - Gallium p hosp hide Trace levels - Ammcnium bromide 1- 5 ps/s (Fe) 1(Mopg/g (Ba) 1-10 p u g (Mn, Pb, Cu) - Organometallic compounds Major levels A L A L A L A L E S A, E L E S E S E S A L Application of new digestion technique, Graphite furnace 267 for determination of Cu, Zn, Pb, Cr Dissolve compound, e.g., H,WO, or F - 369 (NH,),,W,,0,,.5 H,O, in 10% solution of fCH,),NOH, for determination of Al, Ca, Fe, K, Mg, Mo, Na, Si Review of ETA-AAS applications to Graphite furnace 520 analysis of materials associated with the coatings industry Ash under controlled temperature and F Air/C,H, 639 atmospheric conditions in special quartz vessel.Dissolve ash in acid. Results given for Cu, Fe, K, Na De-grease specimen, air-dry and etch for A A.c. arc 742 1 min by suspension in solution of HNO,/40% HF/C,H,O, (8 : 1 : 1).Add C powder, evaporate to dryness, add KCI solution, dry and excite in electrode cavity to determine Al, Fe, Cu, Mg, Mn Description of preparation, analysis and - - 772 applications of metal decanoates as b spectrochemical reference materials 3 3 a, 3 Study of added-matrix effects (G3O3, A - 792 2 GeO,, graphite, MgO, ZnO) Study of effect of Ca on the determination of At, Si, Be, Mg, Sn, Ge, As and Zn Mix (10 : 1) with graphite powder and A 10 A d.c. 1122 ? ignite gently t o 330 "C.Mix residue with 10% NaCl $ A 12 A d.c. ah F - 1186Various - Calcium salts; electrolytes Trace levels E (8) Various - Chemicals ( 5 ) Trace levels Various - Forensic samples - Various - Drugs (10) Trace levels Various - Cadmium mercury telluride ng/g levels ( 9) Various - Domestic refuse - (11) Various - Red lead ( 7 ) 0.1-100 pg/g A E E, A A A E Various - Firerarm pellets, residues - A Various - Thin films CLg/cm3 levels A A Various - Drugs - L L L L S L S L L L (1) For CaCl,, dissolve 12 g in H,O and (2) For CaCO,, dissolve 12.5 g in HCI F Air/propane/ butane (A), Air/C,H, (6) and (C) dilute to 500 ml (Na, K, Mg) (1 : 1) and dilute to 500 ml (Cu, Fe, Mn, At) N,0/C2H, (3) Na/Li electrolyte, 0.5 g to 500 ml (Li) Flames : (A) Na, K, Li, (B) Mg, Cu, Fe, Automatic flame injection method applied F to determination of Ca, Fe, Cu, Pb and Zn in various chemical salts and mineral acids - P ICP AAS and OES methods for Ca, Ag, Cu, A,F - At, Bi, Ni, Fe, Mg, Pb, Zn Direct method, for Ag, Cu, Fe, Mn, Cr, Al, Na, Mg, Si Ash at 480 "C, digest with HF/HNO, F - (3 : 2) followed by HNOJHCIO, (5 : 2) and heat to fuming.Dissolve i n HCI and dilute to volume (50 m i for 6 g sample). Determine At, Fe, Ca, Mg, K, Na, Sn, Cu ,Zn, Pb, Ni by AAS. (Results compared with those given by ASTM methods) Mix (1 : 1) with C powder and transfer 50 mg to electrode cavity. Cover with 20 mg C powder containing 8% NaCI. (An extraction-concentration method i s also given, for concentrations from 5 ng/g to 10 pg/g). Elements : Cr, Cu, Co, Ni, Fe, Mn and V Use of AAS and NAA to characterize F Air/C,H, materials for As, Sb, Cu, Pb, Au, Fe, Zn Etch metal layers with acid, e.g., F Air/C,H, HCI/H,O at 55 "C (Cu, Ni); HCI/HNO, at 65 "C (Au);; HF at 40 "C (Ta) Mn, (C) Al - Graphite furnace A 15 A a.c. N,O/C,H, Review (50 refs.) F - 1266 2 1279 1286 1405 1409 1609 1626 1631 1866 1925 \oTable 4.1B CHEMICALS AND MISCELLANEOUS MATERIALS- coittirrued W a Element X/nm Matrix Concentration Sample treatment Atomization Ref. Tech. Analyte Form Various - Drugs (20) Various - Various (13) A L Review P - 1969 Graphite furnace E S Study of d.c. arc effects for various A D.c. arc 2068 matrices (SiO,, graphite, albite, CdSO,, NaCI/CaO) and internal standards (Pb. Ge, In, Bi) b b