摘要:

I38 Analytical Atomic Spectroscopy 4.2 METALS 4.2.1 Iron and Steel 4.2.1.1 Atomic Emission Methods The application of inductively coupled plasma-optical emission spectroscopy t o the analysis of iron and s t e e l i s now firmly established. I n a review which included 60 references, Koch (1791) discussed the scope of the technique f o r trace element determination i n s t e e l . of the ICP into the analytical scheme of a large steelworks laboratory.Prior t o i t s introduction, 5% of the work load was carried out by classical chemical methods. Over half of t h i s work was transferred t o ICP-OES following the i n s t a l - lation of a 45 channel simultaneous instrument t o determine 31 elements. Over 7000 determinations a month are now made using the technique.of P in s t e e l was the subject of investigation. removal of C u , an i n t e r f e r i n g element, by solvent extraction. Presumably the wavelength employed was 213.6 nm, as the author claimed the method did not require a vacuum system. performance of several P wavelengths, and concluded t h a t 178.3 nm produced superior r e s u l t s . The determination of B i n s t e e l in i t s acid-soluble and insoluble forms by d i s t i l l a t i o n i s time-consuming and requires a h i g h degree of s k i l l .Both ICP and d.c. plasmas have been used as a l t e r n a t i v e s . Thierig (1049) quoted a SD of 0.00014% f o r a 0.0031% B s t e e l and a detection l i m i t of 0.0004%, whilst Flinchbaugh and Fernandez (C6) reported a calibration range from 5 t o 100 ppm, w i t h an estimated accuracy of 2 4 ppm.The ICP has a l s o been applied t o the determination of metallic elements i n precipitates and inclusions in low alloy and f e r r i t i c s t a i n l e s s s t e e l s (422). These were extracted electro- l y t i c a l l y by preferential dissolution of the s t e e l matrix and Cr, Fe, Mn, Mo and Nb were determined. Shibata (C1350) described the integration The determination One paper (786) advocated the Other authors (C14), however, examined the analytical I n t e r e s t continues i n the d i r e c t atomization of s o l i d samples and t h e i r analysis by ICP-OES.Ohls (C259, 555) described the vaporization of c a s t iron and s t e e l samples u s i n g a graphite crucible. A detection l i m i t of approximately 10-llg,for elements determined when dry residues of solutions (10 p l ) on a graphite rod were introduced i n t o a plasma torch has been reported (C1691).The potential of Separate Sampling and Excitation Analysis (SSEA) was again reviewed (C40, C1232). (See a l s o Sections 1.2.1.2, 2.5.1 and 3.1.4.3). source conditions in arcs and sparks t o minimize metallurgical e f f e c t s .Washburn and Walters (1565) suggested t h a t using a high current (800 A ) , high r e p e t i t i o n source (1920 Hz) not only reduced analysis time substantially b u t a l s o coped with ferrous alloys which had previously proved d i f f i c u l t t o analyse. discussed the determination of soluble A 1 i n s t e e l a t the refining stage of Several papers (1005, 1565, 2248) stressed the importance of optimizing Three papers4 pplications 139 production (C259, C290, 1815). Hughes (C290) described r e s u l t s obtained when JK s t e e l s were submitted f o r a n a l y s i s by a method based on t h e p u l s e h e i g h t m a l y s i s o f i n d i v i d u a l A1 spark l i n e i n t e n s i t i e s .Problems were observed which Mere a t t r i b u t e d t o t h e s t r u c t u r e and d i s t r i b u t i o n o f A1 r i c h i n c l u s i o n s . 3.1. (1815) described a method based on t h e observation o f s t r o n g emission i n t e n s i t i e s d u r i n g t h e f i r s t stage o f sparking. o f each i n t e n s i t y i n t h e f i r s t and l a t e r stages was r e l a t e d t o t h e p a r t i t i o n o f 41 between t h e s t e e l m a t r i x and i n c l u s i o n s .Ono g The d i f f e r e n c e between t h e mean Laser e x c i t a t i o n f e a t u r e s more prominently i n work r e p o r t e d t h i s year. A paper by Ozaki e t a l . (1852) described a method f o r analysing l i q u i d s t e e l d i r e c t l y , an 3 b j e c t i v e much sought a f t e r i n t h e past."Giant p u l s e " l a s e r e x c i t a t i o n was used and t h e o p t i c a l axes o f t h e l a s e r and spectrometer coincided. Problems i n the determination o f C caused by t h e generation o f CO a t t h e s t e e l surface were e l i m i n a t e d by u s i n g a c o n t r o l l e d atmosphere. the a n a l y s i s o f s o l i d s t e e l s (1898). Applications t o t h e a n a l y s i s o f c a s t i r o n c o n t a i n i n g g r a p h i t e (124) and a l l o y s t e e l s (C290) were described.This l a t t e r paper a l s o described t h e development o f a method f o r determining d e - c a r b u r i z a t i o n l a y e r s on processed s t e e l surfaces. The same p r i n c i p l e was a p p l i e d t o Papers on t h e glow discharge lamp r e f e r r e d t o b u l k and surface a n a l y s i s . 4.2.1.2 Atomic Absorption Methods The p o t e n t i a l o f AAS f o r r o u t i n e a p p l i c a t i o n f o l l o w i n g 2 d i s s o l u t i o n procedure was w e l l i l l u s t r a t e d (560, 632, 638, 1724, 1800, 1927). Methods were described t o determine C r y Mo, N i , Sn and s o l u b l e A1 i n s t e e l . Coutinho (638) combined AAS w i t h a r a p i d d i s s o l u t i o n procedure t o p r o v i d e a q u i c k method (130 s ) f o r s o l u b l e A1 determination. 0.01-0.08% A l . Others (1216, 1386) described s o l v e n t e x t r a c t i o n procedures as a precursor t o t h e AAS determination of B i , Cd, Cu, Mo and Pb i n s t e e l . Weltz e t a l . (C289) described a Zeeman-effect background c o r r e c t i o n system which was p r e f e r r e d t o a continuum-source system f o r t h e determination o f P i n s t e e l by ETA-AAS.The e r r o r s were w i t h i n 2 0.004% i n t h e range A d e t e c t i o n l i m i t o f 0.002% P was reported. Weltz e t a l . (642) minimized Fe i n t e r f e r e n c e i n t h e h y d r i d e generation determination o f As, B i , Sb, Se, Sn and Te i n s t e e l by t h e a d d i t i o n o f HN03 t o the d i s s o l u t i o n medium.Others (534, 877) described t h e determination o f Sn and Te i n s t e e l by AAS. The working range f o r Te was 10-100 ppm, w i t h a RSD o f 5% a t 44 ppm, and 12% a t 12.5 ppm. and a l l o y s using samples of l e s s than 1 mg loaded i n d i v i d u a l l y and c o n s e c u t i v e l y i n t o a g r a p h i t e furnace.up t o 10 mg t o t a l sample, b u t p r e c i s i o n s t a r t e d t o f a l l f o r copper a f t e r a d d i t i o n s The a p p l i c a t i o n o f s o l i d sample a t o m i z a t i o n continues t o g a i n ground. Hirokawa Takada (559) r e p o r t e d t h e determination o f Pb i n s t e e l , copper and copper For s t e e l , t h e s e n s i t i v i t y o f measurement remained constant140 Analytical Atomic Spectroscopy o f 2.5 mg.Kobayashi (1927) r e p o r t e d t h e determination o f Sn i n i r o n and s t e e l by ETA-AAS. The g r a p h i t e furnace was h e l d a t 2873 K f o r 20 s f o r atomization. l i m i t was 0.1 ppm. Ohls (555, C259) a l s o r e p o r t e d t h e determination o f t r a c e elements between 0.1 and 10 ppm u s i n g s o l i d samples.used i n some determinations t o separate t h e d i f f e r e n t forms o f c e r t a i n elements i n i r o n and s t e e l . c a s t i r o n , and A1 and A1203 i n s t e e l . o f an aerosol from s t e e l samples u s i n g an e l e c t r i c a l spark o r a r c , t h e vapour produced being swept w i t h a i r i n t o an air/C2H2 flame.Sparking was r e p o r t e d t o be s u p e r i o r t o arcing, p e r m i t t i n g t h e determination o f 0.2% C r and 0.1% Mn w i t h a RSD o f 3.8%. The d e t e c t i o n l i m i t was 0.017 ng (0.34 ppm Pb i n a 0.5 mg sample). The d e t e c t i o n Step-wise h e a t i n g was This was i l l u s t r a t e d by t h e determination o f Mg and MgO i n Papp e t a l .(974) described t h e generation 4.2.2 Non-ferrous Metals and A l l o y s Several reviews compared t h e m e r i t s o f various emission and absorption tech- niques. i n non-ferrous metals a n a l y s i s and Shmanenkova (577) t h e same techniques f o r r a r e - e a r t h metal production c o n t r o l . Dorner (716) and Fujimoto e t a l . (867) reviewed t h e techniques a p p l i e d t o l e a d and aluminium a n a l y s i s .Doolan and Belcher (496) compared t h e use o f AES, AFS, AAS and XRF 4.2.2.1 Atomic Emission Methods I n d u c t i v e l y coupled plasma-optical emission spectroscopy i s now being a p p l i e d r o u t i n e l y r a r e - e a r t h and precious metals and various c o r r o s i o n products. Ward (C1331) i l l u s t r a t e d a p p l i c a t i o n s t o n i c k e l a l l o y s and l i s t e d c o n c e n t r a t i o n ranges d e t e r - mined f o r t h e major elements Coy C r y Fey Mo, Nb and N i , and t h e o t h e r elements determined, A l , B, Ca, Cu, Mg, Mn, P, T i and V.Marks e t a l . (C222) described experiences using separate sampling and e x c i t a t on a n a l y s i s i n an i n d u s t r i a l environment.Traces o f B and S i were successfu l y determined as w e l l as major elements i n n i c k e l a l l o y s , b u t s p e c t r a l i n t e r f e ences precluded t h e determination o f P. (C7) who compared r e s u l t s w i t h c e r t i f i e d values f o r A l , Fey Mo and V i n the CRM NBS 173a. Fey Mn, Mo, S i , Sn, V and Z r i n t i t a n i u m a l l o y s .Precious metal a n a l y s i s was the s u b j e c t o f a s e r i e s o f papers (521, C149, C1331, C1419, C1422). I n two o f these (C149, C1419) ICP-OES was combined w i t h f i r e assay procedures and t h e r e s u l t s obtained f o r Pd (0.045 oz/ton) and P t (0.109 oz/ton) were i n agreement w i t h accepted values f o r a US Geological Survey Standard. (471) who used a low energy Nd:YAG l a s e r t o analyse copper a l l o y s .H o r l i c k (550), u s i n g a ruby l a s e r , obtained good r e s u l t s i n t h e a n a l y s i s o f t o t h e a n a l y s i s o f n i c k e l , t i t a n i u m , aluminium, copper and lead a l l o y s , The a n a l y s i s o f t i t a n i u m a l l o y s by ICP-OES was i l l u s t r a t e d by L i p p e r t Other workers (C397) claimed an RSD o f 1% f o r t h e determination o f A1 , Laser v a p o r i z a t i o n was used i n c o n j u n c t i o n w i t h ICP-OES by Kawaqudi e t a l .Carr andApplications 141 a1 umi n i um a1 1 oys and brass. 4.2.2.2 Atomic Absorption Methods Many papers i l l u s t r a t e the scope f o r routine application of AAS following dis- solution procedures. Problems of interferences and lack o f s e n s i t i v i t y , however, were reflected i n the number of papers describing separation and extraction procedures. aluminium,of Cry Cu, Fey Mg, Mn and Zn (465), B i , Cd, Cu, In, Pb and T1 (571), Mn (787), Cu (893) and In (897).The analysis of gallium was the subject of a review of several techniques (536) and extraction - AAS was shown t o be capable o f determining elements i n the range 0.1400 ppb.applied t o the determination of Pd, P t and Rh i n high purity gold and s i l v e r by ETA-AAS (671). Detection l i m i t s were i n the range 2 x lo-’ t o 2 x 10e8g. Headridge (C291, 1558, 1600) reported detection l i m i t s ranging from 2-100 ng g-l f o r the determination of As, Cd, In, S b , Se, Te and Zn in nickel alloys using metal chips placed i n an induction furnace.Five papers reported d i f f e r e n t methods f o r the determi nation, in Direct atomization of s o l i d samples continues t o a t t r a c t a t t e n t i o n . I t was In the nuclear industry there were examples of the application of AAS t o the determination o f t r a c e elements i n sodium. determination of Cay Coy Cry C u , K, L i , Mg, Mn and Pb i n nuclear grade sodium (1409).d i s t i l l a t i o n because of losses of these elements i n t h i s process. l i m i t s i n the l a t t e r case were i n the range 5-10 ppb. were determined by ETA-AAS following separation (1161). 0.001, 0.01, 0.025 and 0.5 ng f o r Cd, Co, Cu and Ni, respectively. D i s t i l l a t i o n was used p r i o r t o the Mahalingam e t a l .(1929), however, determined Cd, Pb and Zn without Detection Trace elements i n uranium Detection l i m i t s wereTable 4.2A IRON AND STEELS Element h/nm Matrix Technique, Atomization, Concen tntion Analyte form Sample treatment Ref. Al Al Al Al Al B B B Ba C C C Cr Cr Cr Cr Cr Cr Cr - - - - 543 455.4 229.7 193.1 - - 351.9 359 357.9 425.4 434.5 520.8 359 Iron and steels Steel Steel Steel Steel Steel Steel Steel Steel Steel Steel Steel Steel, food Tin plate Steel Alloy steels Steels, aluminium alloys Steel coating Alloy steels 0-1 00 rg/ml 0.01-0.08% 0.01 -0.08% - 5 -1 00 rg/ml 0.0004-0.007% 5 - 100 rg/ml 0-0.0006% Trace levels 0-20 rglml Major levels 0.2 - 10 pgiml - Major levels, E, A, S E, S , S E, Laser, L E, Laser, S F, Laser, S A, F, Air/C, H, , L A, F, Air& H, , G A, F, Air/C, €1, A, ETA, L A, -, - A, F, AU/C, H, , L Use of nebulizer with improved mixing chamber Electrolytic dissolution of sample in 10% HC1 to determine soluble A1 Electrolytic dissolution of sample (see ref. 638) Pulse height analysis to determine sol.and insol. A1 Analysis of pulses to differentiate sol.and insol. Al Acid dissolution and mercury cathode separation Comparison of spectrophotometric and spark and plasma emission methods Solvent extraction into a 1:8 solution of 2.6dimethyl- 4.6-octanediol in MePh Arc excitation in carbon cavity after dissolution of 2.5 g of sample in HCI (1 :3), evaporation and ignition, mixing with an equal weight of carbon Study to improve detection limit of C determination Direct analysis of liquid steel by laser excitation (giant pulse) Application of giant pulse laser excitation to solid steel analysis using Ar + 38H atmosphere Laser ablation of the sample Determine Cr in passivating film by dissolving the film in boiling HC1 (5 ml of 50% acid), dilute to 50 ml with water Aerosol generation by electric spark NH,C1 buffer to counter interference of, Fe, Ni and A1 Dissolve 0.1 g sample in 20 ml aqua regiu and 30 ml H, SO,, filter residue; for Cr residue treated with HF and added to filtrate Coating of steel by Cr in vacuum was controlled by measuring absorption of Cr vapour above steel surface Dissolve in HC10, , dilute and buffer with 1% NH,CI.With high alloy (> 4% Cr) use less sensitive 359 nm line 632 638 849 1210 1815 C6 1049 1835 1725 557 1852 1898 482 522 974 993 1381 1533 1724cu Mn Mn Mn Mn Mn Mn Mo 327.4 Steels, zinc, tin 0.0006-0.1 '3 A, ETA, L Steel: dissolve in HNO, Zinc: dissolve in HCI/HNO, Tin: dissolve in HCIO,/HBr, evaporate to dryness and extract Cu from residue by dissolution in HNO, Standard addition method See Cr, ref. 974 See Cr, ref. 1381 Steel Steel Steels, aluminium alloys Cast iron, minerals Steel Steel Steel A, F, L A, F, Air/C, H, , G A, ETA, L 366 974 1381 - 0.05 -0.5 pglml 279.5 403.5 280.1 293.3 E, Laser, S Laser sampling and arc discharge of solid samples 1531 E, Laser, L E, Laser, S A,F,CO/C,H,,L See C, ref. 1852 See C, ref. 1898 Acid dissolution; interference of dissolution media, including HF, H, SO,, HC1, HNO, , H, PO, and HC10, investigated; addition of 1.2 mg/ml of A1 eliminated most interferences See Cr, ref. 993 Solvent extraction of Mo into MlBK See Cr, ref. 1724 See Mn, ref. 366 Dissolve 0.5 g sample in 30 ml aqua regiu, evaporate to 15 ml, dilute to 100 ml with H, 0; 2 ml aliquot diluted to 100 ml with 0.1 N HNO, Examination of performance of six P lines after acid dissolution of 0.5 g of steel in 20 ml of HCO(1 + 1) and 10 ml of HNO, (1 + l ) , diluted to 100 ml 0.2% lanthanum solution as matrix modifier; Zeeman effect background correction Interfering Cu removed by solvent extraction with dibenzyldithiocarbamate Use of low-voltage ax.spark source See P, ref. C289 Direct atomization of solid samples 1852 1898 560 - 317.0 0-3% Major levels - - Mo Mo M a Ni Ni P P P P P Pb Si Si - Alloy steels 313.3 Iron and steels - Alloy steels - Steel 341.5 Stainless steel A, I;, AirIC, H, , L A, F, N, OlC, H, , L A, F, N, O/C, H, , L A, F, L A, -, L 993 1216 1724 366 1800 8-30% - 178.3 Low and high-alloy steels E, P, ICP, L C14 Steels A, ETA, L E, P, ICP, L E, S, S A, ETA, L A, ETA, S A, ETA, L C289 786 83 1 1581 559 C316 Steels 604.3 Cast irons and steels 213.6 Steel Steel, copper, copper alloys - Steels 0.02-0.08% 0.002-0.1 7T2 Method based on molybdenum heteropoly acid chemistry; silicon extracted as dodecamolybdosilicic acid in a mixture of ethoxyethane and pentan-1-01 ( 5 + 1) See Mn, ref. 1531 0-0.5% 25 1.6 Cast iron, minerals E, Laser, S 1531Table 4.2A IRON AND STEELS-continued Technique, Atomization, Element h/nm Matrix Concentration Analyte form Sample treatment Ref.Si Si Sn Steel - Steel 286.3 Metallurgical geological, environmental materials Iron and Steels E, Laser, L E, Laser, S A, ETA, G See C, ref. 1852 See C, ref. 1898 Dissolve sample in HCl/HNO, ( 3 : l ) filter and adjust to 0.3 M HC1; generate hydride using N as carrier and sheath gas 1852 1898 534 5-25 ng/ml Sn Trace levels A, ETA, L or S Acid dissolution in HCl/HNO, and HF/H, PO, : atomization at 2773 K for 4 s.Direct atomization of solid samples at 2873 K for 20 s. Hydride dissociation in an electrically heated quartz cuvette Comparison of methods; ETA preferred for sub-ppm concentrations 1921 Te Steel 0.001-0.01% A, ETA, G 877 TI Process, dust, raw materials E, P, ICP, L A, F, L A, ETA, L E, P, CMP, L E, P, ICP, G E, GDL, S 561 W Various Various (5 1 Various 400.9 407.4 - Steels, alloys Iron steels Cast iron 0.2-80% O-lOO% 0-6% Simplex procedure to optimize conditions Vaporize with spark and pass into plasma Optimization of glow discharge lamp conditions to analyze cast irons containing graphite (C, Si, Mn, S , P) Review of new aspects in atomic spectroscopy, particularly direct atomization of solid samples Review of new developments particularly A1 analysis by pulse height analysis and use of GDL for surface analysis 1098 C40 124 C25 9 E, S, S E, P, ICP, S A, ETA, S E, S, S E, P, ICP, L E, GDL, S E, P, ICP, L Iron, steels Various Iron, steels C290 Various (5 ) Alloy steel precipitates Major and minor levels Electrolytically dissolve - 0.2 g of sample; filter off precipitate and fuse in Na, S, 0, ; extract with 20% tartaric acid and dilute with water (Fe, Mo, Cr, Mn, Nb) Review of AAS and 1CP-OES methods using solid samples Various 0.1 - 10 pg/ml A, ETA, S E, P, ICP, S - Iron, steels Various (8) Various (6 ) Steel E, P, ICP, L Investigation of automatic wet ashing equipment for steel dissolution (Al, As, Cr, Cu, Ni, Mn, P, Si) Steel 0.01-0.1% A, -.L Application in molecular absorption (B, Cr, Nb, P, Ta, 21) spectrophotometryVarious (18) Various (6 ) Various (12) Various (16) Various Various Various Various (9) Various Various (4) Various Various Various Various (31) Various (4) Various (4) Various Various Various - Low-alloy, - Steel high-speed steels Tungsten steels Tungsten steels Iron, steels Ferrous and non- ferrous metallurgy Metallurgical materials Steel, welding electrodes Ferrous, non-ferrous alloys Steels Steel Steel, Ni-alloys Steel, soil, W powder, precious metals Iron, steel, ore, dust, slag Iron, steel, aluminium metal, tin metal Steel Alloy steels Steels, rare and precious metals Steels, ores, oils Direct computerized readings using OES Trace levels A, -, G - E, s, s E.P, ICP, L E, s, s E, -, - A, -, - E, P, ICP, G Trace levels E, P, D.c., L Major levels E, P, L A, F, L E, P, ICP, L F, P, ICP, L E, P, ICP, L O .l - l ~ g / m l A, -, L A, ETA, S E, s, s E, P, ICP, L E, P, ICP, L Hydride generation; interference effects of HCl, HNO, and Fe investigated (As, Bi, Sb, Se, Sn, Te) Analysis time of 20 s for 12 elements in Wcontaining steels Ten elements determined directly, six after separation by precipitation Use of oscillating low voltage spark discharge Review of atomic absorption, emission and X-ray fluorescence in non-ferrous metallurgy, geological prospecting and ore treatment monitoring Review (with 44 references) leading to good laboratory analytical practices High frequency spark excitation to analyse steel and welding wires using Mg electrode (for C analysis) and Armco Fe electrode (Cr, Mn, Mo, Nb, Ni, Si, Ti, V) Vaporize with spark and pass into plasma Trace analysis using d.c.plasma (As, Ce, Ta, W) Comparison of advantages and disadvantages of atomic absorption and plasma emission Optimization of plasma conditions Fluorescence spectrometer using ICP for atomization and hollow cathode lamps for excitation Integration of ICP spectrometer to analytical instrumen- tation of steelworks laboratory Dissolve in H, PO, or mixture of H, PO,, HNO, , H, SO, and HCI; adjust to 4 M H, PO,, add 1% DDC in butyl- acetate; organic phase stripped with 5 ml of 2-4% NH, F solution (Cd, Cu, Bi, Pb) Direct atomization or solid samples in graphite cup cuvette (Ag, Bi, Pb, Zn) Use of high current, high repetition source Use of solutions and dry residues of solutions on graphite rods Automated sequential or simultaneous spectrometer using double monochromator range 178.3-766.5 nm, with high svectral resolution 3 64 2 781 782 100s 1080 1138 1152 C1232 C1281 C1287 C1292 C1333 C1350 1386 1387 1565 C1691 1772Table 4.2A IRON AND STEELS-continued Technique, Atomization, Element klnm Matrix Concentration Analyte form Sample treatment Ref.Various (5 ) Various Various (5 1 Various Various (4 ) Various (4) Steel wires and rods E, A, S Steel Trace levels E, P, ICP, - Iron, steel Steel, aluminium alloys Steel Steel Trace levels E, P, ICP, - Use of 1 .O A arc excitation source to analyse steel wires and rods (Cr, Cu, Mn, Ni, Si) Review with 60 references; possibility of using ICP-OES for trace analysis discussed 1780 1791 Analytical lines and detection limits listed (Al, Cr, Mo, Ti, V) 1926 E, S , S Optimization of spark source conditions 1961 A, ETA, S E, S, S Direct atomization of solid samples in graphite cup-cuvette Optimization of source conditions to allow for different temper cast structures (C, Mn, S, P) 1964 2248 (Ag, Cu, Mn, Pb) Various Steel 0-2% A, F, N, OIC, H, , L Autosampler used in conjunction with sequential AA 2281 (8) spectrometer (Al, Cr, Cu, Mn, Mo, Ni Ti, V) bb % Table 4.28 NON-FERROUS METALS :: 5 Atomization, 2 Technique, Element h/nm Matrix Concentration Analyte Form Sample Treatment Ref.Am Am and Cm samples E, A, L Separation procedures described. Bis-(2ethylhexyl) hydrogen phosphate (I) is used prior to a.c.or d.c. arc excitation of solution applied to carbon: BiF, (or NaCI) powder; also chromatographic procedure with elution using diethylenetriamine penta-acetic acid or extraction using (I) in decane Co-precipitation of As with La(OH), after acid digestion of metal sample in dil. HNO, Extraction using isoamyl alcohol-petroleum ether (4-6):l as solvent; atomization at 400-500°C Dissolve 5 g of sample (or 2 g for contents of Au in excess of 40rg/g) in a 15% solution of SnCI, .2H, 0 in HCI, filter, dissolve residue in aqueous Br-HCI, evaporate to 5 ml, filter and dilute filtrate to 50 ml; if content < 3 pg/g extract Au with 5 ml MIBK Comparison of techniques including fire assay, A.AS, plasma spectrometry coulometry, gravimctry, ctc.Discussion of acceptance of AAS for analysis of Au in solutions and problems with solid sample analysis; results for both methods presented Dissolution of samples in acid at 120-250°C in PTFE vessel prior to ICP analysis Addition of EDTA to remove interference effects or removal of coexisting chlorides by vaporization Dissolve in HNO, (1 :I), adjust to 1.5 M HNO, and co.precipitate Bi with hydrous MnO, Sensitivity increased 3-4 fold by use of sandwich burner with two slots for 0, Interference of Al and Si studied and methods to eliminate these given Atomization using induction furnace and solid samples Sample dissolved in HCI (1 : I ) , Cu and Fe oxidized with H, 0, ; decompose excess H, 0, , add 10% ascorbic acid to prevent interference by chlorides of Cu and Zn See Am.ref. 589 589 457 905 1713 1963 C2291 753 1 1109 478 1755 1600 1663 589 193.7 Cu metal Au solutions Au minerals 0-9.1 W’g A, ETA, L A, ETA, L A, -, L As Au Au Au Au Au solutium Au solutions Alloys and magnetic materials 344.9 Cu- and MI-A1 alloys - E, P, ICP, L B Be 4 -6 @g/g A, ETA, L Bi Ca Metals and alloys Trace levels A, F, Air/C,H, -C,H,,, L Die cast alloys 0.03-0.1% A, F, AU/C, H, , L 422.1 AI-Si alloys - A, F, N,O/C,H,, L 0.002-2 wg/g A, ETA, S Trace levels A, ETA, L Ca 228.8 Ni alloys 228.8 Zn die casts Cd Cd Cm - Am and Cm samples E, A, LTable 4.28 NON-FERROUS METALS-continued Technique, Atomization, Element h/nm Matrix Concentration Analyte Form Sample Treatment Ref.Cr Cr Cr c u c u cu Fe Fe Hg In In L1 LI Mg Mn Mn Mo - Protective coatings Alloys 357.9 Li metal 391.4 Cu -Zn alloys 324.8 A1 metal 324.7 - 248.3 - 303.9 451.1 303.9 670.8 670.8 279.5 219.5 Al, A1 alloys Vanadium melt Li metal High purity Cd, In, Ge, TI A1 alloys Ni alloys Al metal Li Rubber A1 metal Al and A1 alloy? Ores and slags Trace levels Trace levels Trace levels Trace levels Trace levels Trace levels 0-350 Ug/g 0 13-15gg/ml 0.1- 2.0gg/ml 2-3% Trace levels 0 - 3 69 r g / g A, -.L E, P, ICP, L A, F, Air/C, H, or N, O/C, H, , L A, ETA, L E, GDL, S A, F, AUK, H,, L A, ETA, L A, F, - A, ETA, L A, -,G E or A, F, AU/C, H, or N, OK, H, , L A, ETA, S E or A, F, Air/C, H, , L E, S, S A, F, Air/C, H, , L A. F, L A. -, L A, ETA, L A, F, N, OK, H, , L Scope of AAS, XRF and ICP-OES for determining Cr (and Zn) in corrosion resistant coatings Interference of Fe studied; 0.5% H, BO, found to be best suppressor compared with NH,CI and KCI Direct determination after acid dissolution but co- precipitation with LaOH to determine ultra trace levels Study of interference of alloy additions and preparation of of working curves using the Grimm glow discharge lamp To a sample containing less than 25 gg Cu add Na, S, 0, to form Cu-thiosulfate complex, adjust S,O:- to 0.025 M and to pH 5 with 5 ml 2 M acetate solution, dilute to 4 0 ml with H, 0, extract thiosulphate complex with 10 ml 3% Capriquat solution in isoPr OAc and aspirate the organic phase Dissolve 1 g sample in 6M HCI/H,O, by heating in water bath, filter and add EDTA to eliminate A1 interference Continuous determination of Fe in a vanadium melt by absorbance of analyte atoms emanating from melt surface See Cr, ref. 2053 Use of cold-vapour technique involving SnCI, reduction of solution; TI interference eliminated by extracting TI with chlorex from HC1 solutions Dissolve sample in HCI, adjust to pH3 and extract with DDC See Cd, ref. 1600 Comparison of determination by AAS with direct emission spectrometric and flame photometric analysis Determination of Li and ’ Li abundances See Ca, ref. 478 Mn extracted using optimum conditions of 1.68 X l o - ’ M thiothenoyltrifluoroacetone in CHCI, in the presence of 3 X See Cu, ref. 2262 Sample dissolution using LiBO, for fusion and HF and boric acid dissolution M 1,lO-phenanthroline, shaking for 3 min c109 636 205 3 876 893 2262 591 2053 1154 a97 1600 1619 2227 478 787 2262 934Na Ni Ni Ni P Pb Pb Pb Pb Pb Pd Pd Pt Pt Re Rh Rh Sb Sb Se Si crystals - Ni-Au alloys High purity Ni 232.0 Li metal - Fe, Mn, Ni, Co and Cu 537.2 Pb 283.3 - - - 227.5 217.5 - 196.0 Misc.materials Cu-Zn alloys High-purity Cd A1 and A1 alloys Au, Ag and alloys Ag alloys Au, Ag and alloys Ag alloys Cu-Mo-Fe alloys Au, Ag and alloys Ag alloys Cu metal Solder Cu metal Trace levels - - Trace levels Trace levels - Trace levels - Trace levels - Trace levels Trace levels Trace levels Trace levels Trace levels Trace levels 1.4-1 18 Mg/g 10-100ng/g E, Laser, S A, ETA, L A, F, AU/C, H, , L E, P, ICP, L A, -, - E, P, ICP, L E, GDL, S A, F, L A, ETA, L A, ETA, S A, ETA, L A, ETA, S A, ETA, L E, P, ICP, L A, ETA, S A, ETA, L A, ETA, L A, ETA, L A, ETA, L Laser ablation and resonance ionization spectroscopy (LARIS) Study by factorial analysis of matrix effects in AAS analysis of Ni in Au Determination of NiO on high purity nickel by dissolving Ni metal in K Cu C1, , NiO filtered off and dissolved See Cr, ref. 2053 Indirect method involving oxidation to P(V) with KMnO, and reaction with molybdate; extract heteropoly acid into BuOAc Isotopic abundance measurements using ICP-OES and medium -resolution monochromator linked to a Fabry interferometer Review of many methods including AAS, ICP-OES, spectrophotometry, voltammetry and polarography See Cu, ref. 876 Dissolve Cd, adjust pH of solution to 10 by using NH,OH, extract Pb into the organic phase with 4caprinoyl-3-methyl- 1-phenyl-5-pyrazolone into iso-BuMeCo; Fe interference (> 1Opg) eliminated prior to Pb extraction by extracting with iso-BuMeCo from 6M HCI solution See Cu, ref. 2262 Direct atomization of solid samples Separation of Ag as chloride using graphite cup and furnace See Pd, ref. 671 See Pd, ref. 935 Study of matrix effects See Pd, ref. 671 See Pd, Ref. 935 See As, ref. 457 Co-precipitation of Sb with 10 mg Th added to 100-200 ml sample containing 1-10 pg Sb, NH,OH added to give pH of 9.5, filter precipitate, dissolve in 10 ml 2N HC1, dilute to 100 ml, analyse lop1 aliquots Dissolve 5 g of Cu in 50 ml HCI and 30% H, 0, , boil off excess H, O,, add 30 ml HCI + 0.5 ml As (Ill) (1000 mg/l) + 10 ml 50% H,PO, , heat until complete precipitation in 1-2 h, dissolve precipitate in HNO, , add excess Ni(NO,), and dilute to 50 ml 892 2053 644 546 716 876 1162 2262 671 935 671 935 C2358 671 935 457 890 2282Table 4.2B NON-FERROUS METALS-continued Element A / n m Matrix Technique, Atomization, Concentration Analyte Form Sample Treatment Ref.Si Si-A1 alloys Si 25 1.6 Ti metal and alloys Si Si Sn Ta Te Te Te Th Ti TI U V W - 224.6 A1 alloys and steels - Alloys - Cu, Pb, Ni, Se, A1 - metals, Cu and Pb alloys 240.1 Ta/Au alloys 214.3 Heat resisting alloys - High-purity Cu 214.3 High-purity Cu Uranium Ores and slags Geological materials U Ores and slags High purity Mo - E, P, ICP, L 0.25-25 pg/g A, ETA, L A, F, N,O/C, H,, L Trace levels A, ETA, L - E, P, ICP, L ~ A, F, N, O/C, H, , L E - - , > Dissolve sample in 25% NaOH; HC1 added to keep metal salts in solution For flame AAS dissolve 0.5 g sample in 20 ml HC1 + 2 ml H, BF, then add 10 ml5% LaC1, and dilute to 100 ml. For nameless AAS dissolve sample in HC1 (1 :1) and dilute as necessary.Either method improved by extracting Ti into a 12% solution of diantipyrinylmethane in CHCI, in the presence of NH, SCN Dissolve A1 alloys in NaOH + H, 0 and steels in HNO, + HCI A review with 23 refs.Cu, Ni, Se, Cu alloys: digest with H,SO,/HCI/HNO,, extract into trioctylmethylammonium chloride (TOMACI) in butyl acetate. Al: dissolve in NaOH then boil in HCI/H, SO, /H, 0, and extract in TOMACI. Pb and Pb alloys: digest with HNO, then HCl/H, SO,; separate supernatant H, SO,, then TOMACl extraction See Ni, ref. 323 Sample dissolved in HCI/HF/H, 0, and Te separated by co-precipitation with As, phosphinic acid added as reducing agent, precipitate dissolved in HNO, Cu dissolved in conc.HNO, and evaporated to dryness, re- dissolve in 6M HCI followed by addition of 15M NH,OH, Cu separated by passing through Chelex-100 resin See Se, ref. 2282 Th separated from U with tri-n- octylamine in xylene (pre-equilibrated with 6M HCI) See Mo, ref. 934 T1 is extracted from 0.5 M HBr solution into iso-Bu COMe See Pb, ref. 546 See Mo, Ref. 934 Sample reduced with hydrogen and then gaseous iodine (Mo:I ratio of 1:l) for 20-30 h 1209 1712 1872 2038 394 323 334 416 2282 818 934 900 546 934 703b W Ni alloys E: 6’ Sample dissolved in HCI/HNO, and tungstic acid precipitated with a solution containing a mixture of cinchonine and antipyrene, precipitate separated and dissolved in aqueous HF at 120°C in a Teflon bomb See Cr, ref.C109 c109 979 GI Zn Protective coatings A, -, L E, P, ICP, L E, GDL, S A, ETA, S Zn Zn 481.1 213.9 307.6 - Cu alloys Ni alloys See Cu, ref. 876 See Cd, ref. 1600 876 1600 - 0-26 rgig Zr Bauxite, Al Ground bauxite fused with Na,CO, /H, BO,, metals dissolved by H,SO,/HCI, Zr separated by precipitation with NH, at pH5, hydroxides are dissolved in HCI and drops of the 587 solution applied to 5 mm disc of filter paper on a graphite electrode Application to major and trace analysis (Al, Fe, Mo, V, Y) Various (5 ) Ti alloys Cr-Ni steels, Ti A1 alloys High-purity Cu E, P, ICP, L E, P, ICP, L E, S , S E, S, S c 7 c 9 C29 C3 2 C36 C4 1 C42 C114 C149 c222 C231 Various Use of hot phosphoric acid (without HF) to dissolve refractory element prior to ICP analysis Use of synchronous timegated integration to improve signal-to-noise ratio and spectral interferences Application of ECWS (electronically controlled waveform spark) source to trace analysis in high-purity metals; comparative results with d.c.arc for high purity Cu analysis Importance of selection of internal standard spectral lines Application of ICP-OES following vaporization by SSEA (separate sampling and excitation analysis) See Various C41 Deposition of sample on a hot microboat as an aerosol mist; reduction in interference effects claimed (Bi, Pb, Te, T1) Application of ICP-OES following fire assay procedures (Ag, Au, Pd, Pt) Application of SSEA to Ni alloys eliminates dissolution problems using HF Application to determination of rare earth elements (up to 30% by weight) Various Various Trace levels Various Various A1 bronze, monel Al-, Zn-, Mgalloys - E, S, S 0-100% E, P, ICP, C 0-100% E, P, ICP, G - A, ETA, L Various Various Cu, bronze, brass Ni alloys Various (4) Various Precious metals Trace levels E, P, ICP, L E, P, ICP, G E, P, ICP, L - Ni alloys Ni-, Fe-Ti-alloys Ni and Fe alloys Various Various - E, P, ICP, L Flexibility of ICP-OES system for application in R & D Centre.C234 Ultra-trace levels A, ETA, S Application of direct atomization of solid samples and C291 (Deals also with metallurgical and environmental samples) Various Ni alloys E, hollow cathode, S AAS and hollow cathode ES to ultra-trace anaiysis (< 1 @gig) in Ni alloys (Ag, Bi, Cd, In Sb, Se, Te, TI, Zn) - L AVarious (7) Various (7) Various (8) Various (6) E, P, ICP, L E, A, Ax., S E, P, ICP, L A, -.L Table 4.28 NON-FERROUS METALS-continued Technique, Atomization, Element h/nm Matrix Concentration Analyte Form Sample Treatment Ref. Various - Na coolant Trace levels E, P, ICP, L Vacuum distilation of 8 g Na from a dip sample provides a C298 Various - Precious metals - E, P, D.c., L Application of d.c.plasma/echelle spectrometer system to a C315 nitrate solution containing non-volatile impurities which emits < 10 nCi a wide range of precious metal process liquors and effluents addition methods (Cr, Cu, Fe, Mg, Mn, Ni, Si) H, 0, filter and dilute to suitable volume to give 1% absorption; Si determined by dissolving sample in NaOH or KOH solution with H, 0, added to oxidize Si, solution treated with HCI and HNO, (Cr, Cu, Fe, Mg, Mn, Ni, Si, Ti, V, zn) products (Al, Cr, Fe, Na, Ni, Ti, V) Conversion to Al, 0, prior to a.c.arc excitation (B, Cu, Fe, Mg, Mn, Si, Ti) 0.1 g sample dissolved in HNOJHF. HF neutralized with boric acid (Al, Fe, Mn, Mo, Si, Sn, V, 21) 2 ml of a 2 mg/ml NiCI, solution, oxidize the reduced Ni with HNO, solution and dilute to 100 ml with H, 0, add S M NaOH solution and filter, dissolve precipitate (Cr, Cu, Fe, Mg, Mn, Zn) Various High-purity Al Trace levels A, F, AU/C, H, , Interference effects studied, also brief reference to C367 (7 ) (101 N, O/C, H, , L Various - A1 alloys - A, -, L Dissolve 0.5 g Al alloy in 2 ml HNO, , 5 ml HCI and 10 ml 368 Corrosion products Trace levels Study of N/Ar and Ar/Ar plamas for analysis of corrosion 369 Aluminium 0.025 - 1 % 373 Ti alloys 397 High-purity Al Trace levels Co-precipitate with nickel hydroxide after acid digestion, add 465 Various Cu alloys E, P, ICP, C Vaporization by lowenergy YAG: Nd laser, vapour carried 471 Various Fe-Nb alloy Trace levels E, -, s Finely divided alloy sample (200mesh) mixed (7:l) with 490 (4) into plasma (Cr, Cu, Mg, Ni) % (5) NH,H,PO,-NaC1-graphite ( 4 : l : l ) carrier (As, Bi, Pb, $ i? $ B Sb, Sn) - Various Non-ferrous A, -, ~ Review of AAS, AES, AFS, optical emission and XRF 496 Various Al, A1 alloys E, s, s Study of optimum conditions for determining elements 517 (6 ) Various Process liquids, Trace levels E, P, ICP, L Application of ICP-OES to process intermediate, solid 521 (8) solid wastes $ alloys E, -.- spectrometry for non-ferrous alloy analysis in high-purity Al and B-95 alloy (Cr, Cu, Fe, Mg, Mn, Si) E. 2 waste and aqueous solution analysis containing noble metals (Ag, Au, 11, Os, Pd, Pt, Rh, Ru) 0 13 t:Various High-purity Ga Various - CU (6 ) Various A1 alloys, brass - Various High-purity Ga and A1 Trace levels Various Various (4) Various Various - (9) Various - Various - (6 ) Various (8) Various (9) Various (15) Rareearth materials - Cr-Ni steel, Mg- - and Al-alloys High-purity Al, - stainless steel Al, A1 alloys - Steels, alloys Cast iron, Cu alloys - Co and Fe alloys Ni alloys A1 Trace levels E, P, ICP, G A, ETA, I.A, -, - E, -. - E, S, S E, S, S A, ETA, S E, GDL, S A , F, L E, P, ICP, L Comparison of excitation-spectrography, extraction- AAS, SSMS, NAA in terms of number of determinable elements, limits of detection and cost factors Use of micro-spectral analyser, replacing one electrode with the sample (Al, Fe, Mn, Pb, Si, Sn) Laser vaporization of solid and powdered samples (ruby laser) and introduction of vapour into shielded plasma chamber.Analysis of Ga: 2 g sample dissolved in 20 ml of 6 M HCI with gradual addition of 4 ml of 14 M HNO, and gentle heating, concentrate and make up to 100 ml with water adjusting pH to 1.5 -1.8 with NH, ;ammonium salt of diethyl phosphorodithionate used to form stable complexes. Analysis of Al: 1-2 g sample dissolved in 50 ml of 6 M HCI evaporate to dryness and dissolve in 150 ml of water, then as for Ga (Bi, Cd, Cu, In, Pb, TI) Comparison of AAS, XRF, NAA, vacuum extraction (for C, N and 0) and U.V.and visible spectroscopy for rare- earth metal based samples Dissolve 1 g of sample in HCI, add lOOpg Y or Yb, evaporate to syrup, dilute to 50 ml with H, 0, add ascorbic acid to reduce Fe, adjust pH to 1.52 with HCI; diantipyrinylmethane (1.5 g) and KI (5 g) added and lanthanoids extracted into CHCI, (6 ml); discard aqueous layer and CHCI, layer is shaken for 1 min with 9 ml benzene; lanthanoids in the lowest of three layers determined spectrographically (Ce, La, Nd, Sm) Study of memory effects in metal analysis Examination of best a.c.excitation conditions (Cr, Cu, Fe, Mg, Mn, Ni, Si, Ti, Zn) Examination of direct atomization of solid samples of steel, alloys and slags, cinders, scrap, etc., to determine volatile elements.Enhancement of GDL emission with 136.2 MHz secondary inductively coupled r.f. excitation (C, Mn, Pb, Si, Sn, Zn) Use of AAS to analyse alloys used in surgical materials (Cr, Cu, Fe, Mn, Ma, Ni, Ti, W) Dissolve 0.2 g in 40 ml nquu regiu and dilute in 20 ml HCI; larger sample, 0.5 -2 g, required to determine Al, Ma, Zr (Ag, Al, Co, Cr, Cu, Fe, Mn, Ma, 21) Comparison of AAS and ICP-OES indicating theii respective advantages 536 543 550 511 511 584 625 64 I 648 698 122 125 750Table 4.28 NON-FERROUS METALS-continued Technique, Atomization, Element h/nm Matrix Concentration Analyte Form Sample Treatment Ref.Various (12) Various Various Various Various (7 ) Various Various Various (11) Various (6 ) Various (8) Various Various (21) Various (4) Various Trans-plutonium and rare earth metals Noble metals Si single crystals High-purity A1 Cu, low alloy steel - High-purity Ga Alloys, - High purity In - Sn High purity Cd Cu alloys, Al alloys, steels - High-purity In and Ga High-purity U High-purity A1 Trace levels Trace levels Trace levels Trace levels Trace levels Trace levels 0-0.05% Trace levels Trace levels Trace levels Trace levels E, -, - A, -.- E, Laser, S A, -, - E, -, - E, Laser, S A, -, L E, -, S A, -, - E, A, Ax., S E, A, A.c., S A, F, L E, Laser, S A, ETA, L A, ETA, L E, P, ICP, L E, P, D.c., L Direct spectral analysis of impurities 75 1 Book on the AA analysis of noble metals Laser ablation and resonance ionization spectrometry applied to solids Review with 7 3 references comparing AAS, AES, SSMS; sample preparation techniques also discussed Laser step-wise excitation and laserenhanced ionization demonstrated for 7 elements Comparison of extraction - ES, extraction - AAS, NAA and SSMS for multielement analysis Determination of main components in samples by AAS and NAA improved by various techniques, e.g., using flux correction factors.Deals also with nonmetallic inclusions and internietallic compounds. 10 mm diam. rod of In prepared by melting In in glycerine and moulding with a fluoropolymer mould; used as lower electrode with C upper electrode and interrupted a x . arc (220 V, 7.5 A) (Al, As, Cd, Cu, Fe, Mg, Pb, Si, Sn T1, Zn) lOmm diam.rod used as the lower electrode, C as the upper electrode; excitation by interrupted a x . arc (As, Bi, Cu, Fe, Pb, Sb) Pre-concentrate trace metals on a mixed collector of Cd S , MnO, and a-benzil dioxine (Ag, Bi, Cr, Cu, Fe, In, Ni, Pb) Application of laser induced breakdown spectroscopy (LIBS) and time-resolved LIBS; intense laser beam produces atomic emission Matrix removal by extraction with Chlorex from 11 M Dissolve U in cone.HNO,; adjust solution to 3 M HNO, and extract U with dioctyl sulfoxide into xylene, analyse aqueous phase by graphite furnace ETA (Cd, Co, Cu, Ni) Analysis of high salt contents with echelle spectrometer and ICP and DCP 75 2 779 867 880 882 982 1096 1097 1099 1151 k 5 HCI and 8M HBr 8. s. 1155 2. $ 1161 C1234 r, f 5Various - (4) Various (15) Various (8 ) Various - (9) Various Various - (4) Various Various Various Various Various Various - (4) Various (4) Various (6 ) Various (11) Various - (14) Rareearth alloys Ni-Cr alloys, precious metals Mg metal Na (nuclear grade) High-purity metals Precious metal scrap Precious metals Precious metals Au Precious metal sweeps Ni alloys Al, A1 alloys High-purity Sn High purity Pb Nuclear materials ~~ Trace levels Trace levels - - - - - Trace levels - Trace levels Trace levels I'race levels Trace levels - E, P, ICP, L E, P, ICP, L A, -, - A, ETA, L A, F, L E, P, L E, P, ICP, L E, P, L A, -, - A, -, L A, -, S E, P, ICP, L E, P, D.c., L A, ETA, S E, A, L E, A, A.c., S E, P, ICP, L E, P, ICP, L Selection of optimum conditions for analysis of rareearth elements with high melting points (Mo, Nb, Ta, Re) Analysis of precious metal in scrap, sludges and low grade ores and analysis of Ni-Cr alloy by ICP Preconcentration of Mg metal and nitrate with activated carbon as collector (Ag, Cu, Fe, Hg, In, Mn, Pb, Zn) Na distilled off in Ta or Al, 0, crucibles, residue dissolved in dilute acid (Ca, Co, Cr, Cu, K, Li, Mg, Mn, Pb) Comparison of AAS and SSMS; typical results given Analysis by echelle grating plasma spectrometer compared with fire assay methods (Ag, Au, Pd, Pt) Optimization of conditions, up to 10% solid content analysed, comparison with fire assay methods Study of factors affecting performance of plasma emission analysis Assessment of AAS applied to Au analysis, particularly direct analysis of solids Analysis of a range of Ag process and product materials; dissolution in HNO, , dilute to give 6% Ag content Na, 0, fusion followed by acid dissolution in HCI; separation stages also discussed Direct analysis of solids; comparative results with induction furnace atomization and hydride generation suggest ETA to be more sensitive Dissolution in NaOH then internal standard (Tm) and Fe added and solution boiled; after standing, supernatant liquid discarded, redissolve precipitate in NaOH + H, 0, + HCI solution, apply to strong cationexchange resin and following elution of extraneous metals, elements of interest eluted with 4.8 N HCI, solution spotted on treated graphite electrode and spectrum excited (220V, 12 A) 10 mm rod of sample as lower electrode, C counter - electrode; excitation by interrupted a.c.arc (220V, 6.5 A) (As, Bi, Cu, Fc, Pb, Sb) Survey of ICP methods (Ag, As, Bi, Cu, Fe, Sb, Se, Sn, Te, T1, Zn) Review of application of ICP in atomic energy C1299 9 6' C1331 1 1402 1409 1410 C1418 C1419 C1420 C1421 C1422 C1423 1558 1618 1637 1669 C1682Table 4.2B NON-FERROUS METALS-continued Technique, Atomization, Element h/nm Matrix Concentration Analyte Form Sample Treatment Ref. Various (1 8) Various (4) Various (14) Various Various (5 ) Various Various (14) Various (4) Various Various (7 1 Various (4) Various (9) Various (4) High-purity Zn - Cu-Mn alloys - Ni-alloys, heat resisting steels - Metal castings Na metal Gold plating - High-purity Rh Ni alloys Brasses, bronzes In metal - Bronze - Electroplated Cu alloys Ni alloys Trace levels 0-4% ~ - Trace levels - Trace levels Trace levels - Trace levels - Trace levels Trace levels E, A, D.c., S A, F, Air/C,H,, L E, s, s E, S, S A, ETA, L E, P, D.c., L E, A, D.c., S A, ETA, - E, A, D.c., L E, A, A.c., S A, F, ~ A, -, - A, ETA, L Convert to Zn 0 by dissolution in HNO, , evaporate and sinter at 500°C; BaF, used as carrier; d.c. arc excitation (250 V, 10 A) Application of flame AAS (Fe, Ni, Pb, Zn) Fixed time integration; separate curves for 9-60 and 60-76% Ni contents Automatic (computer-controlled)re-calibration procedure Method avoiding distillation step in order to analyse volatile elements (Co, Cr, Cu, Mn, Pb) Determination of Au and metallic impurities in plating baths and plated parts; comparison with fire assay and AAS Examination of buffer ratio and excitation parameters; d.c. arc: 10 A and 20 A, 1 :1 Ar-0 atmosphere Use of microboat within graphite cuvette (Bi, Pb, Te, TI) Study of porosity of graphite electrodes and its effect on solution-residue techniques in d.c. arc analysis See Various ref. 1096 Study of factors affecting precision of results Dissolution of Pd layer on Cu-alloys with dilute HNO, (3:l) and control of conditions (Ag, Cd, Co, Cu, Cr, Fe, Ni, Pb, Zn) Deposition of sample as aerosol mist on microboat in furnace cuvette (Bi, Pb, Te, TI) 1750 1751 1864 1874 1929 2003 2044 C2134 C2147 2225 C2365 C2426

ISSN:0306-1353    

DOI:10.1039/AA9821200138

出版商:RSC    

年代:1982

数据来源: RSC

摘要:

Applications 157 4.3 REFRACTORIES AND METAL OXIDES, CERAMICS, SLAGS, CEMENTS The majority of papers published i n t h i s applications f i e l d concerned the analysis of metal oxides. appeared t h i s year. indicating t h a t existing methodology can be used t o solve the majority of anal- y t i c a l problems. I t i s i n t e r e s t i n g t o note t h a t many methods have been published on the use of the DCP.has commanded most attention. Few papers on the analysis of ceramics and glasses have Very l i t t l e new material has been published, possibly This trend contrasts with previous years where the ICP Overall , the majority o f papers reported the use of FAAS despite the wealth of previous publications. metal oxide analysis, while f o r ceramics, glasses and cements, the preference was f o r FAAS techniques.In general , emission techniques were favoured f o r 4.3.1 Refractories and Cements A comprehensive report on the analysis of cements by ICP-OES was published by Degre (1312). Information contained i n t h i s publication includes standard preparation, sample dissolution and instrument conditions f o r a l l materials encountered i n the cement industry (& cement, unfired clay, limestone, p y r i t e , ashes, slag, dusts and bricks).cements was presented by Falinower (C1288). The analytical techniques discussed included colorimetry, XRF, AAS and ICP-OES. Shishkina e t a l . (692) determined S r in portland cement clinkers by FAAS using a fuel rich air/C2H2 flame. refractory carbides, was reported by Comtois and Kinsey (C33).ground t o reduce p a r t i c l e s i z e and introduced i n t o the DCP as a suspension. Accurate r e s u l t s were obtained f o r CRMs; however, f u r t h e r research was deemed necessary t o improve the precision. A comparison of techniques f o r the analysis of An i n t e r e s t i n g use of a DCP, f o r the determination of various elements in The samples were 4.3.2 Metal Oxides A s i g n i f i c a n t proportion of the papers published on the analysis of metal oxides reported the use of ICP-OES.The determination o f fourteen rare-earth elements i n h i g h purity yttrium oxide was reported by Nai-xiang e t a l . (C152). samples were dissolved i n GM HC1, and detection l i m i t s f o r most elements were in the 0.3 t o 3.0 ppm range.method was superior, i n many respects, t o a c l a s s i c a l d.c. a r c powder method. A similar method was evaluated by Japanese workers (2041). applied t o the determination of Hf and Zr i n zircon (384). The samples were fused with LiB02 and the melt dissolved i n 2M HN03. W i t h use of a high s o l i d s crossflow nebulizer, 2% m/V LiB02 could be aspirated f o r u p t o 3 h without the nebulizer clogging.Hf i n zirconium oxide. The The experimental r e s u l t s indicated t h a t the proposed The ICP was a l s o I s h i i and Satoh (324) reported the ICP-OES determination of Samples were dissolved by heating w i t h (NH4),S04 and158 Analytical Atomic Spectroscopy H2S04 u n t i l d i s s o l u t i o n was completed. d i l u t e H2S04.A detection l i m i t o f 0.06 ug m l ” was reported. -- e t a l . (998) reported the determination o f seventeen t r a c e element i m p u r i t i e s i n high p u r i t y lanthanum oxide. 850 OC f o r 1 h and then mixed w i t h an equal amount o f graphite. was taken f o r analysis. The samples were d i l u t e d 1 + 19 w i t h The d.c. a r c i s s t i l l widely used i n the f i e l d o f metal oxide analysis.Yeh Samples were i g n i t e d i n a muffle furnace a t A 10 mg sample Additional references on t h e preceeding t o p i c - 631 , 1748, 932. The analysis o f aluminium-containing materials i s a subject which s t i l l receives considerable a t t e n t i o n . Markova e t a l . (1050) used a d.c. arc t o deter- mine V i n alumina. The samples were mixed 1 + 1 w i t h a b u f f e r containing 11.2% BaO and 0.1% LuO ( i n t e r n a l standard) i n powdered graphite.The range covered was 0.0001 t o 0.05% V. Other Russian workers determined L i i n aluminium containing intermediate products (1711). The RSD was 5.0% f o r L i concentrations between 0.03 and 1 .O%. The determination o f K and Na i n pure alumina was reported by Choi and Koo (1928) while the determination o f P r and Sn i n an aluminium/zinc spinel was described by Shchanikova e t a l .(1156). 4.3.3 Ceramics and Glasses The determination o f t r a c e elements i n glasses, using a s o l i d sampling technique and ETA-AAS, was reported by Headridge and Riddington (C63). (0.2-10 mg glass chips) were prewashed w i t h CC14 followed by d i l u t e HN03 and inserted i n t o the graphite furnace.Calibration curves were obtained f o r Ag, C r y Fey Mn, Pb, Sb, T1 and Zn using standard glasses. For many samples a RSD o f 10% was achieved. o f Cu, Fey K, Na and Pb i n m i l l i g r a m amounts o f lead glasses (473). were digested i n a capped PTFE vessel w i t h a mixture o f HN03/HC1/HF/HC104 ( 1 : l : l : l ) . o f 20, 50 o r 100 p1 were i n j e c t e d i n t o the spray chamber v i a the a l i q u o t sampling device.recorded on a f a s t response c h a r t recorder. the sample s i z e was l i m i t e d o r when the sample s o l u t i o n was high i n dissolved s o l i d s . The samples The technique o f d i s c r e t e sample nebulization was applied t o the determination The samples Aliquots The mixture was evaporated and redissolved i n 3 m l o f H20.The AA signals were measured by a d i g i t a l i n t e g r a t o r and also This method was preferred only when I n the past year, only a few papers have appeared on the analysis o f glasses and ceramics by inductively-coupled plasma-OES. described a method f o r t h e r a p i d determination o f the components o f glasses and glass raw m a t e r i a l s , while Pyzik (C2148) reported the sample preparation required f o r the determination o f the major elements i n glasses. A more t r a d i t i o n a l spectrographic method was used by Volke and Peter (764) f o r the analysis o f s i l i c o n dioxide c a r r i e r s f o r glass production.Slotova and Dragunova (1895)Applications 159 Atomic absorption spectroscopy has been used t o provide elemental analysis A review of the tech- S t a t i s t i c a l evaluation o f of ceramics of archaeological i n t e r e s t f o r many years.nique was published by Wernisch and Groeger (609). the r e s u l t s from d i f f e r e n t samples helped t o e s t a b l i s h a correlation between the ceramics and the p a r t i c u l a r geological clay s i t e s of origin.by Yasuda e t a l . (2022) showed t h a t a green glaze from an excavated t i l e contained 49% PbO and 2.1% CuO. The techniques of XRF, flame photometry and FAAS were used t o determine Ca, Fe, K , Mg and Na i n an archaeometrical study of Roman bricks (912). of social and economic conditions when the bricks were made. A separate study The r e s u l t s obtained could be used t o indicate the s t a t e A recent publication (ARAAS, 1981, 11, Ref. 1385) described the analysis of Coy Cry C u , Fey Mn and Ni i n optical waveguide materials. A review on this subject was published by Mitchell (1407). Analytical techniques discussed included AAS, AFS and OES.Table 4.3 REFRACTORIFS AND METAL OXIDES, CERAMICS, SLAGS, CEMENTS Technique, Atomization, Concentration Analyte Form Element hfnm Matrix Sample Treatment Ref.C2408 493 886 - Glass Dissolve in HF/HNO, and complex with NH, Ag A1 257.5 TiO, - Conversion of quartz spectrometer t o direct reading spectrometer Ca - y, 0 3 Trace levels A, F, Air/C, H, , L Study of the effect of organic acids and alcohols on AA analysis, effect of AcOH, MeCH,CO,H, MeOH, EtOH, BuOH and iso-Pr OH studied Ca Ceramics E, P, L Study of the effects of Al, Ti, Zr and alkali on the flame photometric determination of Ca in both HCl and H,SO, media 959 Ce Trace levels E, A, D.c., ~ Separation by extraction chromatography using N,,, supported on silane-treated silica beads as the stationary phase; column eluted with a solution (pH 1.90) containing lo-’ M diethylenetriaminepenta-acetic acid and 7 M NH, NO, t o elute Nd, 0, ; Ce then separated (with La and PI) by eluting with 2 M NH, NO, 1748 Cr c u DY ZnO Archaeological sample - y, 0, A, -.- A, -, - E, Electron, S Decomposition of ZnO by fusion with K, S, 0, for AAS Analysis of green glaze of tile excavated in Keong-ju, Korea Application of electron excitation emission spectrometry (15 kV) Dissolve 0.3 t o 0.5 g of sample in 8 ml of ( 1 : I ) HCI, evaporate t o 2 ml and make up t o 25 ml with H, 0; an aliquot is mixed with a suitable volume of K-Y inhibitor solution (3:2) and diluted t o lOml See Al.ref. 493 1970 2022 721 528 573 400.8 Er Yttrium-group metals - Fe Fe 248.8 TiO, NiO-All 0, catalysts E, -. - A, F , Air/C, H, , L 493 987 b Minor levels Sample fused with KHSO, and the flux cake dissolved in HCI; modified double capillary aspiration system used Dissolve sand in tIF/H, SO, acid mixture, fuse insoluble residue with KHSO, or Na, CO, + Na, B, 0, and dissolve product in HCI Dissolve in (NH,), SO, and H, SO, ; dilute with (1 + 19) H, SO, after cooling.Wavelength modulation used Fuse 100 mg of sample with 2 g LiBO, in a Pt dish a t 1000°C for 30 min; pour into 100 ml 2N HNO, , heat t o dissolve, dilute to 100 ml with 2N HNO, ; high solids cross flow mebulizer used Fe Glass sand Trace levels Hf Hf 264.1 277.3 High-purity Zr E, P.ICP, L F , P, ICP, L 3 24 384 z. Zircon 0-1.2%Ha K La Li Mg Mn Na Nb Nd Ni Pb Pb Pr Pt Sb Sn Sr Ta Ta Tb V V Zr 410.4 - 670.4 - 335.8 322 - - 266.0 - 284.0 - 265.7 331.1 543 318.4 357.7 Yttrium-group metals All O3 Ndl '3 Al-bearing materials y2 0 3 Silicates A4 0 3 Carbon, SiO, Garnets NiO-AI, 0, catalysts Archaeological sample Glass, glazed ceramics Ndl03 Al-Zn spinel ZnO Al-Zn spinel Cement clinker Nb-Ta ore Carbon, SiO, '1 '3 TiO, Zircon - Trace levels Trace levels Trace levels Trace levels Major levels Major levels Trace levels Trace levels 0.1-1.5% 0.2-4.0% Trace levels Trace levels Trace levels 0 0001-0.05% 0-5074 E, A, D.c., - A, r, Air/C,H,, L A, F, Air/C,H, , L F, -, - E, A, D.c., - E, A, D.c., S A, -, - E, A, D.c., S A, F, Air/C, H, , L E, A, D.c., S E, A, D.c., S E, electron, S A, ETA, L E, A, D.c., S E, P, ICP, L See Er.ref. 528 Sample fused with Li, B, 0, at 900°C and the melt dissolved in HCI See Ce, ref. 1748 Sample decomposed by fusion with Na, 0, (if free from F) or with Na, CO, -Na, B,O, (if it contains F), cooled and dissolved in H,O See Ca, Ref. 886 A new additive method requiring only a small range in the concentration/intensity curve. See K, ref. 1928 Solution procedure described See Fe, ref. 987 See Cu, ref. 2022 Comparison of AAS (most accurate method) with colorimetric and ion specific electrode methods See Ce, ref. 1748 Sample mixed with powdered C containing 2%S (1 :9) and excited with 7 A source See Cr, ref. 1970 See Pt, ref. 1156 Acid dissolution Powder samples blown through the arc plasma Samples buffered prior to d.c. arc excitation See Dy, ref. 721 Micro pre-treatment using box incorporating three Teflon vessels for decomposition, evaporating vessel, filter holder and five reagent reservoirs Sample mixed (1 : 1 ) with buffer containing 11.2% BaO, 0.1% Lu,O, (internal standard) in powdered C; emission by 12 A d.c.arc See Hf, ref. 384 s 528 -+ 6' 2 1928 1748 1711 886 1988 1928 C2399 C265 987 2022 2025 1748 1156 1970 1156 692 2048 C2399 721 459 1050 384Various Silicates, glasses, cements 0-100% E, P, ICP, G Various (6 ) Refractory metals Various (8) Various (14) Various Various (6) Various (6) Various (5 ) Various Various Various (5 Glass Pure Y, 0, Geochemical, materials TiO, Garnet films Lead glass Archaeological ceramics Trace levels Trace levels Trace and major levels Trace levels Trace levels Trace levels Trace levels A, F, N, OIC, H, , L A, ETA, S E, P, ICP, L E, P, ICP, L E, -, S E, P, ICP, L A, F, Air/C,H,, L A.-, - E, A, S - cn N Table 4.3 REFRACTORIES AND METAL OXIDES, CERAMICS, SLAGS, CEMENTS-continued Technique, Atomization, Element h/nm Matrix Concentration Analyte Form Sample Treatment Ref. Various Refractory carbides - E, P, D.c., L Examination of possible application of d.c. plasma, with its C33 tolerance for high total dissolved and suspended solids, to the analysis of refractory carbides in suspension after pulverizing the matrix with graphite, pressing into a pellet using starch as binder; vapour swept into plasma for analysis Investigation of fuel-rich flame and polarized Zeeman background correction (Al, Co, Cr, Fe, Mo, Si) Direct atomization from solid samples using induction furnace (Ag, Cr, Fe, Mg, Pb, Sb, TI, Znj Sample dissolved in 6N HCI prior to determination of 14 rare-earth elements Review of advantages of ICP in its application to geochemical, chemical, environmental and biological analysis Mix 300-400 mg of sample with C powder (1:l) and transfer into boat type electrode; scan electrode at 0.5-0.6 mm/s (Co, Cr, Cu, Mn, Ni, Sn) Dissolution in H, PO, in a Pt crucible; Zn used as internal standard to correct interference effects (Ca, Fe, Ge, Lu, Acid dissolution in HNO, /HCl/HF or HNO, /HCl/HF/HClO, mixtures;an aliquot of 20-10Opl is nebulized into the flame uiu a capillary to the nebulizer (Cu, Fe, K, Na, Pb) Review of AAS application to ceramics of archaeological interest and relation between these and geological clay sites KCI and CsCI; rareearth elements determined after fractional distillation using Ar-0 d.c. arc dissolve in 150 ml H, 0 and solution passed through P,,, earth elements, precipitate with oxalic acid, dry and sinter at 850°C to form oxides; determine using d.c.arc source (Ce, La, PI, Sm, Y) Spark vaporization of sample after mixing and grinding C43 cs 9 C6 3 C152 C235 409 458 Sm, Y) 473 $ ; g ? 609 Mix sample with spectral buffer containing C powder, PVC 630 % Dissolve I .5 g sample in 10 ml HCI, evaporate to dryness, silica gel chromatography column; elute and extract rare- 631 3 hb b b = Various (8) Various Various Various Various (8) Various (12) Various (5 ) Various Various (17) Various ( 6 ) Various Various (5 ) Piezo electric ceramics Glass Synthetic matrices '41, 0, Silicates Ga and Gal 0, Archeological samples MnO, Scanduim oxide Yttrium oxide '2 '3 Lead glass Trace levels Trace levels Trace levels Trace levels - Trace levels - Trace levels Trace levels Trace levels A, F.L E, A, S E, F, - A, -, - A, -, L E, P, ICP, L E, A, D.c., S E, -, S A, -. A, F, Air/C, H, , L Samples decomposed using HBr containing HF or NH, BF, ; interference in determination of Cr and Zr suppressed by addition of KHSO, and NH,HF, , respectively; air/C, H, and N,O/C,H, flames used (Bi, Cd, Cr, Mn, Pb, Ti, Zn, Zr) Mix sample withgraphite (1:l) and excite using d.c.arc source; sub-ppm amounts also determined by AAS Use of time-resolved spectrography with modified a.c. arc excitation Optimization of 13.5 A a.c. source electrical parameters Dissolve 50-200 mg of sample under pressure with 0.5-1.5 aqua regia in Teflon autoclave; treat with 3 ml48% HF at 120-140°C for 40 min; cool, add 2.8 g H, BO, and dilute with H, 0 to 100 ml (Al, Ca, Fe, K, Mg, Na, Ti, Si) Use of d.c.arc source with and without preconcentration using iso-Pr ether Use of flame photometry, atomic absorption and X-ray fluorescence to analyse Roman settlement materials Al, Mo, V and Ti and 9 other trace elements are separated by 2 different techniques, the first involving anion-cation exchange chromatography and adsorption of the oxalate complexes onto the anionic Bio Rad 1 -X8 resin; the second series is adsorbed on Bio Rad AG 50W-8 and elution with HCI Ignite at 850°C to remove moisture and CO, ; mix with an equal amount of graphite and place 10 mg of the mixture in the electrode. 10 A d.c. arc used to excite the mixture and the weak line of La as internal standard Separate Sc by extraction with Bu, PO, from 13 M HNO, ; evaporate the aqueous phase; spectrographic analysis of the concentrate Buffer the sample with a polychloroethylene, CsCI, C powder (5:15:80) mixture and use of Ar/O mixture with a flow rate of 2.5-5.0 l/min for carrier distikdtion(Ce, Eu, La, Nd, PI, Sm) Atomic absorption and energy dispersive X-ray analysis of composition gradients in quenched binaries of molten salts electrolysed between Ag electrodes Dissolve 1 mg of sample in Teflon vessel with a mixture of HNO, , HCI, H F and HCIO, ; 100pJ sample injected ai' Teflon funnel directly into nebulizer (Cu, Fe, K, Na, Pb) 0, Fe, K, Mg, Na) 764 780 825 828 829 912 932 998 1000 1095 1125 1195Table 4.3 REFRACTORIES AND METAL OXIDES, CERAMICS, SLAGS, CEMENTS-continued Element A h Matrix Technique, Atomization, Concentration Analyte Form Sample Treatment Ref.Various Various Various Various ( 6 ) Various (10) Various Various (14) Various Various (1 2) Various Various (19) Various (14) Cements Cements Glass fibres CrZ '3 Glass Glass y203 Glass - Trace levels Trace levels Trace and major levels Trace levels Major levels Trace levels Trace levels Trace levels A, -, - E, P, ICP, - E, P, ICP, L A, -, - E, -,- A, -, - E, -, - A, -, - E, -, - E, P, ICP, L E, P, ICP, L E, P, ICP, L E, A, D.c., S A, ETA, S E, -, - A, F, - E, F, - Comparison of colorimetry, XRF, AA and ICP in the analysis of cements taking into account accuracy, precision and economic factors Dissolve sample in 5% HCl; filter and make up to 500 ml with 5%HCI (the ash residue after calcination must not exceed 0.2%) Review of AAS, AFS and OES in analysis of trace impurities in fibre optics and glass making raw materials Cr separated from high-purity Cr, 0, by volatilization as chromyl chloride (Al, Bi, Co, Cu, Fe, Pb) Study of some interference effects in AA and OES analysis (Ba, Ca, Fe, K, Li, Mg, Mn, Na, Si, and Zn) Application of ICP to the rapid determination of components in glasses and glass raw materials Dissolve 1 g of Y,O, in HCl and make up t o 100 ml; effect of concn.of Y,O, in HCI on line intensities minimized by keeping same concn. in sample and standard solutions (14 rare earth elements) Advantages and disadvantages of fusion and mixed acid dissolution techniques; results of the analysis of glasses and CRMs Optimum conditions for d.c. arc analysis of NH,AI(SO,), * 12 H,O and A1,0, as a stage in the production of white sapphire and neodymium doped yttriumaluminium garnet single crystals; reference also to laser microanalysis of neodymium in the single crystals Use of graphite cuvette with mini platform C2372 Carrier distillation separation C2387 C1288 131 2 1407 1838 1894 1895 204 1 C2148 2240 Dissolve in 6-8N HNO, and extract with tributylphosphate/ benzene C2412

ISSN:0306-1353    

DOI:10.1039/AA9821200157

出版商:RSC    

年代:1982

数据来源: RSC

摘要:

Applications 165 4.4 MINERALS A continuing requirement c l e a r l y e x i s t s f o r sensitive, accurate and r a p i d techniques f o r the analysis o f minerals and energy-re1 ated materi a1 s. considerations and concern over the environmental impact o f the processing o f i n d u s t r i a l raw materials have emphasized the importance o f determining t r a c e constituents. This i s r e f l e c t e d i n the recent l i t e r a t u r e , where procedures y i e l d i n g lower l i m i t s o f detection have received considerable a t t e n t i o n .element techniques, such as plasma emission spectroscopy, are becoming more widely used, while the number o f papers describing applications o f FAES methods continues t o decline, as noted l a s t year. An extensive review devoted t o the atomic spectroscopic analysis o f coal has been published (513) and Ebdon and co-workers (1609, C2301) have described several approaches t o the determination o f t r a c e and v o l a t i l e elements i n the same material using AAS, AFS and ICP-OES.problems caused i n some determinations by the presence o f high and variable concentrations o f matrix elements , c e r t i f i e d reference materials are an important a i d i n assessing a n a l y t i c a l accuracy, both w i t h i n and between laboratories, and i n developing new procedures.zinc ore concentrate standards prepared by the European Economic Community Bureau o f Reference have been reported (510), as have major and t r a c e element data f o r Egyptian (848) and Japanese (931 ) rock standards. The 1 i m i t a t i o n s o f pub1 i shed t r a c e element values f o r standard rocks were discussed by Date (512) and a l t e r - native synthetic standards prepared from s i l i c a t e gels proposed.Reference materials are also h e l p f u l i n the r e a l i s t i c evaluation o f sample treatment procedures and have been used t o compare the effectiveness o f concentrated HN03, 1M HN03, 3M HC1 and H202/ascorbic acid as leaching agents f o r the determination o f Coy Cu, Pb, N i and Zn i n geological materials (1628), and t o assess a s i m p l i - f i e d separation scheme f o r the determination o f La and Sc i n s i l i c a t e rocks and coal by AAS (1925).Incomplete recovery o f C r from a US National Bureau o f Standards SRM o f urban p a r t i c u l a t e matter treated w i t h aqua regia/HF/H3B03 was reported ( 1636).Economic Mu1 ti- P a r t l y because o f the i n t r i n s i c heterogeneity o f geological samples and the Data on the Cd, Cu, F, Fey Hg and Mn content o f 4.4.1 Atomic Emission Methods - Arc and Flame Sources Oriental and Eastern European papers account f o r over 85% o f the recent l i t e r a t u r e on the applications o f arc emission spectrometry t o mineral analysis, most o f which i s concerned w i t h establishing s u i t a b l e conditions f o r the determination o f 2-10 elements.year. Very few papers dealing w i t h FAES methods were published t h i s -- Matrix effects i n the spectrographic determination o f B y Bay Be, Co, C r y Cu,Analytical Atomic Spectroscopy 166 Ga , r a t ana CaO Mn, Ni, Pb and Zn i n sedimentary rocks and coal ash containing high concent- ons of calcium were studied by Laktionova e t a l .(2049), who reported t h a t yte l i n e i n t e n s i t i e s decreased proportionally w i t h the increase i n the Si02 r a t i o . Simplex l a t t i c e experimental design showed addition of 20% of a buffer containing NaF, S and Si02 (1:2:7) gave the best r e s u l t s f o r the determination of As, Cd, Coy Gay Ge, In, Ni, Sb and Te i n sintered zinc ore (1917).and a 1 ppm l i m i t of detection f o r Hg i n iron ores by adding 1 t o 250 mg of sample excited i n a cavity i n an iron electrode f i t t e d w i t h a bored graphite cap. may be used t o improve precision i n the spectrographic analysis of minerals.Barakat e t a l . (578) preconcentrated Nb and Zr by precipitation from ore solutions onto carbon powder t o which Mo had been added as an internal standard. l i n e s were used i n the determination of Sc and Y i n s i l i c a t e rocks ( 8 2 7 ) , B and W in minerals (937) and Cu, Gay Ge, In, Ni and V i n coals and kerogens (1328). Jiang (1655) added 2% each of Sn02 and Bi(N03)3.5H20 as internal standards f o r the determination of Gay Ge and T1 and f o r In, respectively.Vcirathe e t a l . (1702) used the Si 297.03 nm l i n e , the i n t e n s i t y of which i s influenced by two adjacent Fe l i n e s , f o r the spectrographic determination of trace elements i n rocks. The d i r e c t spectrographic analysis of powders was reported by Prokopchuk et - a l .(597), who determined Au in geological standards by introducing f i n e l y ground samples ( < 0.07 mm) i n t o a d.c. a r c via a stream of a i r and achieved a 5-10 ppm l i m i t of detection. Rusanov and co-workers (509, 881, C1296) claimed t h a t inter-element e f f e c t s were eliminated i n the determination of Hf, Nb, Ta, Th and Zr when powdered samples ( < 10 pm), mixed 1:l w i t h graphite powder, were swept by a stream of Ar into a 130 V, 100 A dual-stream a r c plasmatron. film vaporization was used by Sacks and Goldberg (C2082, 2230) t o determine Cd, Cry Mn, Ni, Pb, S r , V and Zn i n 20-30 pm s i z e p a r t i c l e s ; detection l i m i t s were i n the range O.tL2.2 ng.Pruvcheva e t a l .(494) obtained increased l i n e i n t e n s i t y a t 253.52 nm Internal standardization, w i t h o r without the addition o f spectroscopic buffers , Palladium T h i n 4.4.2 Atomic Emission Methods - Plasma Sources Plasma emission spectrometry i s now widely used in routine geochemical analysis where i t s multi-element capability, r e l a t i v e l y good precision and speed of measurement make i t a powerful and cost-effective technique , especially f o r mineral exploration samples (C148).In p a r t i c u l a r i t i s the inductively coupled, rather than the DCP o r microwave plasma, which i s most commonly employed, and typically 20-30 elements are determined. rapidly, sample preparation often becomes the rate-determining s t e p in the over- a l l analytical procedure and r i g h t l y continues t o receive a t t e n t i o n .- a l . (C16) determined 43 elements i n meteorites by ICP-OES w i t h ultrasonic nebul- Because ICP-OES permits a large number of elements in solution t o be determined Zhang sApplications 167 i z a t i o n , following dissolution of 0.25 g samples i n 1 ml o f aqua regia and 3 ml o f 48% HF in a sealed PTFE bomb a t 115 OC f o r 6-8 h ; 2.8 g of H3B03 was added l a t e r t o complex excess HF. and stream sediments f o r 30 m i n with 20-25 ml.of oxalic acid, f i l t e r i n g through Whatman 44 paper t o remove the undigested residue.To overcome blockage of the ICP torch caused by the h i g h oxalic acid content of the leachate solutions, 5 ml of 50% H202 were added t o the f i l t r a t e s which were then boiled t o dryness and the residue f i n a l l y dissolved in 20% HC1; a Babington nebulizer was a l s o used t o avoid blockage problems.Geological sample preparation f o r ICP analysis was automated by Borsier and Garcia (C1290). In t h e i r novel instrumentation, weighed amounts of material were homogenized w i t h 3 g of Na202 in crucibles and then passed through a furnace f o r 45 min a t 450 OC.automatically dissolved i n d i s t i l l e d water and HC1 and transferred t o the auto- sampler of an ICP emission spectrometer. point, i n the determination of the r a r e earth elements (REE) by ICP emission spectrometry. derived d i r e c t l y from Na202 or LiB02 fusions and HC104/HF/HN03 attacks (427) o r following preconcentration and separation of REE by ion exchange (C11, C151 , 1753).Interference e f f e c t s , a r i s i n g from the complex nature of geological materials and the h i g h concentrations of major rock-forming elements, can impair the analytical performance of the ICP i f uncorrected. Brenner and co-workers (C154, C2146) quantified the spectral interferences caused by Al, Cay Fe, Mg, Mn, P and T i a t the 500-1000 mg-' level , identifying both background enhancement and l i n e overlap interferences. Thompson and Ramsey (C264) c r i t i c a l l y reviewed conventional physical and computational methods of ICP interference correction and proposed a novel i n t e r a c t i v e matrix matching technique f o r the analysis of calcareous rocks, i n order t o overcome the e f f e c t s of high calcium concentrations. of t r a c e elements i n synthetic fuel samples (C2091) and Sc, Y and REE i n geo- logical matrices (C2455).Descriptions of the application of d i r e c t current and microwave plasmas in geochemical analysis are rare. i n sediments u s i n g a DCP, adding 1% La t o a l l solutions t o overcome signal depression resulting from phosphate, and the enhancement e f f e c t s caused by the a1 kal i metals.Motooka and Sutley (1566) boiled 1 g samples of s o i l The fused p e l l e t s were There i s continuing i n t e r e s t , both from a geochemical and an economic stand- T h i s group of elements has been measured i n solutions either An ICP was used as a detector f o r liquid chromatography i n the determination Bowker and Manheim (1576) determined Ba and Sr Additional references on the preceding topic - 999, C2009, 2168. 4.4.3 Atomic AbsorDtion and Fluorescence Methods The large number of AAS papers published recently t e s t i f i e s t o the continuing168 Analytical Atomic Spectroscopy p o p u l a r i t y and effectiveness o f t h i s technique f o r the analysis o f geological materials.elements. However, Kane and Harnly (1589) described instrumentation consisting o f a Xe arc continuum source and an echelle polychromator equipped f o r wave- length modulation, w i t h which they determined simultaneously Coy Cu, Fey K, Mg, Mn, Nay N i and Zn i n solutions derived from the HC1/HC104/HF digestion o f manganese nodules. Many FAAS papers emphasi ze sample preparation schemes f o r geochemical analysis .Acid digestion under pressure i n a PTFE bomb was used i n the measurement o f Mn i n ores (2280), S i i n rocks (2052), t a r sands and f l y ash (328). Fusion o f 50-100 mg o f f i n e l y ground samples w i t h LiB02 (1:7) a t 900 OC followed by d i s - s o l u t i o n o f the melt w i t h HN03 was used by Verbeek e t a l .(392) i n the determin- a t i o n o f A l , Ba, Ca, Fey Mg, Mn, S i and T i i n rocks and s o i l s . Trace constituents o f t e n require separation from the sample matrix and concentration p r i o r t o analysis. Several schemes have been reported, including: solvent e x t r a c t i o n o f the benzoin a-oxime complex o f Mo i n t o 1,2-dichloroethane from acid digested f l o t a t i o n t a i l i n g s (462); p r e c i p i t a t i o n o f B i from dissolved lead ores w i t h mercaptoacetic acid (326); and coprecipitation w i t h Fe( 111) under a l k a l i n e conditions f o r the determination o f V i n molybdenite (1802).i s the normal mode o f sample i n t r o d u c t i o n i n FAAS, b u t Hicks and co-workers successfully used s l u r r y - i n j e c t i o n f o r the determination o f S i i n coal (958, 1124).ores before they can be determined r e l i a b l y by FAAS; AAS methods f o r Ag and Au has been published (1660). Detection l i m i t s o f 20 ppb f o r Au and Pd were obtained by Yang e t a l . (633) using an octyl-disulphide e x t r a c t i o n system and an a i r l x y l e n e flame. Teliya e t a l .(889) extracted Ag as the cyanide complex by the somewhat hazardous treatment o f 0.2" H2S04 solutions o f i t s ores w i t h 0.2% KCN and 0.01M propyldiantipyrylmethane i n l Y 2 - d i c h l o r - ethane. Adsorption o f Au from aqua r e g i a digests onto p l a s t i c foam and sub- sequent desorption w i t h thiourea was reported by Lo e t a l . (500). As, B i , Ge, Pb, Se, Sn and Te i n geological samples by AAS.Crock and Lichte (673, 674, 2266) described a semi-automatic system, based on AutoAnalyzer parts , w i t h which they obtained detection l i m i t s o f 0.2 ppb f o r As and Sb. ences from Fe and N i , which are known t o 1 i m i t the effectiveness o f the hydride generation technique, were claimed t o be minimized by the a d d i t i o n o f NH20H.HC1/ o x a l i c acid and HC1.Guo and Wang (535) employed an unusual double c a p i l l a r y nebulizer system t o determine B i i n solutions o f rocks and minerals i n d i l u t e HN03. and blended j u s t before e n t r y i n t o an air/C2H2 flame; T y p i c a l l y i t i s employed f o r the sequential determination o f 1-5 Solution a s p i r a t i o n ~~ Precious metals t y p i c a l l y require separation and preconcentration from t h e i r a review o f e x t r a c t i o n - Several papers record the use o f hydride generation i n the determination o f I n t e r f e r - Sample solutions and a 2% KBH4 s o l u t i o n were separately nebulized by a i r interference from Cu wasApplications 169 masked by the addition of thiourea and ascorbic acid.C445) improved s e n s i t i v i t y i n the determination of As and Se in coal by hydride generation-AAS through using high i n t e n s i t y temperature-gradient lamps rather than EDLs. Norris and co-workers (C68, Electrothermal atomization i s often used in the analysis of geological mater- i a l s by AAS, p a r t i c u l a r l y f o r the determination of t r a c e constituents.To a c e r t a i n extent, the greater s e n s i t i v i t y i t o f f e r s must be o f f s e t by i t s sus- c e p t i b i l i t y t o matrix interferences , a1 though improvements i n instrumentation and advances i n knowledge of interference mechanisms have eased the problem. ation from the major components of the sample i s typically required. and Keltsch (1165) achieved t h i s f o r As, B i , Cd, Se and T1 by heating powdered rocks t o 1OOC-1300 OC i n a gas stream (20% H2/80% N2 o r 02) and collecting the analytes on a water-cooled condenser, from which they were recovered with 2% HN03 p r i o r t o determination by ETA-AAS.usually by injection of p1 volumes of solution; however, s l u r r y atomization (1545) was used in the d i r e c t determination of As i n coal where a detection l i m i t of 0.1 pg f u e r s t and Grobecker (554) determined 10 elements i n s o l i d NBS reference mater- i a l s by transferring 1 mg portions i n a graphite boat t o a graphite furnace f o r atomization; Zeeman background correction was used.In studies of inorganic and organo-As compounds from o i l shale processing, a graphite furnace AA system was used as a detector i n HPLC equipment (853).described a f eld-portable AA instrument t h a t has recently become commercially available, in which a tungsten ribbon i s used t o vaporize the sample, and having background co rection by Zeeman modulation. in geochemi cal analysis have appeared recently. Cavall i e t a1 . (385) determined Cd down t o 0.4 pg g-l i n lake sediments by AFS using a c i r c u l a r burner and a separated air/C2H2 flame; continuously aspirated a pure Cd solution a t high concentration.Separ- Heinrichs Sample presentation i n ETA-AAS i s was achieved, using Ni(N03)2 and Mg(N03)2 as ashing aids. Kur- Castledine e t a l . (C279) Very few papers describing the application of atomic fluorescence spectroscopy the excitation source was an Ar ICP i n t o which wasTable 4.4 MINERALS Element hlnm Matrix Technique, Atomization, Concentration Analyte Form Sample Treatment Ref.Ag Ag Ag As As As As As As As Au Au Au Au Au Au Au - 193.7 193.7 197.2 - 193.7 - 193.7 197.2 242.8 267.6 242.8 242.8 267 - Ores Rocks sediments Ores Brown coal ash Geological materials Oil shale retort Coal Coal Geological samples Geological material Geochemical samples Ore Geological samples Geological standards Ores Ores Polymetallic ores 1-200 rg Trace levels rg/g levels 0.5 - 10 ng/g 5 -10 r g / s Trace amounts 0.3 g/ton 6 0 rg/g E, A, -, L E, A, F, L A, F, Air/C, H, , L A, F, Hydride, G A, ETA, G A, ETA, L A, ETA, S E, A, A.c., S A, Hydride, G F, F, Air/C, H, , N, sheathed, L A, -, L A, ETA, L E, A, D.c., S A, I’, L E, A, D.c., S A, F , Alr/C, H, , L Six methods compared Dithizone extraction Extraction with isoamyl alcohol Comparison of performance of temperaturegradient lamps with EDL’s Semi-automated hydride generation after H, SO., /HNO, / HCIO, digestion, pair of 40 ft delay coils used for ASH, reaction t o reach equilibrium Liquid chromatograph coupled with AAS Two methods discussed: (i) dissolving in HNO, -HF-H,O,, (ii) slurry atomization Three methods discussed: (i) Hg with non-oxidative pyrolysis and subsequent cold vapour AFS o n the trapping solution; (ii) hydride generation for As and Se on digested coal, (iii) slurry analysis using ICP t o determine Mn Best results using NaCI-S-quartzmixtures as spectrographic buffer (Bi, Ge, In, Sb, Sn) Samples digested with HNO, /H, SO, /HClO, ; HF also if sample with high Si Non-dispersive atomic fluorescence used and two methods of overcoming scatter described Sinter 40g sample at 6OO0C, boil with 6 0 ml 1:l aqua regia and dilute to 150 ml, add 0.5 g plastic foam, shake 30 min, wash foam, dry and heat with 25 ml 3% thiourea; determine Au in the solution Dissolve 4 g ore (containing up to 32 ng Au) in 20 ml HCI and 1 ml Br, pass the solution through column of 0.2 g mercapte cotton in funnel stem, wash 3 times with 6 M HCI, dry ash at 600°C for 2 h; load the residue into ETA Introduce the sample powder in a stream of air into the source and measure a spectral flash of 0.1-1 rs Octyl disulphide - xylene extraction system Molten bead evaporation technique Extraction chromatographic preconcentration of Au using 0-isopropyl-N-met hylthiocarbamate 370 502 889 C445 674 85 3 1545 1609 2047 2266 c449 500 516 ; fi b 597 3 633Rare and non-ferrous - metals Samples pretreated (to effect activation) in a planetary mill in presence of K persulphate at ratio of sample to metal balls of 1.5-10, sample then dissolved in mixture of HNO, and HCI Fusion with Na, CO, , dissolve water and aspirate into plasma Fusion with Na,CO,, leach with 1:1 HCI, treat with NaCl solution to make final NaCl concentration 2 mg/ml; NaCl suppressed the ionization of Ba Au B Ba 240.8 - Geological materials - Ores 20 r g / m l E, P, ICP, L A, F, N,OIC, H, , L 542 497 Ba Ba Sediments - Rocks, minerals - E, P, D.c., L E, P, S 1576 1777 C2252 The introduction of powders and aerosols into arc plasmas was studied Pulverized samples fused for 30 min at 1050°C in graphite crucible in a K, Co, -Liz B, 0, (1 :9) flux with a 1 :5 sample to flux ratio (0.2g sample), melt dissolved in 4% V / V HNO, solution and diluted to volume Ba Geological samples 50 rg/g-40% Be Bi 313.1 Phosphorites 223.1 Lead concentrates Trace E, A, Ax., - 1.5 -500 r g / g > 1 rgk A, F, AirlC, H, , L A, F, Air/C, H, , G 821 326 Sample dissolved with HCI + HCIO,; Bi precipitated with mercaptoacetic acid 0.5-1.Og sample dissolved in HCI-HNO,.The sample solution and 2% KBH, solution separately nebulized and blended before entry into flame for AAS of Bi as the hydride 223.06 Rocks, minerals 535 Bi Bi Ca Cd Rocks, ores Volcanic rocks Copper ores A, F, L E, P, ICP, - A, -, L Addition of Me,CO increased signal 3-5 fold 986 1071 93 3 - 228.8 Solvent extraction of Cd from buffered solution at pH 11 .O with MlBK Sample, up to 1 g, treated with 1 mlaqua regiu and 7-10 ml of 40% HF at 90°C for up to 4 h, 50 ml saturated solution H, BO, was added and the solution again heated at 90°C for up 4 h, 5 ml 2% KCI added as ionization buffer and solution diluted to lOOml The use of Zeeman effect gave highly reproducible results The interference of Fe, Na and Ni was suppressed by dissolving nitrates of these metals in 5% HNO, and Cd Standard siliceous reference material A, ETA, L 1636 Cd c o Geological samples - Coal ash A, ETA, - A, F, Air/C, H , , L 1714 1850 analysing these solutions in a strongly oxidizing air/C, H, flame Samples were dissolved by fusion with borax and NaOH; interferences were eliminated by using a solution containing tartaric acid, borax and NaCl both with sample and standard solutions 643 Cr Cr ores refractories - A, F, Air/C,H,, LTable 4.4 MINERALS-continued Technique, Atomization, Concentration Analyte Form Sample Treatment Ref.Element h/nm Matrix Micro amounts A, F, Air/C,H,, L 1-2 g sample dissolved in HF, HCIO, and HNO, , fumed and residue dissolved in 5 ml HCI (1 :1) and 20 ml H, 0 (Cd, Co, Ni, Pb, Zn) Four leaching agents, conc.HNO,, 1M HNO,, 3 M HCI and H, 0, -ascorbic acid, were compared; conc. HNO, was considered best The low temp. air/gasoline flame minimizes the interference of other metals Sample treated with a citrate-bicarbonate-dithionite solution followed by a HF-boric acid solution Fe determined in the concentrations obtained as insoluble residues from treatment with HCI and HF Sample, 0.5 g.treated with HF and HCI and Ge isolated as hydride Three types of hydride generator compared Sample mixed with base (1 + 1) prepared from SiO, - alumina-Fe, 0, -MgO-CaCo, (24:6:4:3 :3) by grinding and ignition at 1000 to 1100°C and 2 parts of buffer [ Li, Co, - Zincdust] - SO,-Sb,S,-NaF (3:2:3:l:l)containing26 each of SnO, and Bi(No,), .SH, 0 - 250 mg sample excited in cavity in iron electrode A commercial instrument modified for cold vapour AA Sublimation of Hg at 170-600°C Hg liberated by pyrolysis at 800°C In strongly alkaline media the interfering effects of Au, Pt and Se do not appear.The reaction flask contains 30 ml406 V / V KOH and 2 ml 10% m/V tin (11) chloride solution A special d.c. arc nebulizer is used A high temperature combustion technique is used and the liberated Hg is absorbed in acidified K MnO, solution and determined by cold vapour AAS - 520 1628 646 1962 2050 585 670 1655 C2306 494 629 645 691 1518 1591 1666 1987 989 Cu Minerals Cu - Geological materials Fe Clays Sedimentary materials Sedimentary rocks Coal ashes Fe - Fe - Ge 265 Down to > 3-8 pg/l Ge - Ge 265.12 270.96 Rocks Minerals 1.3 @gig 1 pg/g-0.1% E, A, D.c., S Zircons Iron ores Ores Ores minerals, rocks minerals Coal Gcological materials E, P, ICP, L E, A, D.c., S A, -, G E, Chamber electrode, F, -,G F, Cold vapour, S A, Cold vapour, G 1 - 20 Pg/g 0.2 ng/ml-l pg/mL 10-5Pgglg-l% 50 X pg/g 5-25 pg/g 0-100g/tonne Geological materials Coal 0-250mg Traces Hg 253.7 Hg A, A, D.c., S A, Cold vapour, G 1.4-2.6% A, -, - K Rocks0.01 -0.1 rg/g E, -, L Samples were dissolved in a 1 :1 mixture of HCI and HCIO, (0.5 g in 40 ml).SiO was eliminated with HF, residue fused with Na, B,O, and the fused mass dissolved in 2N HCI and added to the sample solution Laser micrographic spectrometry used to excite the sample 1490 2 3 (0 La 408.7 Monazite 1749 820 .Mg Mn Titano ferrite Carbonate rocks 4.5% E, Laser excitation, S A, -, L Solution in 0.1N HCI + H, 0, (30%) contains Mn from carbonate and non-carbonate fractions while solution in 4 M NaOH + H,O, (36%) contains Mn from non-carbonate fractions; difference between these two value (determined by AAS) gives Mn in carbonate fraction 250 rng ore dissolved in 6 ml and 1 rnl HNO,/ HCI (3:l) by heatingfor l h a t 150"C, 10mlH,BO, and lOml3%H,O, added and the solution diluted to 100 ml A, F, Air/C, H, , L Mn 279.5 313.3 Ores 2280 462 701 Mo Flotation tailings A, F, L Digest the sample with HF in a PTFE vessel, heat to dryness, add HNO, IHCIO, (3: 1) + cold water and 2-benzo-oxime, stirring for 5 min, and extract with chloroform Mo Argillites A, F, Air/C, H, , L 0.5-1.Og samples were calcined at 500°C for 2 h, treated with HF for several hours and heated with H, SO, to white fumes; solutions were diluted with 1 :1 HCI and La added to eliminate matrix effect A simplified acid decomposition method was used for the ore analysis and dissolution in dilute HNO, E, P, ICP, L 0.2-5.0'72 E,F,N,O/C,H,,L Effective decomposition based on fusion with Li metaborate Nb 316.3 322.5 Nd - Reference ore Y, Al garnet Mineral, ore, rock OKA-1 C153 1166 1090 1674 1958 492 1665 1723 - E, A, S A new carrier mixture consisting of C and quartz is proposed (Co, Cr and V) Ni - 0.01-0.1 Mg/g A, F, Air/C, H, , L Sample (0.2-0.5 g) digested with HNO,/HF and residue treated with HCIO, ; extraction of NaDDC complexes is made with CCI, - E, -.- 0.01 7-0.0148 A, -. - - Ni Rocks Ni - Pb Pb Serpentine Soil, pyrite Geochemical exploration samples Rocks Boiling with concentrated HCI was most suitable sample dissolution procedure 50g sample mixed with 5Og PbO, 5 g starch, 5Og Na,CO,, 30g Na,B,O, and 30gglass;to themixtureisadded0.15g AgNO, -Na,Co, (l:l), fuse at 1200°C, Ag beads dissolved in HNO, The metals were separated by fusion, NiS was used as the collector Pt 247.6 0.05-1 .Ofig/ml A, ETA, L I .6 pg/l-l g/ton A, ETA, L Pt Rare earths - Ores, tailings, geological materials Chalcogenides 2007 371 0.1 - 1 .ow E, A, or S, -L -1 P Table 4.4 MINERALS-confinued Element Rare earths Rare earths Sb Sb Sb Sb s c s c s c s c Se Se Si Si Si Si SiO, Sn h/nm Matrix Technique, Atomization, Concentration Analyte Form Sample Treatment Ref.- 231 217.6 - 335.31 - - - - 25 1.6 286.3 Geological materials Traces E, P, ICP, L Ore concentrates Incinerator dusts Smelter flue dusts Geological material Mineralogical samples Silicate rocks Silicate rocks and coal Geological materials Silicate rocks Ore beneficiation Minerals, concentrates Coal ash Coal Rocks Carbonate rocks Geological materials Ores, soils - E, P, D.c., L 25-500 rg/ml A, ETA, L 0 - 1 20 rg/g A, F, Air& H, , L A, Quartz tube, G 0.2 -5 .O rg/g E, Laser, S E, -.- A, F or ETA, L E, P, ICP, L - A, ETA, L 63Channel emission spectrometer used on samples prepared by cation exchange with a HNO, gradient and anion exchange with a HC1 gradient Sample eluted with IN HNO, and eluate mixed with aqueous Mg (NO,), to obtain samples which were ashed for deter- mination of Sb Sample heated with HBr (20 ml) until white fumes appeared, then cooled and diluted to 100 ml for analysis After digestion with H, SO, /HNO, /HCIO, mixture the Sb is liberated as SbH, Co-precipitate the Sc with Ca oxalate and hydrated Fe(l11) oxide Separate Sc, Y and REE from matrix elements by open column ion exchange chromatography Dissolve the sample by acid treatement and pass through a column of Dowex 50 W - X8 cationexchange resin, elute the common ions with 1.85N HCI and the rare earths with 6N HCI Fuse sample (0.5 g) with 2.5 g Na, 0, in a ZrO, crucible and extract the melt with H, 0, filter the solution and neutralize with HNO, Slurry injection AAS Slurry injection AAS Describes the beneficial effects of water cooling the N, O/C, 11, flame Describes an improved method of plotting and using calibration graphs Treat the sample (50 rng) with HF in closed vial at 110°C for 2 h, centrifuge and dilute to volume Fuse 0.5 g ground sample with 2 g Na, 0, in Zr crucible at 725°C for IOmin, cool, add 3 ml H,O and 3.5 N HCI until the precipitate dissolves, add 2 ml saturated ascorbic acid then 10 ml MIBK, extract and nebulize the extract 1753 2009 354 483 673 2350 827 1925 C2455 C2466 995 1801 958 !A 1124 3 1603 4 !A 1778 E.b b b a s. 3 Sr 460.7 Ores - E, F, Air/C, H, , S Mix the sample with graphite and transfer a 50 mg portion to a graphite capsule, atomize into an air/C, H, flame and measure emission Dilute the sample (1 :1) with powdered C and excite in 18 A a.c.arc between C electrodes Atomize at 2650°C for 20s; reduce interference by adding La,O, t o the standards and samples and AlCI, to the standards before analysis Decompose the sample by boiling with dilute HCI and HNO, 579 Sr Apatite fractions 0.05-5% E, A, A.c., S 990 1100 Rocks A, ETA, S Sr 1104 2320 244 Sr Ti TI 460 264.3 276.8 Apatite concentrate - llmenite Cement, rock 0-5 Pg/g E, F, Air/C,H,, L A, F, L A, F, Air/C, H, , L Dissolve sample in HNO, /HF/HClO,, add large amounts of citric and ascorbic acids and eltract TI as NaDDC complex in MIBK Fly ash 0-2 ng Rocks Traces Carnellite Limestone, raw cement 0.07-2Opg/g A, ETA, S A, F, L A, ETA, - A, F, Air/C,H,, L 554 806 1069 1091 TI TI TI TI - - 276.8 Extract the APDC complexes of the metal with MIBK and nebulize the extract Extract the APDC complex with MIBK TI Deep sea ferromanganese - nodules Fluid inclusions in quartz 1-1000 r g / g Phosphate rocks, 0-9 ng crude oils Standard rocks - Molybdenite 1809 E, P, ICP, L A, ETA, L U V - 318.5 Rock samples dissolved in HNO, /HCIO, /HF, final digest made up to volume with HCI 3 20 E, P, D.c., - A, -.- 999 1802 V V Fuse sample (2.5 g) with ( I 2 g Na, 0, and 2 g Na, CO, , dissolve melt in H, 0 and neutralize with HCI, add Fe solution until a total of 100 mg Fe is present in solution and precipitate the Fe with NH,OH, dissolve the precipitate with HC1 add SOmg Al in solution and determine the V by AAS W W Yb Ores 285.1 Rocks soil 398.8 Phosphate minerals 0.01-1.00%~ Trace 1217 1803 474 Digest the mineral sample with concentrated H, SO, /HNO, , extract the Yb with DEHP solution 1153 1577 Yh Zn Silicate rocks Coal fly ash A, ETA, L A, ETA, LTable 4.4 MINERALS-continued Technique, Atomization, Element h/nm Matrix Concentration Analyte Form Sample Treatment Ref.Zr Zr Various Various (43) Various Various Various (4 ) Various (10) Various (9) Various (13) Various (16) Various Various Various (6 1 Various (6) Various (10) 257.14 Rocks E, -, S Preconcentrate the Zr by precipitation of the ore solution onto 578 spectroscopically pure C powder to which Mo has been added as internal standard, load the powder into the cavity of a graphite electrode for excitation Fuse the sample with a mixture of Na, CO, and K, CO, , separate the Zr from large amounts of Na and K by precipitation of the hydrated oxides before nebulization Dissolve the sample by multi-acid digestion or by Li metaborate fusion, separate and preconcentrate using ion exchange procedures (Rare earths) Dissolve sample (0.25 g ) with mixture of aqua re@u/HF in a sealed Teflon bomb, heat at 115°C for 6-8 h E, P, ICP, L E, P, ICP, L E, P, ICP, L A, F, - E, P, ICP, L E, P, ICP, L - Partial digestion methods are designed to attack oxide and sulphide phases selectively - (Au, Ag, Pd, Pt) - Silicate rocks 848 c11 C16 C68 C148 C150 C151 C154 C154 C155 C156 C264 C267 C279 328 392 - Geological materials Trace levels Meteorites Major, minor and trace levels Trace levels Brown coal Complex geological samples Precious metals Trace levels 1 - 100 P d g - Geological materials E, P, ICP - 0 , DY, Eu, Gd, La, Nd, Sc, Sm, Y, Yb) Geological materials Major, minor and trace levels E, P, ICP, L Dissolve sample (1 g) by mixed acid HF-HCIO, -HNO, attack; sample and standard solutions matched for total solid content by adding NaNO, (Al, Ca, Fe, K, Mg, Mn, Na, P, Ti) Dissolve samples by fusion with Li carbonate and boric acid E, P, ICP, L Geological samples, glasses Bauxite Micro-components E, P, ICP, L Dissolve in HCI-HNO, -HF at 160°C in Teflon bomb or fuse with NaOH 0.001 5 -8.7% Calcareous rocks Coal Geochemical drilling samples Fly ash from tar sands E, P, ICP, L - E, P, ICP, L A, ETA, - Introduce the sample as a slurry to the plasma Zeeman modulation employed (Ag, Au, Co, Cu, Ni, Pb) A, F, Air or N, O/C, H, , L A, F,N,O/C,H,, L Digest the sample with aqua regia and HF in pressure bomb; add H, BO, (Al, Fe, Ni, Si, Ti, V) Fuse 100 mg sample with 700 mg LiBO,, dissolve the melt in 4 ml HNO, and 30 ml H, 0 (Al, Ba, Ca, Fe, K , Mg, Mn, Na, Si, Ti) - Rock.soil Major, minor and trace levelsVarious (8) Coal, fly ash Trace levels A, Quartz tube, G 396 Dissolve 200 mg sample inHNO,/HCl/HF in bomb, heat to 1OO"C, add boric acid to neutralize HF, filter and dilute to volume, treat with NaBH, (hydride generation) (Al, Bi, Ge, Pb, Sb, Se, Sn, Te) Fuse 0.2-1 g sample with Na,O, or LiBO, and dissolve the melt in 4-10% HNO, (Rare earths) Dissolve 10 mg sample in dilute HCI and dilute with H, 0 to 50 rnl (Ca, Fe, Mg, Mn, Zn) Mix the powdered sample with graphite powder ( l : l ) , sweep into a dual stream plasma (130 V, 100 A) (Hf, Nb, Ta, Th, Zr) Blow the powdered sample through an arc discharge (Ba, Cs, Li, Rb, Sr) Mix the samples with graphite and Li,CO, (Co, Cr, Ni, Sc, Sr, Ti, V) Various Geological materials 50-200 pg/g E, P, ICP, L 427 Various (5 ) Various (5 ) Manganese minerals Major levels E, P, ICP, L 488 Rocks Trace levels E, P, S E, A, S E, -, S 509 649 720 Various (5 ) Various (7 ) Various (17) Various Various (9 1 Various (6 ) Various Various (23) Various (11) Various (5 ) Crystalline rocks Siderites Meteorites E, P, ICP, - 741 Coal Rocks - A, -, - Major and trace elements A, ETA, - 846 848 - - (Ba, Cd, Co, Cr, Cu, Ni, Sr, V, z n ) Chrysotile asbestos Minor and trace levels E, -, - - (Cr, Cu, Fe, Mn, Ti, V) 887 Volcanic ash Geochemical standards Phosphorite ores - E, P, ICP, L Major and minor levels E, P, ICP, - 919 931 980 - E, P, ICP, - Release the elements As, Bi, Cd, Se and TI at 1000-1300°C into a flowing carrier gas and trap on a water cooled condenser.Dissolve in an aqueous solution of 2% HNO, and nebulize the solution (As, Bi, Cd, Se, TI) Fuse the sample with Liz B, 0, , dissolve in aqueous HCl (As, Cr, Cu, Mn, Ni, Pb, Sb, Sn, V, Zn) - (Ca, Cd, Cu, Ga, Mg, Mn, Pb, Zn) Geological samples Trace levels A, ETA, L 1165 1194 Various (10) Various Various (8) Various Various Various (7) Coal, fly ash Ashes, rocks Coal, fly ash Major and trace levels Major and trace levels E, P, ICP, ~- E, P, ICP, S 1211 1231 Geological ores - Geological samples Trace levels Ores 0.05-5% E, P, ICP, L E, P, ICP, L E, P, ICP, L 1237 C1290 C1294 - (Al, Fe, Mn, Nb, Si, Ti, Zr)Table 4.4 MINERALS-continued Element A/nm ~ Matrix Various (19) Various Various Various Various (32) Various (10) Various Various Various Various (12) Various Various (7) Various (6) Various (21) Various (9) Various (9) Various (12) Mineral ores - Minerals, ores Precious metals Geological samples Geological materials Manganese nodules - Ores, minerals Optical glass - Bauxites, red mud - Rocks - Slags, ashes - Geological materials Coal, kerogens Silicate rocks Zinc ore Heavy mineral concentrates Sedimentary rocks - Technique, Atomization, Concentration Analyte Form Sample Treatment Ref.E, P, - Apply a two-stream plasmatron with non-consumable electrodes C1300 E, P, - A or E, -, - E, ICP, - E, ICP, L - A, F, Air/C, H, , L Minor levels E, A, S Trace levels E, P, ICP, - E, P, ICP, - Trace levels, E, -, - Major levels Trace levels E, P, ICP, - A, P, ETA, - E, -, - E, A, D.c., S - Major levels - E, A, S Major levels E, A, D.c., - E - - 3 , Trace levels - (Non-metals) Boil 1 g sample with 20-25 ml 5% oxalic acid, filter, wash undigested residue with H,O, add 5 ml 50% H,O, to each filtrate, boil to dryness add 20 ml 20% HCI to residue and dissolve, filter Digest 50 mg sample at 200°C (1 h) with HC1, HC10, and HF in PTFE (Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Zn) - (Rare earths) - (Rare earths) - (Bi, Cd, F, Pb, Se, TI, Zn) Use a buffer containing K,SO, 30, S 50, C 10, and Na,SO, 10% (Cu, Ga, Ge, In, Ni, V) Volatilize a powdered sample, plus buffer diluent, from a graphite electrode by means of a gas-jet stabilized d.c.arc, excite in an Ar-0 atmosphere Add 20% of a mixture of NaF, S, and SiO, (1 :2:7) to the powdered sample (As, Cd, Co, Ga, Ge, In, Ni, Sb, Te) Prepare synthetic standards from a base mixture containing Fe,O, (63L TiO, (101, SiO, ( l o ) , A1,0, (lo), MgO ( 5 ) , Mn,O, (11, NaH,Po, (1)% (Ag, Ba, Co, Cr, Cu, Pb, Sn, V, Zn) C1301 C1417 C1428 1566 1589 1661 C1683 C1694 1702 1738 1808 1828 1851 1917 2045 2049b 'c1 B Various - Standard rock samples - E, -, - - (Cd, Cr, Mn, Ni, Pb, Sr, V, Zn) C2082 $ (8) Various Coal - E, P, ICP, L Prepare a slurry of the sample for direct analysis 2089 Various Coal materials Trace levels E, P, ICP, L C2091 Various - Coal Trace levels E, P, ICP, Ash the sample and dissolve in a mixed acid (HCI-HNO, -HF) C2092 Various Coal All levels E, P, ICP, - - C2 144 (33) - - C2146 Various Geological materials All levels E, P, ICP, - Various Geological materials Trace levels E, P, ICP, L Separate Fe as the hexachloride into butyl acetate, extract C2159 (8) Various River sediments Trace levels E, Ag film, S Use the highly luminous Ag vapour plasmas produced by the 2230 (8) 3 using a PTFE bomb the trace elements using mixed APDC and DDC in chloroform (Bi, Cd, Co, Cu, Ni, Pb, V, Zn) electrical vaporization of Ag thin films with 960 J, 8 kV, 1200 pH discharges as atomization and excitation sources (Cd, Cr, Mn, Ni, Pb, Sr, V, Zn) distillate in acid KMnO, solution follow by SnCI, reduction, aeration with Ar and AFS in continuous mode, digest sample with HClO, and liberate As and Se hydrides for AAS, H, flame (As, Cu, Fe, Hg, Mn, Ni, Se, V) Various Coal Trace levels F, Hydride, G For Hg determination use non-oxidative pyrolysis, collect C2301 A, ETA W2), L (9) E, P, ICP, L

ISSN:0306-1353    

DOI:10.1039/AA9821200165

出版商:RSC    

年代:1982

数据来源: RSC

摘要:

180 Analytical Atomic Spectroscopy 4.5 A I R ANALYSIS The reader who, on r e c e i v i n g ARAAS, t u r n s f i r s t t o t h e a p p l i c a t i o n s t a b l e s w i l l already have noted t h a t t h e number o f p u b l i c a t i o n s concerned w i t h a i r a n a l y s i s has n o t changed markedly i n r e c e n t years. much o f a novel n a t u r e which w i l l prove o f r o u t i n e p r a c t i c a l use.I f any t r e n d can be detected, i t i s a p o l a r i z a t i o n o f p u b l i c a t i o n s towards two extremes: e v a l u a t i o n o r minor improvement o f w e l l - t r i e d methods and r e p o r t s o f e x o t i c instrumental techniques u n l i k e l y t o see r o u t i n e use f o r many years, i f a t a l l . The l a t t e r case i s p a r t i c u l a r l y n o t i c e a b l e i n t h e AES area.It i s , however, d i f f i c u l t t o f i n d 4.5.1 Sample Preparation Taylor (C284) has described a re-usable sampling device f o r Hg based on a tube coated w i t h s i l v e r e d alumina, t h e c o l l e c t e d Hg being t h e r m a l l y desorbed. tubes may be used f o r l o n g o r s h o r t sampling periods and gave a n e g l i g i b l e blank.Atmospheric Hg has a l s o been c o l l e c t e d on glass f i b r e f i l t e r s , from which i t was f r e e d by HF v o l a t i l i z a t i o n o f t h e s i l i c a f i b r e s (C1897), and by passing a i r samples through KMn04 s o l u t i o n s (1739). determinations o f metals i n dusts have appeared. complexed Mn w i t h 1-(2,4,6-trimethylpheny1)-1,3-butanedione and TOPO, i n acetate b u f f e r , b e f o r e e x t r a c t i o n i n t o benzene.Pb i n t o CHC13 using NaDDC a t pH 2.5, w h i l e F r a n c e t i c e t a l . (675) used APDC and pH 3.3-3.5. co-workers (1127) c o l l e c t e d a l k y l s e l e n i d e compounds i n a i r by cryogenic trapping, f o l l o w e d by t r a n s f e r t o a GC column c o n s i s t i n g o f 10% polymetaphenyl e t h e r on 80-100 mesh acid-washed Chromosorb W.It was p o s s i b l e t o measure d i m e t h y l d i - selenide and d i e t h y l s e l e n i d e a t l e v e l s down t o 0.2 ng m-3 u s i n g an o r d i n a r y CC i n t e r f a c e d t o an e l e c t r o t h e r m a l atomizer. The same workers used a s i m i l a r technique (1899) f o r s p e c i a t i o n s t u d i e s o f f i v e t e t r a a l k y l Pb compounds.A personal m o n i t o r i n g method has been r e p o r t e d (567) i n which alkyl-Pb species were c o l l e c t e d on a glass fibre-carbon f i l t e r , t r e a t e d w i t h methanolic i o d i n e , and subsequently determined by FAAS. C o l l e c t i o n from 120 1 samples allowed Pb t o be measured a t concentrations as low as 0.01 mg m-3.The Several r e p o r t s o f improved s o l v e n t e x t r a c t i o n preconcentrations f o r FAAS Smirnova and Vackova (960) Nemets e t al. (1727) e x t r a c t e d Cd, Mn and Speciation u s i n g GC combined w i t h AAS continues t o be o f i n t e r e s t . Jiang and 4.5.2 Atomic Absorption and F1 uorescence Methods Very few i n t e r e s t i n g r e p o r t s o f flame atomic absorption methods have appeared d u r i n g t h e p a s t year.Jackson (1607) described t h e s e r i e s o f "standard l a b o r a t o r y methods" published by t h e UK Health and S a f e t y Executive f o r t h e FAAS determin- a t i o n o f heavy metals i n d u s t samples c o l l e c t e d from i n d u s t r i a l atmospheres.I n most cases elements such as Cd and Pb may be r a p i d l y and r e l i a b l y monitored a tApplications 181 l e v e l s down t o 0.1 TLV u s i n g 120 1 a i r samples. A comprehensive method f o r Ca and Mg i n atmospheric p a r t i c u l a t e s was described by Yamashige and Shigetomi (453). The p a r t i c u l a t e s and q u a r t z f i l t e r s were digested and d i s s o l v e d by h e a t i n g t o dryness t h r e e times w i t h 5 m l o f 45% HF, adding 20 m l o f warm concentrated HN03 p l u s H202, t a k i n g t o dryness and f i n a l l y d i s s o l v i n g i n 50 m l o f 0.5M HC1 c o n t a i n i n g 350 mg o f S r 2 + t o reduce m a t r i x i n t e r f e r e n c e s .Determination by FAAS using an air/C2H2 flame allowed measurement o f 3 t o 25 pg o f Mg and 30 t o 300 pg o f Ca w i t h e r r o r s o f l e s s than 5%.Two papers have reviewed p a r t i c u l a r aspects o f e l e c t r o t h e r m a l atomic absorp- - t i o n . N o l l e r e t a l . (523) provided an extremely d e t a i l e d survey, w i t h 474 references, s p e c i f i c a l l y concerned w i t h sampling and a n a l y s i s o f metals i n atmospheric p a r t i c u l a t e s by ETA-AAS.Ottaway (2036) b r i e f l y discussed general aspects of ETA-AAS b e f o r e e v a l u a t i n g i n d e t a i l two new developments: p l a t f o r m and probe atomization. He a l s o described t h e design o f a f u l l y auto- m a t i c ETA-AAS monitor f o r t h e determination o f metals i n atmospheric p a r t i c u l a t e s .The r e p o r t e d d e t e c t i o n l i m i t s f o r 10 1 samples were 5.5 ng rn-3 f o r Cd and 36.0 ng rn-3 f o r Pb. atmospheric Hg vapour u s i n g e l e c t r o s t a t i c accumulation i n t h e furnace tube. sampling e f f i c i e n c y was b e t t e r than 90% under optimized c o n d i t i o n s , a l l o w i n g a d e t e c t i o n l i m i t o f 50 ng mq3. mination o f As i n atmospheric aerosols, a f t e r d i s s o l u t i o n u s i n g 50% HN03 a t 60 OC i n an u l t r a s o n i c a l l y a g i t a t e d PTFE bomb.the c h a r a c t e r i s t i c c o n c e n t r a t i o n was 0.01 ng, which i s s i m i l a r t o t h a t obtained by hydride generation AAS. Midgley (1788) described a continuous atmospheric monitor f o r sulphur d i o x i d e based on t h e AAS measurement of Hg.Sample a i r was drawn i n t o a r e a c t i o n vessel c o n t a i n i n g Hg+ i o n s and any SO2 present reacted t o form elemental Hg which was released from s o l u t i o n and swept i n t o a c o l d vapour d e t e c t o r by t h e f l o w o f a i r . The method has a d e t e c t i o n l i m i t o f 0.2 ppb SO2 and a l i n e a r range o f up t o 100 ppb.i n a i r was determined (613) by bubbling t h e sample through a s o l u t i o n o f CdS04 a t pH 6.5. measurement o f Cd by AAS. R i g i n (1224) determined CO by r e a c t i o n w i t h HgO, u s i n g Co304 as an a c t i v a t o r , and measuring t h e evolved Hg vapour by AFS. t h e use o f T o r s i and co-workers (1126) r e p o r t e d an ETA-AAS method f o r The A comprehensive r e p o r t (387) described t h e deter- When N i was used as an a d d i t i v e Data were r e p o r t e d f o r marine and v o l c a n i c dusts.Several r e p o r t s have appeared o f i n d i r e c t determinations by AAS. Marshall and The RSD was t y p i c a l l y 1 t o 2% a t t h e S 2 0 ppb l e v e l . The p r e c i p i t a t e d CdS was f i l t e r e d and d i s s o l v e d i n HN03 p r i o r t o A t t h e TLV c o n c e n t r a t i o n o f H2S t h e RSD was 1.4%. Hydrogen sulphide 4.5.3 Atomic Emission Methods New a p p l i c a t i o n s f o r t h e i n d u c t i v e l y coupled plasma continue t o be reported.Broekaert and co-workers (2027) described t h e multi-element a n a l y s i s o f aerosol samples c o l l e c t e d w i t h cascade impactors.The samples were digested i n HF/HN03182 Analytical Atomic Spectroscopy a t 170 OC, and free fluoride was complexed w i t h H3B03 p r i o r t o the determination of Al, Cay Cr, C u , Fey Mg, Mn, Pb, S r , V and Zn using a 3 kW N2 cooled Ar ICP. By using only 2.1 ml f i n a l sample volume, i t was possible t o achieve both t r a c e and minor element analysis on a single 0.1-1mg sample.determinations per hour were achieved. determination of Be, Cd, Mn, Ni, Pb, Zn i n p a r t i c u l a t e matter collected on fibrous and membrane f i l t e r s and subsequently dissolved i n acid. Various sample handling problems were discussed. The same author has also described (2264) the use of ICP-OES f o r the d i r e c t determination of s l u r r i e s of atmospheric partic- ulates.The samples were collected on polystyrene f i b r e f i l t e r s which were dis- solved in xylene w i t h ultrasonic a g i t a t i o n , t o produce a slurry. of sample i t was necessary t o grind the s l u r r y p r i o r t o nebulization, apparently because r e l i a b l e r e s u l t s were obtained only f o r p a r t i c l e s of < 10 pm diameter.Results were reported only f o r Fe i n this preliminary work. Finally, Sugimae has reviewed (1141) environmental applications of ICP-OES i n a short paper with 21 references. described the use of a DCP t o determine Be i n industrial atmcspheres over the range 0.001 t o 5 ug m1-l. I t was noted t h a t the minimum detectable quantity was 0.0036 pg Be per sample and t h a t Fe interfered a t levels greater than 2 mg Fe per sample. Matherny and Ondasova (372) gave a detailed description of the spectro- graphic analysis of a i r p a r t i c u l a t e samples u s i n g a medium voltage spark dis- charge between c a p i l l a r y electrodes.The samples were dissolved and Al, co, Cry C u , Fey Mg, Ni, Pb and Zn determined a t levels down t o 0.4 pg m1-l.The average overall RSD was, however, only 15%, which i s not as good as w i t h a conventional arc source. Thirty multi-element Sugimae (C1686) described the ICP-OES With some types Other emission sources have not been neglected. Chang and co-workers (807) - ~ - The number of reports concerning novel emission sources has been unusually high. Only those where an application t o a i r samples was a major part of the study a r e mentioned here. a copper shock tube, as the emission source t o determine Cry In, Mn, Ni and Ti i n airborne dust, The samples were collected on PTFE f i l t e r s .Addition of 0.2 mg Na2C03 t o each sample improved s e n s i t i v i t y s u f f i c i e n t l y t o allow measure- ments down t o about 10 ng of each element per f i l t e r .Sacks and Swan (C2083) analysed dust deposits using their exploding film technique (see ARAAS, 1980, 10, 32). Cremers and Radziemski (C1317) monitored C 1 2 and F2 i n a i r using laser- induced breakdown spectroscopy. The high temperature (25 000 K and above) i s s u f f i c i e n t t o break down the halogen molecules and excite a n a l y t i c a l l y useful atomic emission. 40 ppm f o r F a t the 658.6 nm l i n e , w i t h a l i n e a r working range u p t o about 1000 ppm.The same system has a l s o been used (C241) f o r real-time monitoring of airborne Be a t levels down t o 5 pg m-3 using the Be(I1) doublet a t 313.1 nm. Kosasa e t a l . (125) used an Ar/H2 plasma, induced i n Detection l i m i t s were 20 ppm f o r C1 a t the 837.5 nm l i n e and I tApplications 183 was noted that the laser spark technique requires only optical access t o the sample area and i s thus well-suited t o measurements i n hostile environments.Table 4.5 AIR AND PARTICULATES Technique, Analyte Form A, ETA, Hydride, G Concentration Atomization, Sample Treatment Ref. 0-1 rg/m’ 387 Digest filter in bomb with 50% HNO, followed by ultrasonic agitation at 60°C for 5 h, open bomb heat to dryness and take up in 2 ml 1% HNO, Element h/nm Matrix As 197.2 Air As - Air 0.3 &n3 A, ETA, Hydride, G Collect on filters, treat with NH,/H,O, solution, evaporate and dissolve residue in HCI; add NaBH, to generate ASH, into heated silica tube for absorption measurement Review and comparison with polarographic, colorimetric and absorptiometric methods None Filter dust subjected to plasma ashing, residue extracted with HNO, 487 575 C24 1 350 807 96 2 878 1224 45 3 572 765 1727 2036 C1317 612 c1317 2264 823 As - Air A, ETA, Hydride, G < 5 rglm’ 0.004-0.26 1 ng/m3 Be 313.1 Air Be - Air E, Laser plasma, G A, -, L 0.001-5 pg/m3 0.42 ng/m3 10’ molec./cm3 Industrial aerosols Aerosols Argon - E, P, D.c., L A, -, - E, Metastable transfer, G F, Cold vapour, G React CO with HgO in presence of Co oxide activator; determine evolved Hg by AFS Acid digestion of particulates compared Draw air through cellulose ester or glass fibre fiiter and treat with HNO, Ca 422.7 Airborne particulates Cd 228.8 Air 0.8-9.5% 1.5-300 rg/m3 30 rg/m3 5 r g i l A, F, Air/C,H,, L A, -, L Cd 228.8 Air Cd - Air Adjust pH of sample solution to 2.5 with HCI; add DDC and CHCl, for extraction, then repeat procedure, evaporate and dissolve residues in HNO, and add ethanol Review and description of automatic air metal monitor Cd - Air particulates c u - Respirable coal dust F 685.6 Air Fe 259.9 Air particulates CI 837.5 Air A, ETA, ~ E, Laser plasma, G A, -, L E, Laser plasma, G E, P, ICP, L Wet ashing Dissolve filter material in xylene and slurry particulates ultrasonically H 486.1 Inert gases, Helium, Neon, Argon 7 x 10-5 Voi % 4 x v0i % 2 x lo-‘ vol% E, P, ICP, Gb B Hg Hg Hg Hg Hg Hg Hg Hg Mg Mn Mn N 0 Pb Pb Pb Pb Pb Pb Pb Pb Pb - Air Air - Phenyl-mercury acetate in Air (PMA) Air Ail 0-lOpg 0.002pg 50ng/m3 A, Cold vapour, G A, Cold vapour, G E, P, ICP, G A, -, L F, XRF, - A, ETA, Vapour A, -, L - Air, particulates 253.7 Air - Suspended dust 285.2 Airborne particulates - Welding atmospheric dust - Air - Argon Helium Neon - Argon 217 Tetra alkyl lead in air 283.3 Air Air Air in firing ranges Air particulates Lead acid battery plant atornosphere Air Air - Tetra-alkyl lead in atmosphere - - - 0.5-1.7% - 0.01 mglm' A, -, L A, -, Vapour A, -, Vapour A, F, Air/C,H,, L A, -, L A, -, L E, P, ICP, G E, metastable transfer, G A, F, Air/C,H,, L A, F, Air/C,H,, L A or E or XRF A, -, - A, ETA, S A, F, Air/C,H,, L A, -, L A, -, - F, XRF, - A, -, GC-AA, G Comparison of techniques Collect on 0.5 urn PVC filters and dissolve with conc. HNO, at 70 "C for 90 min Electrostatic accumulating furnace KMnO, used to absorb Hg from air, solution analysed by AAS Collect Hg in ICI solution or KMnO, solution Dissolve glass fibre filters in HF releasing Hg as vapour See Ca, ref. 453 Mineralize with hot HNO,/H,O,; Mn complexed with 1-(2,4,6 trimethylphenyl)-l,3-butane dione and trioctyloxophosphorane in acetate buffer and then extracted with benzene, extract shaken with dil. HNO, and aqueous phase analysed See Cd, ref. 1727 - Draw air through glass fibre - carbon fibre filter to collect alkyl lead species with methanolic iodine, heat filter with HNO, and Br then dilute with HNO, Draw air through cellulose ester or glass fibre filter which is then treated with HNO,/H,O, Review of methods Electrostatic accumulating furnace Collect Pb on filter, digest with dilute HNO, See Cd, ref. 1727 Comparison of methods C284 C285 611 1126 1739 1790 1829 1897 453 960 1727 1159 878 561 574 599 85 1 1128 1197 1727 1789 1899Table 4.5 AIR AND PARTICULATES - continued Element h/nm Matrix Concentration Atomization, Sample Treatment Ref.Analyte Form Pb S SO1 SO1 S S Se Sr Sr V Various ( 5 ) Various (9) Various Various (4) Various (5) Various (6) Various (5) Various (10) Various Various Various (1 1 ) Various (9) Various (1 1) Various Various (10) - Air particulates 228.8 (Cd) H,S in air - Exhaust fumes - Air Particulates, plumes Alkyl selenides in air - Air - Aerosols - Airborne diw - Airborne dust - Air particulates Atmospheric particles Atmospheric dust Urban road atmosphere Airborne particles Atmospheric moisture condensates - Respirable coal dust - Air - Air - Air particulates Aerosols Urban particles Airborne dust 36 nglm’ 1.4 pgglml ~ 0.2-1OOppb 4 pg so:-/m3 0.2 ng/m3 3.6 - 13.2 ng/m3 6.7 nglm’ 0.5 d l 0.001 -0.1 pg/m’ - A, ETA, S A, -, L E, F, G A, Cold vapour, C E, F, - A, ETA, GC-AA, G A, -.L A, -, - A, F, -, L E, P, Ar/H, Shocktube, S E, S, Medium voltage, L A, ETA, - A, -, - A, -, - A, -, - E, P, D.c., S A, -, - E, P, ICP, - A, F, - F, XRF, - E, P, ICP, L A - __ > , E, P, ICP, L E, P, Metal film, S E, S, A.c., - See Cd, ref. 2036 Pass air containing H,S through acid solutions (pH 6.5) of CdSO, to form CdS, filter off and dissolve in HNO,; determine Cd as indirect measure of S Displace Hg with SO, from HgZt reagent and determine by cold vapour AAS Dimethylselenide, dimethyldiselenide and diethylselenide sampled from air by cryogenic trapping See Be, ref. 350 Dissolve sample and extract V a t pH 3.3-3.5 with tetramethyl- enedithiocarbamate into CHCI,, destroy complex with mineral acid Review, 474 references Filter collection followed by mineralization Review, 25 references Concentrate condensates on C powder - Review, 21 references Filter collection followed by acid digestion Paper filters containing particulates dissolved in HCl and HNO, Collected on impactors and dissolved in HF/HNO, at 170°C - 2036 613 76 7 1788 1196 1127 350 96 2 675 125 372 523 74 2 85 2 916 917 96 1 1114 1607 1686 1854 2027 2083 C2400

ISSN:0306-1353    

DOI:10.1039/AA9821200180

出版商:RSC    

年代:1982

数据来源: RSC

摘要:

Applications 187 4.6 WATER ANALYSIS The large number of papers published recently indicates the key r o l e which atomic spectroscopy continues t o play i n the inorganic analysis of waters and e f f l u e n t s . Atomic absorption methods, especially those u t i l i z i n g ETA o r involving a vapour generation step, remain particularly popular f o r the determination of single o r limited groups of elements, while ICP-OES has become firmly established f o r multi-element detection.A general review of techniques has appeared (666). Statutory requirements and general concern over water pollution have combined t o focus a t t e n t i o n on the determination of t r a c e constituents. o f careful sampling and quality control programmes i s being recognised, and a good example of a t o t a l analytical approach t o the measurement of t r a c e elements i n natural waters i s t h a t reported by Ihnat (922), which described the determin- ation of Cd, C u , Pb and Zn i n streams draining agricultural watersheds i n southern Ontari 0.The importance 4.6.1 Sample Preparation I n t e r e s t in the measurement of t r a c e elements i n waters has resulted i n a large number of papers t h a t described sample treatment procedures f o r the separation and concentration of t r a c e analytes.Reviews o f f l o t a t i o n techniques (1412), general methods f o r preconcentration, a l b e i t primarily directed towards XRF measurements (2214), and the influence of naturally occurring organic materials on preconcentration and detection techniques (1038) , have appeared.Conventional complexation and solvent extraction remains popular, w i t h a variety of systems being used, including: 8-hydroxyquinoline/l,2-dichloroethane (1074) and 5-bromosalicylaldoxime/chloroform (1831) f o r C u ; 2-ethylhexane-l,3- di ol /toluene f o r B (694) ; tetrabutyl ammonium bromide/dimercaptomal eoni tri le/MIBK f o r Fe (1952) ; APDC/carbon tetrachloride (925) and di thizone/TOPO/carbon t e t r a - chloride f o r Cd (1677); aluminium cupferrate/methyl s a l i c y l a t e f o r Cu and Fe (460); and NaDDC/chloroform f o r B i (1719).Danielsson e t a l . (2261) preferred Freon-TF over other solvents f o r the extraction of di thiocarbamate complexes of Cd, Cu, Fe, Ni, Pb and Zn from esturine waters, because of i t s low aqueous solubi 1 i t y and greater tolerance t o varying phase m i s c i b i 1 i t y caused by s a l i n i t y variations.From an examination of 30 organic solvents, Miyazaki e t a l . (2265) concluded t h a t diisobutyl ketone was the most s u i t a b l e f o r use w i t h APDC i n the determination of Cd, C u , Fe, Mo, Ni, Pb, V and Zn i n r i v e r and seawater by ICP- OES.In an extended procedure, Brueggemeyer and Caruso (966) e r t r a c t e d Pb w i t h chloroform as i t s di thiocarbamate complex; evaporated the solvent, and then treated the residue w i t h methyl l i t h i u m t o form tetramethyl lead vapour which was trapped on a short column of Porapak Q before being determined by quartz furnace-AAS. Mu1 ti-element preconcentration procedures have again a t t r a c t e d a t t e n t i o n , a s188 Analytical Atomic Spectroscopy noted l a s t year.Thompson e t a l . (1541) described a simple and r a p i d evaporation technique f o r use w i t h ICP-OES. P a r t i a l losses were observed f o r Ag, As, Be, Mn, Mo, Sb, T i and Z r , b u t the method was considered applicable t o the determination o f 16 elements i n t y p i c a l r i v e r waters. on the use o f complexation w i t h 8-hydroxyquinoline followed by adsorption onto C18-bonded s i l i c a gel (see ARAAS, 1981, 11, Refs. 2154 and 2222) f o r the m u l t i - element preconcentration o f trace metals from seawater. Shreedhara-Murthy and Ryan (2218) concentrated Cd, Cu, Hg and Pb from fresh and seawater w i t h micro- c r y s t a l l i n e c e l l u l o s e onto which dithiocarbamate groups had been introduced.Polydithiocarbamate chelating resins were used (C240) t o obtain a concentration factor o f 200 i n the determination o f H f , Nb, Ta, T i , U and Z r i n seawater by ICP-OES. Azumi e t a l . (2028) q u a n t i t a t i v e l y coprecipitated Coy C r ( I I I ) , Cr(VI), Cu, Mn, N i , Pb and Zn by t r e a t i n g water samples w i t h 100 mg 1 - l F e ( I I 1 ) and 2% diethyldithiocarbamic acid a t pH 7.A s i g n i f i c a n t number o f reports o f electrodeposi t i o n methods appeared t h i s year, mainly i n connection w i t h AAS. c e l l employing commercially available graphite furnace tubes as the working electrode f o r the preconcentration o f Hg.Deposition was enhanced by a t h i n - layer flow-through configuration and a detection l i m i t o f 0.08 ppb was obtained. An amalgamated Au wire cathode was used w i t h a P t wire anode t o c o l l e c t Cd a t the 10 ng-l l e v e l from a c i d i f i e d lake water samples, which were s t i r r e d and purged w i t h N2 over a 6-day period (771). d i s s o l u t i o n o f the Cd w i t h 0.2 m l o f 10% HN03.Further work has been reported (318) F r i c k and Tallman (1129) described a f l o w Detection was by ETA-AAS, f o l l o w i n g Additional references on the preceding t o p i c - C297, 1953, 2031. Appropriate sample treatment procedures have been used t o f a c i l i t a t e studies o f element speciation, which t y p i c a l l y involves the determination o f the amount o f analyte present i n d i f f e r e n t oxidation states o r i n organic o r inorganic forms.A general review o f techniques has appeared (1463), and Ebdon and co- workers (1606, C2300) have discussed the p r a c t i c a l i t i e s o f coupling chromato- graphic and atomic spectroscopic systems f o r speciation studies. Chau e t a l , (2430) reported the d i r e c t and simultaneous determination o f t e t r a - , tri- and d i - a l k y l Pb and inorganic Pb by GC-AAS.Various methyl-Sn species and Sn(1V) were q u a n t i t a t i v e l y extracted i n t o 0.1% tropolone i n benzene from 100 rnl samples o f lake water a f t e r a d d i t i o n o f 40 g of NaCl (769). Sn compounds were separated on a gas chromatograph and atomized i n a quartz furnace f o r AAS detection.Persson and Irgum (400) separated inorganic As from dimethylarsenate by passing seawater samples through a Dowex AG50W-X8 ion- exchange column and e l u t i n g w i t h 0.1M H3P04 followed by 1M NH40H. The separation o f C r ( I I 1 ) and Cr(V1) p r i o r t o t h e i r determination by AAS has been accomplished by s e l e c t i v e coprecipitation w i t h cobalt-l-pyrrolidinecarbodi t h i o a t e (615) and also by i o n exchange (C312). Procedures used t o separate tri- and hexa-valent Following butylation, theApplications 189 As and Sb included: solvent extraction of As(II1) with APDC o r diethyldithiophos- phoric acid i n chloroform (2256), o r of Sb( 111) with N-benzoyl-N-phenylhydroxyl- amine (332); and d i f f e r e n t i a l hydride generation f o r both elements (417). 2224. Additional references on the preceding topic - 3 , 81 1 , 1132, 1399, 1473, 1904, 4.6.2 Atomic Absorption and Fluorescence Methods Flame atomization i n AAS has reached a stage of considerable maturity and i s widely used i n laboratories f o r the analysis of waters and e f f l u e n t s . Currently the U K Department of the Environment i s publishing a s e r i e s o f recommended o r t e n t a t i v e methods f o r the examination of waters and associated materials , several of which now rely on FAAS.(1485) involve the addition of 100 ppm of Cs as an ionization suppressant. Evap- oration i s used t o concentrate samples p r i o r t o the determination of Cu (667) and Zn (814), while f o r Co (1470, 1706) and Ni (1471) e i t h e r evaporation o r solvent extraction with APDC/MIBK i s recommended.A HN03 digestiom-FAAS procedure i s given f o r the determination o f Cd, Cr, C u , Ni, Pb and Zn in sewage sludge. I t i s noteworthy t h a t even w i t h such a long-established technique a s FAAS, detailed studies of i t s application t o real samples s t i l l reveal unexpected problems.Severe interferences i n the determination of Cr, Fe and Mn i n waste water samples with an air/C2H2 flame were described by Thompson and Hydes (C253, 2287). observed t h a t the e f f e c t s were both related t o fue1:oxidant r a t i o s and varied between d i f f e r e n t instruments; a marked suppression of the Mn signal by as l i t t l e as 5 ppm of Si was strongly instrument dependent.A novel approach t o the determination of high levels of Ca i n sewage sludges and liquors by using the 430.3 nm non-resonance 1 ine was reported ( 1 549). thermal atomization-AAS, most described quite straightforward applications of t h i s popular and s e n s i t i v e technique. studies of matrix interferences, which l i m i t the effectiveness of conventional ETA-AAS i n the analysis of waters and effluents where chloride i s usually present.Matrix modification by the addition of various compounds such as c i t r i c acid (856), ascorbic acid (1365), ammonium s a l t s (325, C2155), LaC13 (1514) and Pd (1919) remains the most common approach t o overcoming the problem. However, instrumental changes, notably the use of the L'vov platform, a r e l i k e l y t o provide greater freedom from interferences, and reports of the application of platform atomization t o the determination of Cd (C2174) and A1 (1359) i n seawater, and Mg i n saturated NaCl (2226) have appeared.Procedures f o r the determination of K (1484) and Na They Of the r e l a t i v e l y large numbers o f papers published t h i s year on electro- Many of these were concerned in part with Additional references on the preceding topic - 501, 171 5, 1720.For the determination o f elements such as As, Hg, Sb and Se, a vapour gener- ation s t e p combined w i t h AAS detection remains a popular technique, but l i t t l eI90 Analytical Atomic Spectroscopy work of a t r u l y innovative nature has been published recently.ferences during reduction remain a problem in those methods where samples a r e treated typically w i t h NaBH4 t o generate v o l a t i l e hydrides. Welz and Melcher (2178) have reported t h a t t r a n s i t i o n metal interferences i n the determination of As i n waste water may be minimized by carrying out the reaction i n 6M HC1. Pre- treatment of groundwaters by passage through an Amber1 i t e XAD-8 anion exchange resin column was used by Roden and Tallman (1454) t o reduce s u b s t a n t i a l l y the e f f e c t s of naturally occurring organic compounds on the measurement of Se( IV) and Se(V1) by a hydride generation-ETA-AAS procedure.NaBH4 as the basis of very s e n s i t i v e methods f o r the determination of B i (1871) and, unusually, N i (1130), i n seawater.In the l a t t e r case, elemental Ni is stripped from solution as nickel carbonyl by a mixed stream of CO and He gas, collected i n a liquid N2 t r a p , and f i n a l l y atomized i n a quartz furnace. Once again , very few papers describing atomic fluorescence methods have appeared. Demers and co-workers (452, 1089) have pub1 ished f u r t h e r descriptions of a commercial ICP-AFS instrument (see ARAAS, 1981, 11, 60) and i t s application t o the multi-element analysis of a CRM water.used f o r the determination of Hg (1765). given extensive d e t a i l s of a method involving reduction w i t h SnC12 and entrapment of the Hg vapour i n acidified KMn04 solution prior t o AFS detection; a l i m i t of detection of 1.6 ng 1-1 was reported.Chemical i n t e r - Lee u t i l i z e d reduction with Cold-vapour AFS continues t o be Bertenshaw and Wagstaff (1554) have 4.6.3 Atomic Emission Methods The l i t e r a t u r e on atomic emission methods continues t o be dominated by papers dealing w i t h applications involving plasma sources, p a r t i c u l a r l y the ICP. A general description of multi-element emission spectroscopic methods of analysis of i n t e r e s t t o the water industry has been published (1482).Reports of FAES methods are now rare, although i t was recommended as an a l t e r n a t i v e technique t o AAS by the UK Department of the Environment (857) f o r the determination of K i n raw and potable waters. I t was a l s o used (1458, 1857) i n an i n d i r e c t pro- cedure f o r the determination of low concentrations of SOP- i n r a i n , where BaS04 was added t o samples and the equilibrium concentration of Ba determined by FAES w i t h a N20/C2H2 flame.Two papers report the determination o f fluorine a t t r a c e levels i n waters by AES a t the 685.6 nm l i n e , following gas chromatographic separation. Feldman (1613) claimed t o detect down t o 70 pg F by excitation of a difluorodiphenyl s i l a n e residue i n a He glow discharge.Chiba e t a l . (875) excited F atoms from trimethylfluorosilane i n an atmospheric pressure MIP using a modified Beenakker TMOIO cavity, and reported reasonable agreement w i t h ion-selective electrode measurements on seawater. A capacitively coupled microwave plasma was employed (424) t o determine As i nApplications 191 sewage sludge, while M i l l e r e t a l .(770) used a M I P as a detector f o r C1- containing compounds i n the determination o f ppb l e v e l s o f t r i c h l o r o a c e t i c acid i n water, f o l l o w i n g methylation and gas-chromatographic separation. source f o r multi-element analysis. A review, w i t h 71 references, o f the applications o f ICP-OES t o waters has appeared (809) and several general d i s - cussions o f the technique were presented as conference papers (C236, C237, C239).Miyazaki e t a l . (401) have published f u l l e r d e t a i l s o f t h e i r procedure (ARAAS, 1981, 11, Ref. 878) for the i n d i r e c t measurement o f low l e v e l s o f P i n waters. Reduced molybdoantimonylphosphoric acid was extracted i n t o d i i s o b u t y l ketone and Mo determined a t the 202.03 nm l i n e o r Sb a t the 206.83 nm l i n e .A detection l i m i t o f 5.2 pg P m l - 1 was claimed f o r a 500 m l sample. son (1474) combined s e l e c t i v e reduction and t h e i r hydride generation-ICP-OES procedure (ARAAS, 1981, 11, Ref. 376) f o r the determination o f As species i n r i v e r waters.Emission measurements i n the V.U.V. region have been used t o determine B r and I i n brines (C238) and SO4- i n natural waters v i a the S 180.73 nm l i n e (C313, 2030). metals i n freshwater, by the use o f a heated spray chamber t o desolvate and s t a b i 1 i ze the sample aerosol , were reported ( 1855). metric detection o f isotopes i s being a c t i v e l y pursued (see Section 1 .2.1 .5).Edelson and Fassel (697) employed a high r e s o l u t i o n spectrometer t o obtain a m u l t i - i s o t o p i c analysis o f U when simulated solutions from a nuclear p l a n t were aspirated i n t o an I C P . The inductively-coupled plasma i s c l e a r l y now i n widespread use as an emission Pahlavanpour and Thomp- 2 Improvements i n s e n s i t i v i t y f o r the determination o f trace The use o f atmospheric pressure plasmas as i o n sources f o r the mass spectro- 4.6.4 ComDarison o f methods A review of atomic absorption and chromatographic methods f o r the determination o f Se i n water has been published (1035). appeared, i n which a recurring theme i s the wide discrepancy between reported values f o r trace constituents.r e s u l t s f o r the determination o f Hg i n seawater (1486). Good accuracy and precision were obtained f o r samples spiked w i t h HgC12 b u t serious e r r o r s occurred a t low, natural concentrations. From a 14-laboratory comparison (1644) o f sampling devices f o r c o l l e c t i n g seawater i n which Cd, Cu, Hg, Mn, Mo, N i , V and Zn were subsequently determined, i t was concluded t h a t the differences found were caused predominantly by a n a l y t i c a l r a t h e r than sampl i ng e r r o r s .Results from 20 laboratories (2288), which determined t o t a l Fe i n d r i n k i n g water by a v a r i e t y o f c o l o r i m e t r i c and AAS methods, suggested t h a t s i l i c a t e interference i n the l a t t e r procedure was p a r t l y responsible f o r the spread o f the data.Several sets o f resul t s from i n t e r - 1 aboratory comparison exercises have Thirty-two laboratories i n 16 countries compared Additional references on the preceding t o p i c - 693, 1468, 1469, 1598.Table 4.6 WATERS, SEWAGE AND EFFLUENTS Element A/nm Matrix Technique, Concentration Atomization, AnaIyte Form Sample treatment Ref.As As As As As As As As As As B B B Ba Ba Ba Be Bi 193.7 Dimethyl arsinic acid in water 228.8 193.7 - - - 193.7 - 193.7 553.6 553.6 - 306.7 Seawater Sewage, sludge, iron, steel Water, acids Water, soil Ground and cistern water Polluted waters River water Waste water Bottled mineral water Biological materials Coking and tar plant effluent Natural and geothermal water High salt waters Rain water Paper mill water Natural waters Sea water 0- 150 &g/I 0.27 pg/l 3-500 pg/g 5 -52 @g/l - > 0.02 mg/l - 0.2-50 &I > 1 .o fig/l - - - 0-5 mg/l - > 5 x lo-” g 4-25 ng/l A, ETA, L A, F , Air/N,/H,, Hydride, G E, P, CMP, Hydride, G A, ETA, L A, ETA, Hydride, G A, ETA, L A, ETA, L A, P, ICP, Hydride, G A, -, Hydride, G A.F, N,/Air/H,, Hydride, G E, P, ICP, L E or A, F, N,O/C,H,, L E, F, N,O/C,H,, L A, ETA, L A, ETA, L A, ETA, L Pass through Dowex AGSOW-XI resin; elute inorganic As with 0.1M H,PO,, monomethyl arsenic acid with 0 . 0 2 ~ NH, and dimethyl arsenate with 1M NH, As(II1): sample + 40% citric acid, adjust t o pH 5 with 10% NaOH, add NaBH, solution. As total: add concentrated HC1 + 40% KI and then NaBH, to generate arsine Digest sewage sludge in aqua regin (220”C, 2 h), evaporate filtrate to residue, dissolve in HCI + H,SO,; arsine generated into CMP - As oxidized t o As (V) with HNO, Matrix modification Extract As(II1) with APDC or diethyldithiophosphoric acid.Extract As(V) after reduction to As(1II) back extract into Cu(I1) solution to break down As chelate; add Ni(NO,), as an ashing aid Reference materials as standards; samples decomposed by HNO, under pressure Extract into 2-ethylhexane-l,3-diol in toluene Indirect sulphatc determination; t o 25 ml of sample add 25ml0.023M KMnO, + 7-15 mg BaSO, Solvent extraction with of Be as Be acetylacetonate Add HNO, to pH 0.7, boil for 1 h and filter, add tartaric acid 5% EDTA, adjust pH to 9.3 with aq.NH, and NaDDC to precipitate Bi, extract precipitated complex with CCI,, evaporate to dryness, dissolve residue in 6M HNO, 400 417 424 481 938 1072 1073 1474 C2178 2256 C208 694 1858 637 1458 2286 1201 1719~ Bi Br C C Ca Ca Ca Ca Cd ~ -~~ ~~- ~ Wastewater, seawater, urine Brine 43 1 Oil in water - Trichloro acetic acid ~ ~~ ~ Matrix modification and solvent extract for pre-concentration Dilute brine 1 g to 10 g with distilled water A, ETA, L 0.5 mg/l-5 g/l > 10 mg oil/l r g / l E, P, ICP, L E, F, -, L E, P, GC-MIP, G A, F, Air/C,H,, L A, F, -, L A, F, -, L E, P, ICP, L C238 (0 713 770 505 024 1549 2224 385 Extract acid with Et,O, derivitize to CI,CCO,Me with CH,N,, inject into GC with pre-column enrichment 1 ml sample + 1 ml 5% SrCI,, dilute to 10 ml Preconcentrate Ca with CCI, form of 8-oxyquinolate complex 422.7 Ground water Purified watcr - 430.3 Sewage sludge, liquors - Surface waters, 228.8 Lake sediments sediments 0.01 -0.2 mp/l 0.5-3.0g/l - Fractionate metal forms using distilled water size-exclusion chromatography 300 mg sediment + 5 ml each of H,O, HClO,, HNO, and HF, heat gently to evaporate to dryness, take up residue in 2 ml HNO, dilute to 25 ml; excitation source is an ICP with Cd (lOg/l) nebulized.Preconcentrate Cd by co-precipitating Cd with FeS0,.7H,O and air oxidation Preconcentrate Cd on Au wire Complex Cd with APDC and preconcentrate with CCI, Digest 0.5 g with HF/NH,/HClO, (10:4:1 ml) in Teflon bomb; suppress Na and K interferences with 1% (NH,),PO, and 1% (NH,), SO, Ignite sample at 550°C for 2 f h leach in 3MHCI for 2 h, then filter Preconcentrate electrochemically 0.1 - 100 fig/g F, F, Air/C,H,, L Cd Water 0.05-6 pg/l A, F, -, L 472 I71 925 1105 Cd Cd Cd Lake water Seawater organisms Sediments 3 1-4 1 ng/l - 0.4 mg/l A, ETA, L A, ETA, L A, ETA, L Cd Sewage sludge 1-3 X lo3 mg/l 1444 2031 C2174 Cd Cd Natural waters Seawater, urine Potable waters 1-4.5 pg/l > 0.013 pg/l > 0.04 pg/l 0- 100 pg/l A, ETA, L A, ETA, L 200 ml sample: add 1 ml HNO,, evaporate to 20 ml, dilute to 150 ml, neutralize with 10% NaOH and 3% HCI, dilute to 200 ml, add 4 ml 1% ammonium pyrrolidine-1-carbodithioate, extract with MIBK; nebulize organic phase Ion exchange separation of Cr(V1) and Cr(II1) prior to determination Co-precipitate Cr(V1) with Co (11)-pyrrolidine carbodithioate complex, adjust to pH2 to separate Cr(III), and determine To acid solution add 1.5 ml of 3.5% Zr OH and NH, to pH 9.5, filter precipitate and add 2 ml HNO,, heat to dryness, redissolve in 0.5M HC1 and dilute to 10 ml Co 240.7 A, F, Air/C,H,, L 1706 Cr Cr Cr Environmental samples A, ETA, L C312 Seawater A, -.L 615 Seawater 746Table 4.6 WATERS.SEWAGE AND EFFLUENTS-continued Element h/nm Matrix Technique, Concentration Atomization, Analvte Form Sample treatment Ref. Cr c r c u c u c u c u c u F Fe Fe Fe Fe Fe Fe Fe 'H ZH Hg Hg Hg - - 324.7 - - - 685.6 248.3 248.3 - - 248.3 248.3 248.3 Ha Du 253.7 253.7 Bottom sediment Sediments Waters, snow, anions, cations Potable waters Seawater Seawater, brine and salt Natural waters Water, urine River, tap, waste water, snow Underground and tap waters Seawater Coal liquid streams Water Raw and potable water Potable water Enriched water Sea water, filtrates. suspensions Artificial seawatei Various waters - 0.9-4.3 pg/l 1 - 100 pg/l 5 -200 pg/l 7.5-7.5 x lo4 pg/s 2.5-14pgg/l 21 -307 pg/l rg/l 0-200 pg/l 0-200pg/l 0.03% 1.5-394 ng/l 0.7-5.0 ng 1.0-19.3ng 500 ng/l > 0.06 mg/l A, -, L A, -, L A, F, Air/C,H,, L A, F, -, L A, ETA, L A, -, L A, -, - E, P, MIP, L A, F, Air/C,H,, L A, F, Air/C,H,, L A, ETA, L A, ETA, L A, ETA, S A, ETA, L A, Cold vapour, L Alkalj fusion and acid extraction Alkali fusion or acid extraction Selective extraction of Cu with Al(Cup),-methyl salicylate at pH 3.5 - Preconcentrate with 8-hydroxyquinoline-l,2-dichloroethane system Extract Cu complex of 5-bromosalicylaldoxine into CHCI,, decompose with HNO,/HClO, Selective extraction with fluorinated p-diketones in m-xylene Extract F from acidified sample with Me,SiCI solution (solvent: MePh), inject extract into GC and detect with MIP Adjust pH to 3.5-5.0 with acetate buffer, add 5.0ml of 0.01M aluminium cupferrate/methyl salicylate and shake for 5 min To sample of < 24 pg Fe, add 10 mg dimercaptomaleonitrile, 1 ml of 1M acetate buffer and 2 ml of 0.03751~ tetrabutyl ammonium bromide solution, dilute to 50 ml and extract the ion pair with MIBK See Cr, ref. 746 Ion pair extraction of dimercaptomaleonitrile complex Direct nebulization of sample containing 1% HCI Determine methl mercury by eluting from macroreticular chelating resin with 4MHC1, extract with C,H,, back extract with glutathione solution, decompose with KMnO,/ Preconcentrate Hg ions and organic Hg on dithiocarbamate bonded silica gel, determine Hg by heating gel in ETA Decompose organomercury compounds with KMnO, in conc.HCI or BrCl in organic solvent HZSO, 920 1131 460 667 1074 1831 1900 875 460 46 8 746 914 1952 2287 2288 936 3 464 562~ Riverwater sediments - - Seawater 300 - Potable water > 500 pg/i - Natural water - - Water > 0.08 pg/l - Methylmercury in - - Waste water, sludge - water 253.7 Drinking water 0-700 ng/l 253.7 Hair, urine, tuna 3-5 X 10-'-3.0ppb 253.7 Water, wastewater 0.1 - 10 pg/l - Water 0.01 -1 .Opg/l - Raw and potable water c 10 mg/l - Boiler feed water 0.01 -0.2 mg/l - Surface waters, - Seawater rsll 285.2 Ground water - sediments, pure water 279.6 Raw and potable water 0-200 pg/l 202.0 Phosphorus in natural > 5.2 ng/l waters Natural water > 0.3 pg/l - Seawater > 0.05 ng A, Cold vapour, L A, Cold vapour, L A, ETA, L A, ETA, L A, ETA, L F, Cold vapour, L A, Cold vapour, L A, Cold vapour, G E, P, Ring discharge, L E, F, L A, F, Air/C,H,, L A, F, L E, P, ICP, L A, -, L A, F, Air/C,H,, L E, P, ICP, L E, -, L A, -, L - Treat with H,SO, and halide to 0.001-0.1 N HISO, and 0.001-1M halogen ion, pass through activated C column, desorb at 600-1O0O0C, heat desorbed Hg to 600°C to remove 0, then determine Anion exchange and preconcentration of Hg on Dowex AGIX8 resin Electrochemical preconcentration Studies of selective adsorption resins to adsorb methyl- mercury Hg S stabilization toward drying or alternatively the formation of Hg dithionate is employed Collect Hg vapour in KMnO, solution, reduce and pass vapour to fluorescence cell Digest in 2.5 ml of 1OM KOH at 90 "C for 15-30min, centrifuge and dilute supernatant to lOOml with 1% NaCl after addition of 7.5 ml HNO, and 1 ml 1% K,Cr,O,, Hg vapour generated with SnCI, on NaBH, Rinse stream mixed with 1% SnCI, in 3% H,SO,, air passed to reduce, Hg vapour extracted at gas/liquid separator and determined See Ca, ref. 505 See Ca, ref. 924 See Ca. ref. 2224 See Cr, ref. 146 See Fe, ref. 2287 Indirect determination of P in waters; add 500 ml ammonium molybdatejantimony potassium tartrate, add ascorbic acid and extract into di-isobutyl ketone Preconcentrate on charcoal followed by spectrography Reduce to Ni metal with NaBH,, form the carbonyl and strip from solution with He-CO mixed gas stream, collect in N, trap and then determine with heated quartz-tube atomizer 616 $ 619 5 665 1075 1129 1132 1199 1554 1614 2029 C2398 85 I 505 924 2224 746 2287 401 1036 1130Table 4.6 WATERS, SEWAGE AND EFFLUENTS-continued Element h/nm Matrix Technique, Concentration Atomization, Analyte Form Sample treatment Ref.P Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb s (-SO,) s (-SO,) Sb Sb Sb Sb Se Se Se 202.0 (Mo) Natural waters 206.8 (Sb) - Aqueous - Sediments - Sewage sludge 217 Borehole and river - Mineral waters - Seawater - Water 217 Aqueous water 217 Aqueous Natural water - Water 180.7 Natural waters 180.7 Natural waters 21 7.6 Water 217.6 Seawater - Natural water - Water, soil - Coal ash, water ~ Environmental waters - - - 5-200ng 35 mg/l 1-3000 mg/l - >0.1 pg/l > 0.08 mg/l 0.05-10000mg/l > 1 ng - > 0.8 ng E, P, ICP, L A, Quartytube, L A, ETA, L F, F, L A, ETA, L A, ETA, L A, ETA, L E, P, D.c., L A, F, Air/C,H,, L A, F, Air/C,H,, G A, ETA, L A, GC-AAS, G E, P, ICP, L E, P, ICP, L A, ETA, L A, Hydride, Air/N,/H, G A, Hydride, Air/N,/H,, G A, Hydride, ETA, G A, -.- F, Hydride, - - Indirect determination of phosphorus; sample + ammonium molybddte and antimony potassium tartrate, add ascorbic acid and extract into di-isobutyl ketone Extract Pb" into CHCI, as dithiocarbamate complex, evaporate solvent, methylate residue with Me,Li to Me,Pb, trap analyte vapour on a short column (Porapak Q) then elute into quartz furnace See Cd, ref. 1105 See Cd, ref. 1444 Add 1% HNO, and 0.05% La as lanthanum chloride to solutions I Preconcentrate on a tungsten filament Preconcentrate on polymaleic anhydride resin, elute with HNO,, analyse with washings Dithizone/CHCl, extraction followed by back extraction using HNO, Determination of ionic dialkyl and trialkyl lead in water by extraction with dithiocarbamate and benzene followed by butylation and GC Selective separation and differential determination of Sb(II1) and Sb(V) using N-benzoyl-N-phenylhydroxylamine See As, ref. 417 Generate stibene by reduction with Zn Review HNO,/HCIO, digestion Review 40 1 966 1105 1444 1514 1856 1953 C214.5 2213 2250 C2421 C2430 C313 2030 332 417 874 938 1035 1202 1399~ ~~ Se Sn Sn Sn Sn Ta Te U V V V Zn Zn Zn Various (8) Various (7) Various Various ( 5 ) Various (7) Various Various (3) 196 Ground waters Water 224.6 Rocks - Natural sediments 286.3 Marine organisms - Natural water - Water Tank solutions - Seawater - Seawater - Suspended particles 213.9 Polluted stream 307.6 - Potable waters 213.9 Seawater - Geothermal brine - Drinking water - Oil shale leachates - Agriculture water - Seawater - Sediments, nodules, - NBS water, NBS leaves plankton, seawater 0.32-1 .Owg/l > 0.4 pg/l 0.001-0.14 mg/l > 0.3 wg/l 0.09 mg/l 1.7-100 pg/L 2.4-24 U g J L 0-500 mg/l - > 1 .o wg/l A, F, Hydride, G A, GC-AA, G A, Hydride, quartz A, GC-AA, G A, Hydride, F, G E, -, L A, ETA, L F, P, ICP, L A, ETA, L A, ETA, L A, -, S A, ETA, L A, -, L A, ETA, L A, ETA, L A, ETA, L A or E, P, ICP, L A, F, -.L A, F, Air/C,H,, L E, P, ICP, L E, P-MS, MIP, L ~~~~ ~ ~ ~ ~~~ ~~~ ~ ~ Humic acid and other groundwater interferents removed by passing through XAD-8 ion exchange column; results compared with KMnO,/HCl digestion procedure Speciation of methyltin(1V) and tin(IV), by extraction into C,H, containing tropolone from water saturated with NaCI, butylate and analyse by GC-AAS Fusion of powdered rock with Li metaborate followed by digestion with HF/H,SO,.The evolved hydride is swept to electrically heated quartz tube. Oxalic acid and 1,lO- phenanthroline are used to supress Fe, Cu, and Ni inter- ferences Methylation of Sn(1I) compounds in preference t o Sn(IV) Acid decomposition of samples followed by La(II1) co- precipitation and conversion t o stannane with 2% Na tetra- hydroborate (111).See Nb, ref. 1036 Te(1V) in water extracted with KI and MIBK, back extract with NH,OH; Te(V1) is reduced to Te(1V) by boiling HCI solution Isotopic analysis Vanadium concentrated by complexing with N-phenylbenzo- hydroxamic acid Extract with tetramethylene dithiocarbamate Collect suspended solids by high volume sampler and determine V Add NH,NO, to eliminate chloride interference or complex chloride with silver Preconcentrate by evaporation Add citric acid Coprecipitation of trace metals with Co or In-APCD complex tube, G - - Add nitric acid to pH 4 then 2% DDC to complex metals, stir and add activated charcoal, settle, pour off solution and dry charcoal, extract metals with 1 :2, HNO,/water Pressure-filter water through millipore (0.45 wm) filter followed by LiBO, fusion Isotope dilution technique 0 (r, 76 9 1170 1473 1877 1036 617 697 582 1133 1989 3 25 814 856 C89 c 9 5 C96 ClOl C104 C147 C160Table 4.6 WATERS, SEWAGE AND EFFLUENTS-continued Technique, Element k/nm Matrix Concentration Atomization, Sample treatment Ref.AnaIyte Form Various Various (6) Various (8) Various (17) Various (10) Various Various Various (1 2) Various (10) Various Various Various (3) Various (8) Various ( 5 ) Various (6) Various (4) Various Various (13) Various Various - Reference standards - Silicone oil in non aqueous solvents, natural waters - Seawater - Water - Surface waters - Seawater - Water or uranium - Environment samples, - Water, sewage, sludge solutions sediments, shell fish - Waters - Waters - Estuarine waters - Seawater Sediment cores Deionized water Marine sediments, biological materials Water, stainless steel and low alloy steel Water - Wastewater - Water > 0.01 pg/l - 0.4-25 pg/l > - - - Mg/l level - - - 0 -4 pg/l - 1-200 mg/l 0.1-20% > 0.001 ng/l > 0.01 mg/l E, P, ICP, L E, P, D.c., L E, P, ICP, L E, P, ICP, L E, P, ICP, L E, P, ICP, L E, P, ICP, L A, F, Air/C,H,, F, XRF, L E, P, ICP, L E, P, ICP, L A, ETA, L A, ETA, L A, ETA, L F, P, ICP, L A, ETA, L E, P, ICP, L A, E, F, -, L Reference materials used as standards Extract silicone oil from water with hexane; extract trace metals from water with pyrrolidine carbodithioic acid in chloroform Summary of preconcentration techniques and author’s procedure of preconcentration on silica immobilized 8-hydroxyquinoline - - Preconcentration using poly (dithiocarbamate) chelating resin at pH5 or pH8-9 depending on elements Uranium extracted into tris-(ethylhexyl) phosphate leaving impurities in aqueous solution Sediments dissolved in 8N nitric acid, shell fish digested in nitric acid L Aquo regia digestion of sewage sludge Electrochemical preconcentration Metals chelated with 8-hydroxyquinoline and selectively adsorbed onto C,, bonded silica gel Sample leached with 25% AcOH-0.25M hydroxylammonium chloride and residue dissolution with HC1-HNO, -HF- H,BO, mixture Digestion with conc.HNO,/H,SO,/HF in sealed Teflon vessel at 120°C and 3 atm for 3 h;alternatively digest with SMHNO, Trace elements preconcentrated on tungsten wire and then a tomized Review of atomic spectroscopy for water analysis C208 C229 C236 C23 7 C239 C240 C242 C243 C25 8 C280 C286 C297 318 365 390 45 1 452 501 618 666b g Various Various (4) Various (6) Various (6) Various Various Various Various (9) Various Various (3) Various Various (7) Various (8) Various (7) Various (4) Various Various (10) Various (1 2) Various Various Various (8) Various Various (7) Various VdrioUS (1 2) Various (14) Various Sewage Drinking water, leaves, H,SO, Natural waters Natural waters Surface waters Waste water Waters Waters Waters Waste water, effluents Coal fly ash leachates Estuarine sediments Sewage sludge Waste water Fresh waters Water Surface waters Sediments Natural waters Humic and fulvic materials Urban snow Water and low alloy steels Natural waters Seawater Suspended particles Water/acid solutions Seawater A, -, L A, Hydride, -, G E, P, ICP, L E, P, ICP, L E, P, ICP, L E, P, ICP, L E, P, ICP, L E, Hydride, P, ICP, G E, P, D.C., L A, ETA, L A, ETA or F, L A, ETA, L A or E, -, D.c.or ICP, XRF, L A, ETA, L F, P, ICP, L Spectrochemical A, -, L r:, XRF, - E, P, ICP, L A, ETA, L ~~ ~~ Digest with HNO,/H,O, - Trace elements concentrated by re-extraction with diphenylcarbazone and C,H,N in toluene Trace metals extracted with N-cinnamoyl phenyhydroxyl- amine and 8-oxyquinoline.extracts dried at 8O-9O0C, ashed at 500-200°C and atomized a t 2100-2400°C for 5s - (Heavy metals) Review (Heavy metals) Review - (Heavy metals) - Persulphate digestion followed by heating at 95 "C in 6M HC1 - (Heavy metals) Metals desorbed from chelating resins or ion exchange resins Digest sample with HC1 and HNO, after calcination at 450°C in presence of NH,NO, Multielement standards for calibration - Preconcentration by ion exchange Filter with 0.45 pm millipore and dissolve in HNO, 693 % 700 9' 712 744 745 76 8 809 812 813 854 859 896 918 921 922 926 967 994 1037 1038 1039 1089 1134 1198 1200 C1302 1365N 0 Table 4.6 WATERS, SEWAGE AND EFFLUENTS-continued Element h/nm Matrix Technique, Analvte Form Concentration Atomization, Sample treatment Ref.Various Various (7) Various (7) Various (10) Various ( 5 ) Various (5) Various (10) Various Various (32) Various (3) Various Various Various (6) Various ( 5 ) Various Various (4) Various Various (10) Various (13) Various ( 5 ) Sewage sludge A, F, N,O/C,H, or Air/C,H,, ETA with hydride, L - E, P, ICP, L Water and wastes 0.02-I.Omg/l A, ETA, L Waters d - m g / l Saline waters p g / l levels A, F, Air/C,H, and ETA, L A, F, -, L Sediments, sewage sludge - A, F, -, L - Water and waste water Waters and sediments - Waters - Seawater - Environmental samples - Raw sewage - Sewage sludge - Seawater, fuel oils - Seawater - Natural waters Fresh water Synthetic water - Sewage sludge - River, sea and wastewaters A, -, L E, -, L E, P, ICP, L A, ETA, L A or E or F, F or P or ETA, - A, -, L -50 mg/l A, F, Air/C,H,, L E, P, ICP, L A, ETA, L A, -, L E, P, ICP, L A, -, L A, -, L E, P, ICP, L Homogenization with 1% V/V HNO,, digestion with HNO,/H,SO, or HNO,/H,O, or HNO,/HCIO, or HNO,/MF or HNO,/H,SO,/H,O,: hydride generation for As, Sb, Te Preconcentration using floatation-separation technique Review of Environment Protection Agency methodology Preconcentration with Chelex-100 resin after ozone bubbling t o break down metal complexes in water Comparison of extraction techniques Interlaboratory comparison Review Evaporate 15 ml to 1 ml in aluminium block Selective extraction of Cu, Pb and Cd on Chelex-100 resin Review of atom cells as detectors for gas chromatography Pretreatment with HNO, and HCI; then extract metal ion as tartrate complexes which are absorbed on Dowex 2X-8 column for elution and determination Reflux with 6M HCI and 2 drops of acid washed kerosine (to prevent foaming) for 15 min, cool and wash into tube to boil wet sludge with HNO, Comparison with NAA, X-ray emission and polarography Interlaboratory study Comparison of digestion procedures using: dry ashing followed by aqua regia, aqua regialHN0, and HNO, followed by H,SO,, and dry ashing 1401 1412 C1436 1446 1466 1468 1469 1482 1541 1598 1606 1616 1678 C1695 1720 1740 1855 1903 1990 1991b : Various (4) Various (6) Various (8) Various ( 6 ) Various (3) Various (50) Various ( 6 ) Various (7) Various Various (6) Various Various ( 5 ) Various (4) Various (6) Various (8) various ( 5 ) Various (1 4) Various (3) Various (8) Bottom sediments Sediments Water Distilled and river water High purity primary loop cooling water Fly ash leachate High salt water, ocean water Waters and wastes USGS water samples High salt matrices Plating bath solution Seawater, tz;1 water Brine Estuarine waters Waters, seawater, river water Natural waters Waters, sediments Petrol, seawater, water Aqueous solution A, F.Air/C,H, or Air/ prop/but, L - A, ETA, L 0.1 - 1 .O mg/l A, -, L - A, ETA, L A, -, L 0-1 0 pg/l E, P, ICP, L E, ETA into P, ICP, L - A, ETA, L E, P, ICP, L A, ETA, L E, P, ICP, L A, ETA, L 0 - 1 5 0 p&/l A, ETA, L - A, ETA, L E, P, ICP, L - - 1-60 ng A or E, ETA or P, ICP, L A, F, -, L A, GC-F, Air/C,H, with heated tube, G A, ETA, L Diluted samples acidified t o 1% HNO, and homogenize Add NH,Fe sulphate solution, adjust t o pH7 and add diethyldithiocarbamic acid, filter precipitate and dissolve in HNO, - Matrix modification To filtered seawater add 50 mg/l trien DTC cellulose and shake for 30 min, filter and ash cellulose at 500°C.Dissolve ash in 100 pl HNO,, dilute to 1 ml and determine To lOOml of sample, add 20 ml Freon-TF and acetate buffer + 1 :1 APDC/DDC, separate Freon phase and back extract metals into 100 pI with HNO, Digest 500 ml of sample with HNO,, chelate with APDC at pH 2.4 and extract metals into DlBK in preference to MlBK Trace metal speciation by GC-AAS: for dimethylselenium and dimethyldiselenium mixtures use 3% Dexil-300 column on Chromosorb WHP; for tetra-alkyl lead use 5% Carbowax 2OM on Chromosorb 750 at 170 "C and 64 ml/min N,; for dialkyl mercury compounds use Fame column at 90-170°C To 100 ml sample add 1 ml of ammonium acetate buffer, adjust to pH 4-5 or 8-9 using dilute HNO, or aqueous ammonia, pass through column containing SM-7 resin and elute with 10 ml 1% HNO, 1992 $ 2005 5 3 2028 2032 2033 2034 C2068 C2093 C2107 C2155 C2188 2218 2226 226 1 2265 2283 2289 2300 2345202 Analytical Atomic Spectroscopy Useful intra-laboratory comparisons have been made of both general techniques and of methods f o r the determination of individual elements. Playle e t a l . (858) compared the ferron colorimetric method, the lumogallion fluorimetric method and an ETA-AAS procedure f o r the determination o f A1 i n water. They found t h a t the lumogallion method was the most s e n s i t i v e , had few interferences and was applicable down t o about 1 pg 1 - l . quality standards, Eaton e t a l . (2283) compared the p r a c t i c a l , as opposed t o the manufacturer's, detection l i m i t s a t t a i n a b l e with ICP-OES, FAAS and ETA-AAS and highlighted the f a c t t h a t the former were typically poorer than the l a t t e r by a f a c t o r of 5 t o 10. sewage sludge, i t was concluded (854) t h a t treatment w i t h K2S208 a t low pH, followed by heating a t 95 OC with 6M HC1 was the best procedure t o use p r i o r t o the determination of As, Sb and Se by hydride generation-ICP-OES. In the context of s t a t u t o r y water From a comparison of 5 sample digestion procedures f o r Additional references on the preceding topic - 1990, 2034.

ISSN:0306-1353    

DOI:10.1039/AA9821200187

出版商:RSC    

年代:1982

数据来源: RSC

摘要:

Applications 203 4.7 SOILS, PLANTS AND FERTILIZERS The number o f publications i n t h i s subject area has again been very high, partic- ularly popular topics being sample extraction o r digestion, investigations of ETA-AAS and the routine use of ICP-OES. atomic spectroscopic methods a r e s u f f i c i e n t l y r e l i a b l e f o r most analyses of agricultural materials, and i t is becoming increasingly unusual f o r authors t o confirm t h e i r r e s u l t s by comparison w i t h a " t r a d i t i o n a l " analytical procedure.There is no longer any doubt t h a t 4.7.1 Sample Preparation Attention continues t o be given t o a extraction procedures. compared the effectiveness of e i g h t extraction solutions f o r Al, Cd, C u , Fey Mn, Ni and Zn using 25 s o i l s of diverse o r i g i n .Five chelating agents (EDTA, HEDTA, DTPA, EGTA and NTA) used a t 0.005M concentration and pH 5.3 (using ammonium acetate/acetic acid buffer) were compared w i t h 0.1N HC1 , ammonium acetate/ a c e t i c acid a t pH 5.3 and the DTPA micronutrient s o i l t e s t a t pH 7.3. differences i n performance were noted, and discussed i n terms of equilibrium calculations, but i t was not possible t o recommend a single "ideal" procedure.Combs and Dowdy (2318) found t h a t extraction of dredged s p o i l s w i t h DTPA ( a t 0.005M and pH 7.3 w i t h 0.005M CaC12 and 0.1M triethanolamine) gave concentrations of Cu, Ni and Zn which correlated well w i t h the uptake of these elements by barley and rye grass, although the Cd r e s u l t s did not correlate. -- e t a l .(1066) reviewed the ISFEI method f o r determining extractable n u t r i e n t elements i n s o i l , and recommended t h a t NaHC03 be replaced w i t h 0.25M NH4HC03 and t h a t the use of activated carbon t o decolourize e x t r a c t s be avoided, in order t o obtain quantitative recovery of P and t r a c e elements. Many reports have appeared o f comparisons of digestion procedures f o r plant material.again, they do a t l e a s t help the plant analyst t o evaluate the consequences of u s i n g his chosen method f o r a p a r t i c u l a r element. For example, Knight (1625) carried out y e t another exhaustive analysis of NBS orchard leaves determining 1 2 elements, including As, Be, Cry Cu, Fey Mn, Mo, Pb and Z n , by four procedures avoiding the use of HC104.Dry ashing was deemed best f o r a general multi- element approach but wet digestions (HN03/H2S04 and HN03 alone i n single o r repeated digestions) proved superior f o r p a r t i c u l a r groups of elements. Simil- a r l y , Bird (1465) compared dry ashing a t 500 OC w i t h HC1/HN03 digestion f o r Cd, Cry C u , Ni , Pb and Zn i n grass, corn and wheat.Net ther method could be recom- mended as having an overall s u p e r i o r i t y , although dry ashing was found t o be quicker and e a s i e r . H u n t (1187) reported t h a t extraction of various plant mater- i a l s w i t h d i l u t e HC1 was equally effective a s wet digestion f o r the determination of Cay K and Mg. during wet digestion of biological material w i t h a variety of commonly used Norvell (C2094) Marked Van der Merwe Although i n many ways such studies are merely covering old ground Robberecht e t a l .(1397) used 75Se t o monitor elemental losses104 Analytical Atomic Spectroscopy procedures. The observations, too numerous t o mention here, should be noted by any analyst carrying o u t t h i s type o f determination.compared HF/HN03/KMn04 digestion w i t h f i v e v a r i a t i o n s o f H2S04/HN03 digestion f o r Hg determi nations. c a t a l y s t was equally e f f e c t i v e and avoided the need f o r expensive PTFE bombs. Gestring and Soltanpour (339) compared several p l a n t digestion procedures f o r B determination, and highlighted the contamination problem w i t h any s o r t o f glass apparatus.Use o f HN03 i n Nalgene b o t t l e s was recommended. Several reports o f s p e c i f i c digestion procedures are also worth noting. Nonaka and co-workers (342) studied i n d e t a i l the elemental losses which occurred during d r y ashing o f NBS orchard leaves and bamboo leaves under various experimental conditions, including the e f f e c t o f a s i l i c a dish.No losses occurred f o r the a1 k a l i n e earths , r a r e earths, A1 , Coy Fey Mn, V and Zn, over the 200-800 OC temperature range, b u t a v a r i e t y o f problems were noted w i t h As, B r , C1, C r , Hg, Sb and Se. Welsh and Frost (1464) described a r a p i d digestion procedure f o r Hg i n sewage sludge and p l a n t materials. Samples (0.1 t o 1.0 g) were heated a t 160 OC, i n i t i a l l y w i t h HN03/V205 and subsequently w i t h the a d d i t i o n o f H2S04.Hg using SnC12/HC1 reductant. ized O2 combustion technique f o r the determination o f trace elements (As, B, Cd, C r y Cu, Fey Hg, I , Mn, Pb, Sb, Se, Te and Zn) i n organic materials. Excellent r e s u l t s were obtained f o r 7 NBS reference materials, but only about one sample per hour could be handled.Wen and Geng (911) treated EDTA soi 1 e x t r a c t s w i t h e i t h e r APDCIMIBK o r HCl/ascorbic acid/MIBK t o concentrate Cd, Cu, Pb and Zn. Shan e t a l . (1123) extracted Se from s o i l digests, using 1 ,2-diamino-4-ni trobenzene, which produces 5-ni tro-2,lY3-benzo- selenadiazole, i n t o organic solvent f o r d i r e c t determination by ETA-AAS.Oxine/ CHC13 e x t r a c t i o n o f p l a n t digests was used (1817) f o r the spectrographic deter- mination of Cu, Fey Pb and V, the organic e x t r a c t being added t o graphite powder containing 0.1% Pd as i n t e r n a l standard. Speciation studies appear t o be o f p a r t i c u l a r i n t e r e s t i n s o i l analysis. Woolson and co-workers (1117) investigated the s o i l metabolism o f alkyl-As herbi- cides using anion-exchange HPLC t o separate arsenite, arsenate, cacodylic acid and monomethylarsonic acid (MAA) followed by ETA-AAS.Anion exchange was also used by Austenfeld and Berghoff (1731) t o separate arsenite and arsenate (only the l a t t e r being retained by the A63-X4A r e s i n ) , and by Takamatsu e t a l .(1783) i n a study o f s o i l p o l l u t e d w i t h As. This l a t t e r group found arsenate t o be the major component, b u t were also able (using ETA-AAS) t o i d e n t i f y and determine a t the ppb l e v e l arseni t e , monomethylarsonate (MMA) , dimethylarsinate (DMA) and two new organo-As compounds. Several types o f l i q u i d chromatography (gel perme- Dehairs e t a l .(1414) The former was best o v e r a l l , a1 though H2S04/HN03/H202/V205 The procedure was optimized t o s u i t the cold vapour determination o f Knapp e t a l . (532) described a p a r t i a l l y mechan- Sample preconcentration techniques continue t o be reported.Applications 205 ation, i o n exchange and adsorbent r e s i n ) were used i n conjunction w i t h ETA-AAS by Butterworth and Alloway (1472) t o investigate the major Cd species i n pol- l u t e d s o i l s ; o v e r a l l l e v e l o f Cd contamination.the organo-Cd species present were found t o vary markedly w i t h the 4.7.2 Atomic Absorption and Fluorescence Methods Reports continue t o appear on applications o f flame atomic absorption methods t o s o i l and p l a n t analysis, b u t there i s no doubt o f the growing p o p u l a r i t y o f ETA and vapour phase techniques.Harnly e t a l . (1572) evaluated t h e i r "SIMAAC" technique (see ARAAS, 1980, 10, 70) using an air/C2H2 flame f o r the simultaneous multi-element AAS determination o f Cay Coy C r y Cu, Fey K, Mg, Mn, Nay N i and Zn i n various NBS s o i l and b i o l o g i c a l CRMs.A l l r e s u l t s f o r Coy C r y Cu, Fe, K, Mn and Zn (using one s e t o f compromise conditions) were w i t h i n 25% o f the c e r t i f i e d values; found t o s u f f e r serious matrix interferences. Lau, Ure and West (2257) deter- mined Se i n p l a n t material using O2 f l a s k combustion and atom-trapping flame AAS (see ARAAS, 1981 , 11, 85); considerable modifications t o the technique overcame severe matrix interferences. Mn d i r e c t l y i n s o i l s by i n t r o d u c t i o n o f s l u r r i e s i n t o air/C2H2 ( f o r Cu) o r N20/C2H2 flames.ous a g i t a t i o n o f the s l u r r i e s (prepared i n 20% isopropanol-water) i t was possible t o achieve 1 2 % RSD. Lowe e t a l . (545) determined I i n s o i l s , plants and f e r t i l - i s e r s by d i r e c t AAS i n a N20/C2H2 flame using a c a p i l l a r y discharge lamp as the 1 l i g h t source and an Ar-sheathed o p t i c a l system.was obtained using the 183.0 nm l i n e . (2239) o f the problems o f As determination i n p l a n t materials. Analyses were c a r r i e d out i n the range 2CL300 ng As per g o f dry material, b u t severe i n t e r - ferences were experienced fromP contained i n the matrix and H2S04 used i n the wet digestion.A s ( I I 1 ) t o allow e x t r a c t i o n i n t o toluene. Suzuki and Ohta (1870) investigated the use o f thiourea as a matrix modifier f o r Cd and observed no interferences during the analysis o f b i o l o g i c a l materials w i t h a Mo microtube atomizer. Ma and Wu (1648) determined Ce, Eu, Nd and Sc i n s o i l s using a p y r o l y t i c graphite tube l i n e d w i t h Ta o r W .respectively, and r e s u l t s obtained on HF-HN03 s o i l extracts correlated w e l l w i t h those obtained by NAA. using ETA-AAS. which overcame the problems which a r i s e i f mg amounts are taken d i r e c t l y ; o f ensuri ng homogenei ty and of weighing the samples . N i was generally a t o r below the detection l i m i t and Ca and Mg were Stupar and A j l e c (1512) determined Cu, Fe, Mg and With adequate grinding (0.5 h i n a wet b a l l m i l l ) and continu- A detection l i m i t o f 9 pg m l - Reports received concerning electrothermal atomic absorption included a study It was necessary t o perform a preliminary reduction o f As(V) t o The detection l i m i t s were 100, 0.2, 20 and 0.2 ppm, Considerable i n t e r e s t has been shown i n the d i r e c t analysis o f s o l i d samples Jackson and Newman (C314) described a s l u r r y technique f o r s o i l s Grobenski and co-workers206 Analytical Atomic Spectroscopy (548) described an a l t e r n a t i v e approach using a special sampling tool f o r the introduction of material i n t o the furnace.Good r e s u l t s were achieved f o r various CRMs of plant materials, provided t h a t matrix interferences were overcome using a variety of specialized techniques. Fagioli e t a l . (952) compared s o l i d sampling w i t h conventional wet digestion (H2S04-H202) f o r determining Cu and Mn i n maize roots. analysis, small sample s i z e and l e s s r i s k of contamination, but RSDs were 7.7% and 5.7% compared w i t h 1.7% and 0.7% obtained w i t h a liquid sample.Favretto and co-workers (1627) made a similar comparison f o r Pb i n vine leaves and sea- weed and found no s i g n i f i c a n t differences i n the mean r e s u l t s obtained by the two techniques . of elements. Schnitger and Lieck (735) determined Se in forage samples w i t h a detection l i m i t of 7 ng following HN03/HC104 digestion, removal of i n t e r f e r i n g cations by ion exchange and the generation of Se hydride using NaBH4.-- e t a l . (723) determined c a s s i t e r i t e Sn in s o i l s and sediments w i t h a detection l i m i t of 0.2 pg g-l , RSD of 12% and a throughput of 60 samples h-l. decomposed w i t h NH41, the sublimate dissolved i n t a r t a r i c acid and NaBH4 used f o r the production of SnH4 i n a continuous f l o w system.reported the s e l e c t i v e determination o f arseni t e and arsenate i n s o i l e x t r a c t s using an automated hydride generator. using 1 M ammonium c i t r a t e and a r s i n e generated by adding 4% NaBH4 solution i n aqueous 0.5% NaOH.hydride generation programme repeated f o r the determination of As(V). Two i n d i r e c t AAS methods a r e of i n t e r e s t . seaweed u s i n g a cold vapour Hg spectrometer, the method depending on the decrease i n Hg(I1) absorbance a t 253.6 nm caused by the presence of I-. a c i d i t y (3 t o 4M HN03) there was no interference from C1- o r Br- and a detection l i m i t o f 2.5 pg was achieved.those obtained by NAA. Vijayakumar e t a l . (321) reported an extremely laborious i n d i r e c t procedure f o r Se i n plant materials based on FAAS measurement of Cd via the generation of iodine. the liberated I extracted i n t o benzene, then back-extracted i n t o an aqueous solution of ascorbic acid and treated w i t h Cd-phenanthroline sulphate.The resulting complex was then extracted w i t h nitrobenzene f o r determination i n an air/C2H2 flame. and an RSD of 2% achieved i n the range u p t o 15 vg Se. The former was found t o have many advantages such a s rapid Determinations using hydride generation continue t o be reported f o r a number Gladwell Samples were Tsalev and Petrov (1659) The e x t r a c t s were buffered t o pH 4.5 On completion, 9M HC1 was added t o the same solution and the Kuldvere (1539) determined I i n A t the optimum Results f o r various samples were comparable w i t h Se was allowed t o react w i t h KI in acid medium and I t was claimed t h a t various interferences could be overcome 4.7.3 Atomic Emission Methods As m i g h t be expected, the major share of the reports i n t h i s p a r t i c u l a r subject area are again concerned w i t h use of the inductively coupled plasma as theApplications 207 emission source. Mermet e t a l .(1182) have reviewed recent applications t o biological materials, while Schrader (1721) has contributed a s e r i e s of a r t i c l e s covering use of the ICP f o r the analysis of plants, foods, s o i l s and sludges.A potentially useful development f o r s o i l and plant analysis has been described b r i e f l y by Beaty e t a l . (C2207), who used a conventional ICP spectrometer f o r d i r e c t analysis of briquetted powders, thus avoiding the usual problematical digestion procedures. A unidirectional high voltage spark between the sample plus graphite powder briquette and a counter electrode produced a representative dry aerosol which was swept i n t o the ICP by a stream of Ar.described multi-element analysis procedures i n routine use. Jones (1984, C212) determined B , Ca, C u , Fey Mg, Mn, K, P and Zn i n 34 Magruder f e r t i l i z e r standards w i t h excellent r e s u l t s and a l s o obtained r e s u l t s f o r 10 additional elements (Al, Bay Cd, Cr, Nay Ni , Pb, Si and S r ) which were in good agreement w i t h values determi ned by a1 t e r n a t i ve techniques.R i andey and co-workers (1 41 5) gave a detailed description of the determination o f major elements i n s o i l s , based on Sr(BO2l2 fusion and dissolution i n 2% HN03. Mo i n plant materials using extraction w i t h 8-hydroxyquinoline t o overcome the problem of spectral interferences by Cay Mg and Fe.Good agreement was obtained w i t h c e r t i f i e d values f o r various NBS SRMs and the confidence interval on a single Gestring and Soltanpour (347) deter- mined B i n s o i l e x t r a c t s and HN03 digests of plant materials, comparing r e s u l t s favourably in the former case w i t h those obtained by the standard azomethine-H colorimetric method. Various workers have Lyons and Roofayel (1520) determined determination was 6.1% ( p = 0.05).The use of hydride generation w i t h ICP-OES was reported (1122) f o r the deter- mination of A s , B i , Ge, Sb, Se and Sn i n various plant materials. Detection 1 lim t s f o r simultaneous multi-element determination ranged from 0.02 ng ml- f o r As t o 0.8 ng ml-1 f o r Sn, w i t h a precision a t 10 ng ml-1 of b e t t e r than 6% RSD Difficulties encountered i n u s i n g a similar system f o r As, Hg, Pb, Sb, Se and Sn were discussed by Carr and Cooley (C2481).Optimum overall s e n s i t i v i t y was obtained w i t h 0.5 t o 1% acid concentrations, but higher acid strength was necessary t o reduce t r a n s i t i o n metal interferences.In s p i t e of the current popularity of the ICP, reports continue t o appear concerning the use of other emission sources. i n conjunction w i t h ETA f o r the determination of P and S i n grass samples by chemiluminescent emission. achieved. ion exchange separation on Zeocarb 225, a f t e r ashing the samples and dissolving the residue i n 20% HC1. elements i n s o i l s (1510), analysis being carried out w i t h the minimal sample preparation of mixing w i t h graphite powder containing Eu and Pd as internal standards.A cool Ar/H2 flame was used (2219) Detection l i m i t s of 5 and 10 ng respectively were I t was necessary t o overcome chemical interferences using a preliminary A d.c. a r c spectrographic method was described f o r 21 Aziz e t a l .(1363) described a MIP-OES method i n which sample208 Analytical Atomic Spectroscopy solutions were atomized u s i n g a graphite furnace. multi-element determination of Cd, Coy Cry C u , Fey Mg, Mn, Ni, T1 and Zn ranged from 1-50 ng m1-l. Results f o r NBS SRMs agreed well with the c e r t i f i e d values. Portnaya and Chelnokova (576) determined Pb i n plants and s o i l s over the range 1-50 ng by co-precipitation w i t h chrornpyrazol(I1) iodide in 0.2M HN03, ashing the p r e c i p i t a t e and measuring the Pb spectrographically.described an improved method i n which N i n the sample was converted t o NH3 gas (by gentle heating i n a weak flame o r i n a furnace a t 500 OC f o r 1 m i n ) which was then excited i n a high frequency discharge.spectrum and the relationship of i t s features t o the 15N concentration and t o the accuracy of the method were discussed. % in 0.366-1.37 atom % 15N. small amounts of plants and s o i l s i n which samples containing 1&50 ug N were processed by a micro-Dumas method i n sealed glass discharge tubes. obtained w i t h an RSD of about 1% by c a l i b r a t i o n against data obtained by mass spectrometry.Another micro-method was reported by Lazeeva e t a l . (406) i n which the N released from biological samples was collected i n a 0.3 rnl, 1-2 mm wide c a p i l l a r y and excited i n a 20 MHz discharge. Readings were taken from the N2 band spectrum a t 297.7 nm when 15N < 50% and a t 380.4 nm f o r higher concent- rations. Detection limits f o r the Several groups have reported emission methods f o r n i trogen-15. Yamamuro (907) The interpretation of the The l a t t e r was improved t o ? 0.002 atom Lemasson e t a1 .(840) described a method f o r very Results were The RSD was 10% f o r 0.37-20% 1 5 N 4.7.4 Compari son of Methods West (454, 1604) has reviewed the applicat techniques t o the determination of biosign on of various atomic spectroscopic f i c a n t t r a c e elements i n s o i l s , emphasizing t h e i r complementary nature.analysis of s o i l s by ICP-OES, XRF, SSMS and NAA and compared r e s u l t s f o r f i v e topsoils analysed by XRF and by AAS a f t e r LiB02 fusion. Ure (C253) also dis- cussed the problems of e f f i c i e n t t o t a l element analysis of s o i l s by agricultural and environmental laboratories and compared the advantages and disadvantages of di f f e r e n t spectrometric techniques.Two reviews have appeared (1007 , 1203) con- cerning the problem of Cd contamination of s o i l s and analytical methods which may be appl i ed. analyses was reported by Yamagata (1742). and sediment were obtained by about 200 laboratories using AAS with solvent extraction where necessary. 100 ppm C u , Pb and Zn and the extraction determination of 1 ppm Cd was around lo%, while t h a t f o r As was about 20%. r e s u l t s f o r multi-element analysis of various crops w i t h those obtained by wet digestion followed e i t h e r by d i r e c t ICP measurement o r by a complexation-ICP Berrow and Ure (1032) discussed the A comparitive study on the interlaboratory r e l i a b i l i t y of environmental Data on As, Cd, Cu, Pb and Zn i n s o i l The overall RSD f o r the d i r e c t determination of Wolnick e t a l .(C2197) compared NAAApplications 209 scheme. The FAAS o r ETA-AAS determination of Ni in plants and sewage sludges was compared w i t h r e s u l t s obtained by dimethyl glyoxirne solution spectrophoto- metry (1643). c i t y and rapidity, whereas f o r plants ETA-AAS was preferred because of i t s b e t t e r precision and lower detection limit.ICP-OES determination of hot-water-soluble B w i t h the azomethine-H colorimetric method. Results f o r the analysis of western Oregon soils were comparable. The l a t t e r method was preferred because of i t s simplicity, speed and accuracy.FAAS was chosen f o r routinesludge analysis because of i t s simpli- Parker and Gardner (1031) compared theTable 4.7 SOILS, PLANTS AND FERTILIZERS ~ ~~ Element h/nm Matrix Technique, Concentration Atomization, Analyte Form Sample treatment Ref. As 193.7 Sediments Trace levels A, ETA, L Digest the sample using aqua regia, hydrofluoric acid and boric acid.Subsequently modify the matrix by adding nickel nitrate prior to injection into ETA Liberate ASH, from solution of the sample Separate the As from soil extracts by HPLC Extract 5 g sample with either H,O, 1M ammonium acetate (pH 4.8 or 7) or 9M HCI. Introduce extract into mercury hydride system Separate As by an ion-exchange technique Separate As by solvent extraction-anion exchange chromatography C296 525 1117 1659 1731 1783 2239 C2481 339 34 7 103 1 1120 1756 1119 1721 1889 1472 1870 1985 Biological sample Soils Soils Trace levels - A, ETA, G A, ETA, L A, Hydride, L As - As As 193.7 - As As - As 193.7 As - B - - Plant material Soil A, -, L A, ETA, L 0-7 ng/g 20-300 ng/g Trace levels Trace levels Plant material Environmental samples Plant samples A, ETA, L E, P, ICP, L E, P, ICP, L An evaluation of B blanks resulting from wet digestion and dry digestion methods B Soil extracts, plant tissue Soils E, P, ICP, L B E, P, ICP, L Obtain clear hot water extracts by using 0.02MCaC1, solution instead of distilled H,O Manure of Ba treated cattle Orchard leaves (NBS 1571) Leaves, plant tissue 4.4-25.2 pg/g Ba Be 313.11 Trace levels (0.01 pg/g) E, P, ICP, L Wet ashing produced higher results than dry ashing (Mg, Zn, Mn) Ca Ca - - Soil extracts, spinach, orchard leaves Soils, plant materials E, P, ICP, L Ca E, F, L A, ETA, L Repress the negative effect of A1 on emission by the addition of Ce compounds [> 1000 pg/mlCe(III)] Separate Cd by gel permeation, resin absorption, or ion- exchange chromatography Minimize interferences from various matrices by using thiourea Polluted soils 70-478 ~ g / g Cd Cd Cd - - Biological standards Soils A, ETA, L A, ETA, S- - - - - - - 253.7 254 - - 183 184 187.6 206.2 253.6 - - - 386.4 297.7 380.4 - Soil extracts Soils Soils Soils E, P, ICP, L A, F, L A, ETA, L A, F, Air/C,H,, L d 2318 s.U C2413 5 1030 1735 APDC and MIBK extraction employed Extract soil samples with 1N HNO, Digest sample with mixture of HNO,/HClO,/HF and evaporate to dryness, dissolve the residue in 0.1N HCI, complex Co with APDC and extract with MIBK Remove the interference of K and Ca by addition of NH,NO, or ascorbic acid at the 1% level - Use a lMHCl solution to overcome matrix effects completely 0.02-0.08 Mg/g A, ETA, - Plant fibres 1733 Protein, spinach Environmental samples Environmental samples Plants A, -, - A, ETA, L A, -, - A, Cold vapour, G 1757 726 1058 1414 - Trace levels - 10-2OoMg/g Reduce the Hg(I1) formed during digestion to Hg(0) with NaBH,(l%).Extract from solution with N, at 180ml/min, dry over Mg(CIO,), and measure in 30 cm cell TreatO.l-1.0gsample with5mlHN0, and 100mgV,O,, heat at 160 "C for 5 min, cool and add 5 ml H,SO,. Evolve the Hg by treatment with 10 ml 10% m/V SnC1, .2H,O for measurement in cold vapour cell Use dihydroxymaleic acid for reduction of Hg Use citric acid as matrix modifier Maintain an atmospheric pressure discharge between two Nb electrodes in a silica tube through which a mixture of He and I passes.Use the 183 nm emission line generated for measurement of the I absorption in the flame The decrease in absorbance of Hg(I1) caused by I in cold vapour AAS is used to determine I Add 0.5MHCI to plant material in a screw cap bottle and heat for 15 min at 30"C, cool, filter and measure concentration of K, Ca, Mg by AAS Treat the samples with HF-HNO, (2.5-5 mg of soil per ml of mixed acid) and analyse the solution directly Eliminate interferences from Ca, Mg and Fe on the prominent Mo wavelength by 8-hydroxyquinohe extraction Sewage sludge A, Cold vapour, G 1464 Environmental samples Soil Soil, plants, fertilizers A, Cold vapour, G A, ETA, L A, F, N,O/C,H,, G 1868 1888 545 Seaweed Dried plant samples 2-25 Mg - A, Cold vapour, G A, -, L 1539 1187 1648 798 1520 Soil Trace levels - - A, -, L E, P, ICP, - E, P, ICP, L Silicate fertilizer Plant material 0.37-20% 0.3-6.3% E, -, - - E, P, H.f.discharge, - Excite the compressed N in capillary (1-2 mm wide) with h.f. discharge (20 MHz, SOW 406 Biological samples 53 1 Organic materialsTable 4.7 SOILS, PLANTS AND FERTILIZERS-continued Element h/nm Matrix Technique, Concentration Atomization, Analyte Form Sample treatment Ref. 'IN 'SN 'SN N Na Na P Pb Pb Pb Pb Pb S (as S,) Se Se Se Se Sn - Rice plants - Biological material - Plant tissues 174.2 Orchard leaves (NBS -SRM) - Clays, soils 0.3-1.37% E, P, H.f.discharge, - Change the N in the sample to NH, gas by gentle heating with a weak flame or in a furnace at 500°C for 1 min Ion-exchange chromatography in sample preparation Transform the NH, to W, by the Dumas method 907 94 9 95 3 2330 1160 1760 689 5 76 808 1627 1708 202 1 2219 321 735 1123 2257 723 40 t.ig 100-10oot.ig _ _ - 1 , E, -, - E, P, ICP, L Triethanolamine and BaC1, used as reagents, BaCI, alone interferes the least Schistosoma mansoni (worms) Fertilizers Plant ash, soil, water Co-precipitate the Pb with chrompyrazol(I1) iodide in 0.2M HNO, medium.Collect the precipitate, ash, determine the Pb spectrographically - Snowmobile trails 283.3 Seaweed, vine leaves, mussel - Biological tissues - Orchard soils 136 pglrn' 0-4 ng A, -, - A, ETA, L Prepare a slurry or a solution of the ashed sample Dissolve the sample in a HN0,-HCIO, mixture for AAS or use HCI extraction of the sample for ICP spectrophotometers Digest 0.5 g sample with MgNO, solution and ash the resulting solution at -450°C.Dissolve the ash in lOml HCI and dilute to 50 ml with H,O Make use of reaction of Se with KI in acid medium. Liberated I reacted with Cd. The Cd concentration determined by FAS Digest in a mixture of HNO,/HCIO,. Separate interfering ions by ion exchange Digest with H,SO,/HCIO,, extract Se with 1,2-diamino-4- nitrobenzene Burn the pelletized sample in 0, flask, absorb in 2.5M acetic acid, collect for 2 min on Al coated SiO, tube in flame Decompose the sample with NH,I, collect the sublimate in a separate condenser and dissolve in tartaric acid; reduce Sn to hydride 3 84 Grass samples 100-700 ng E, F, Air/C,H,, L 228.8 (via Cd) Plant materials 0-15 pg Trace levels 0.25-0.41 pgig A, F, Air/C,H,, L A, Hydride, G - Forage samples 196.0 Soil A, ETA, L 196.1 Vegetation A, F, Air/C,H,, L A, Hydride, G Soils, sedimentsSn Various (1 2) Various (1 9) Various (7) Various ( 5 ) Various (6) Various Various (13) Various (14) Various (14) Various Various (10) Various (6) Various ( 5 ) Various (12) Various (1 2) Various Various Various Various (20) Various Various Various (1 1) 224.6 Environmental samples - Agricultural crops - Fertilizers Trace levels Major levels Trace, minor, major levels Trace levels A, ETA, G E, P, ICP, L E, P, ICP, L Decompose sample with NH,I, collect the sublimate in cold trap and dissolve in 20 ml 2M HCI for AAS - 1053 $ C76 2 F’ c212 C213 C253 C287 C3 14 342 454 532 548 5 94 606 6 90 76 1 799 847 91 1 1066 1070 1121 1191 1362 - Agricultural samples E, P, ICP, L Extract soil sample with 20 nil 0.025N H,SO,/O.OSN HCl mixture (B, Ca, K, Mg, Mn, P, Zn) Extract samples in acid for AAS and ICP (Al, As, Cd, Pb, TI) Extract in hot HNO, (Cd, Cu, Mn, Ni, Pb, Zn) Prepare a slurry in water and transfer aliquots onto graphite platform for graphite furnace AAS The loss of elements during dry ashing was investigated AAS, ICP and spark source mass spectrometry compared Mineralize the sample by combustion in pure 0,, collect volatile trace elements in cooled receptor and dissolve in acid (2 ml) for emission spectrometry Use sampling tool to introduce solids into the graphite tube ~ (Ag, Co, Cu, Eu, Fe, 11, Mn, Na, Pb, Pt) - (B, Co, Cu, Mn, Mo, Zn) Wet ash with H,SO,/H,O, (Ca, K, Mg, N, Na) Ash the sample as follows: 180°C for 2h, 300°C for 2 h , 530°C for 4 h.After ashing, boil the sample with 6NHC1, dilute to lOOml and store in polythene vessels - Soils - Sewage sludge, soils - Soil Major and trace levels - Trace levels A, -, - E, -, ICP, L A, -, L A, ETA, S - Plant materials - Soils - Organic samples Trace levels Trace levels Trace levels A, -, S A, -.-, E, P, ICP, - E, P, ICP, L - Spinach leaves, - Vegetable !,latter - Paddy leaves - Plants - Plant material bovine liver A, ETA, S Trace levels Trace levels - Major and trace levels - NPK fertilizers - Sediments, soils Trace levels Trace levels Extract Pb-210 and Ra-226 by a sequential chemical procedure Apply an APDC-MIBK extraction to a 3.5 g sample after treatment with 35 ml of O.OSN EDTA (shaking for 1 h) Substitute the activated C method for decolorization of soil extracts by 0.25 mol NH,HCO,/dm’, adjusting the pH to 8.1 with NH,OH - Soil Soil Trace levels A, F, L - Plant ashes - Biological materials - soils Trace levels 0.025-1 .O pg/g Treat samples containing < 1O%C with HNO,/HCIO, or HCIO,/HF mixtures to obtain complete dissolution Orchard leaves, bovine liver Transfer 1 g dry substance to Teflon vessel, add 40 ml concentrated HNO, and 1 ml H,O,, add lOml HCIO, and fume; dilute to volume 3 wTable 4.7 SOILS, PLANTS AND FERTILIZERS-conrinued Element A/nm Matrix Technique, Analyte Form Concentration Atomization, Sample treatment Ref.Various (10) Various (9) Various Various (21) Various Various (19) Various (7) Various (8) Various (1 2) Various (14) Various (7) Various Various (1 8) Various (9) Various (7) Various - Orchard leaves, bovine liver 0.125-2.0 pg/g - Soils - Grass, corn wheat - Soils, limestones - Soil, slurry - Plant, animal tissues - Tomato ieaves - Orchard leaves, - Plant material bovine liver - Plants - Soil.sediment - Biological materials Plant, animal tissue Fertilizers Soils Plant tissues, soil Major levels Trace levels - Trace levels Trace levels - Major and trace levels Trace levels Trace levels Trace levels Trace levels - - E, P, ICP, S A, F, Air/C,H,, L E, A, Dc., S A, F, S E, P, ICP, L E, P, ICP, L A, F, Air/C,H,, - E, P, ICP, L A, -, - E, -, S E, P, ICP, L E, P, ICP, L A, F, L E, P, ICP, S Decompose sample in HClO,/HNO,, take up residues in 0 . 1 ~ H N 0 , ; final concentration 0.01 g/ml (Cd, Co, Cr, Cu, Fe, Mg, Mn, Pb, TI, Zn) Fuse 0.1 g sample with 0.9g Sr(BO,), at 1100°C in induction furnace; dissolve in 2% HNO,, dilute to 200ml (Al, Ca, Fe, K, Mg, Mn, Na, Si, Ti) Digest with HNO,/HCI mixture and compare results with dry ashing in Pyrex beakers Add graphite powder to the samples Grind soil for + h in a wet ball mill (ethanol) and continuously agitate the slurry Extract the elements for ICP determination, and form hydrides of As, Sb and Se for AAS (Ca, Cd, Co, Cr, Cu, Mn, Mo, Ni, V) - (Ca, Cu, Fe, K, Mn, Sr, Zn) Digest with (a) HNO,/H,SO,, (b) HNO, alone, (c) repeatedly with HNO, or (d) apply direct dry ashing; (d) was best for multielement analysis Decompose 1 g of the powdered plant with HNO,/H,SO, mixture at 105 "C and nebulize the solution directly Determine Cu, Pb and Zn (lOOpg/g) by direct AAS, but 1 pg/g Cd requires solvent extraction (As, Cd, Cu, N, P, Pb, Zn) Digest with HNO,/HCIO, and extract the trace elements with oxine/CHCI, at pH 3.5 and 8.5, mix the CHCI, solution with graphite powder and analyse spectrographically Separate the elements by ion exchange on Chelex-100 resin Extract with ammonium citrate and determine the P with ICP (B, Ca, Cu, Fe, K, Mg, Mn, P, Zn) Extract the elements from solution buffered at pH 5.3 with five chelating agents for comparison of efficiencies; marked differences observed (Al, Cd, Cu, Fe, Mn, Ni, Zn) Eliminate digestion of samples to prepare solutions for ICP by powder briquetting of the sample; produce a dry aerosol by means of a unidirectional high voltage spark that is carrier borne by Ar gas to the ICP 1363 1415 1465 1510 1512 1560 1570 1572 1625 C1697 1742 1817 1940 1984 C2094 C2207b 'cr - Digest with HNO,/HClO, or HNO,/HClO,/HF mixtures C2208 Various (8) - Biological SRMs - A, F, L Acid digestion, with study of parameters leading to precise C2338 Various - Biological, agricultural Major, minor trace E, ICP (echelle), - - C2471 Various (20) - Plant samples E, P, ICP, L and accurate results (Ca, Cu, Fe, K, Mg, Mn, Na, Zn) samples levels 215

ISSN:0306-1353    

DOI:10.1039/AA9821200203

出版商:RSC    

年代:1982

数据来源: RSC

摘要:

216 Analytical Atomic Spectroscopy 4.8 FOODS AND BEVERAGES The use o f atomic spectroscopy f o r t r a c e element analyses o f foods and beverages i s now w e l l e s t a b l i s h e d and several review papers have appeared. Some deal w i t h s p e c i f i c aspects o f t h e a n a l y s i s , such as sample p r e p a r a t i o n (709) o r h y d r i d e generation (660), whereas o t h e r s a r e concerned w i t h t h e a n a l y t i c a l technique, - e.g., AAS (1189), NAA, ICP-OES, HPLC (1190) o r ICP-OES (843) o r w i t h a s p e c i f i c type o f m a t r i x such as wines and a l c o h o l i c beverages (344, 345). 4.8.1 SamDle Preoaration Wichman e t a l . (C2307) described a r a p i d and d i r e c t method f o r measuring t r a c e elements i n food. u l t r a s o n i c d i s i n t e g r a t i o n and nebulized d i r e c t l y i n t o t h e flame o r plasma atomizers.Suspensions of homogenates o f s o l i d foods were prepared by A PTFE n e b u l i z e r was used t o minimize blockage. -- Wet ashing o f foods w i t h HN03/HC104 mixtures can g i v e low recoveries o f Sb, b u t these losses were prevented by t h e a d d i t i o n o f H2S04 t o t h e r e a c t i o n m i x t u r e (2346).d i g e s t i o n . Keunnen (2018) d i s s o l v e d 1 g amounts o f a v a r i e t y o f a g r i c u l t u r a l products by h e a t i n g f o r 30 min w i t h 6M HC1 a t 80 OC i n sealed polythene b o t t l e s . The determination o f Pb i n s o f t d r i n k s was achieved by separation o f Pb from s o l u t i o n s o f ashed samples by c o - p r e c i p i t a t i o n onto Zr(OH)4.was dissolved, perhaps s u r p r i s i n g l y , i n HC1 f o r a n a l y s i s by ETA-AAS (1028). Q u a n t i t a t i v e separation o f methylmercury compounds from f i s h f l e s h was achieved by s o l v e n t e x t r a c t i o n o f t h e i o d i d e complex i n t o benzene from a K I ascorbic a c i d medium (1938). as 50 ng, was recovered i n a s i n g l e e x t r a c t i o n using a 1O:l r a t i o o f aqueous t o organic phases.A more r a p i d p r e p a r a t i o n o f foods f o r t r a c e element analyses i s pressure The p r e c i p i t a t e More than 95% o f methylmercury, a t l e v e l s as low 4.8.2 Atomic Absorption Methods The anti-foaming agent dimethylpolysiloxane was determined down t o 0.2 ppm i n j u i c e s and beers by flame AAS w i t h a N20/C2H2 flame f o l l o w i n g separation by ad- s o r p t i o n onto F l u o r o s i l and e l u t i o n w i t h wines were made i n d i r e c t l y u s i n g FAAS by t h e formation and e x t r a c t i o n o f am- monium phosphomolybdate i n t h e determination o f Mo (1611). e x t r a c t i o n were used f o r pretreatment i n t h e FAAS determination o f Cd and Pb i n m i c r o b i o l o g i c a l l y produced feeds (1704). The recoveries o f b o t h elements ranged from 93-105% and concentrations i n t h e feeds were g e n e r a l l y below 5 mg k g - l . 5 ppb f o l l o w i n g dry-ashing w i t h added Mg(N03)24g0. w i t h c e r t i f i e d values o f NBS reference m a t e r i a l s . Lower l e v e l s o f Se down t o 0.5 ng were determined by combining GC separation o f t h e piazselenol complex w i t h analyses by AAS u s i n g a heated q u a r t z tube and an a i r / H 2 flame (C2101).MIBK (797). Measurements o f PO4 3- i n Wet ashing and s o l v e n t Hydride generation AAS was used (1670) t o measure As and Se i n foods down t o Good agreement was obtainedApplications 217 Measurements of organic arsenicals added t o animal feeds,at 20-50 growth stimulants, were made by electrothermal atomization AAS follow tion i n t o 1% r ~ ~ f i (NH4),C03 solution and d i l u t i o n w i t h CH30H (1707).e r i e s were 103.6% a t 25 ppm and 104.5% a t 50 ppm, w i t h RSDs of 4.0 - ng exti-ac- The recov- 4.3%. The Cyclohexyl t i n hydroxi de and r e s u l t s of analyses agreed we1 1 w i t h AOAC methods.related compounds were measured i n oranges, orange j u i c e and tea by ETA-AAS (495). The recoveries from the basic alumina column used f o r sample clean-up ranged from 82 - 107% and the detection l i m i t was 6 ppb i n oranges and orange j u i c e and 50 ppb in green tea. An i n t e r e s t i n g matrix modification f o r the determination of Cd i n wines and beers by ETA-AAS was the addition of Al(N03)3 which allowed ashing temperatures of u p t o 650 OC t o be used without loss of Cd from the a-A1203 matrix formed during the ashing stage (114).T h i s method produced RSDs of 1.8 and 5% f o r the analysis of wines and beers, respectively, and a detection l i m i t of 6.5 pg Cd. May and Brumbaugh (113) used NH4H2P04 as a matrix modifier i n the determination of Cd i n f i s h t i s s u e s by ETA-AAS.Reproducible atomization p r o f i l e s of Cu and Pb were obtained during the analysis of foods by ETA-AAS using a molybdenum-tube atomizer by the addition of thiourea (2019). technique of ETA-AAS w i t h matrix modification using NH4H2P04 was reported t o over- come matrix interferences i n the determination of Pb i n foods (1874) and i n f i s h t i s s u e s (1113).Other i n t e r e s t i n g ETA-AAS applications included the sequential multi-element analysis of wines (2319) and foods (641). The l a t t e r method used computer control of spectrometer operation and data handling t o enable one person t o make 7000 elemental analyses i n 8 working days w i t h RSDs of 0.4 - 3.9%.A combination of the L'vov platform 4.8.3 Atomic Emission Methods Evans and Dellar (1543) evaluated a t great length a d i r e c t reading inductively -- coupled plasma emission spectrometer f o r mu1 ti-trace-element analysis of foods. They found good agreement w i t h t h e i r FAAS r e s u l t s f o r the d i r e c t determination of C u , Mn, Ni and Zn but suggested t h a t t h e i r preconcentration procedure f o r other determinations was inadequate f o r dietary studies of a wide range of foods.Ishii e t a l . (1621), however, found good agreement between ICP-OES and FAAS f o r the analysis of 8 elements i n 24 v a r i e t i e s o f s h e l l f i s h . reported f u r t h e r [see ARAAS, 1981, lJ, Ref. 1700) on t h e i r hydride generatiowICP- OES system f o r the determination of As, B i , Ge, Sb, Se and Sn i n foods.Their method gave good agreement with reference values of NBS standard materials w i t h detection l i m i t s ranging from 0.02 pg 1-1 f o r As t o 0.80 g 1-' f o r Sn. A d.c. a r c plasma was used f o r the determination of As, Cd, Cu, Pb and Zn in wheat and wheat products, giving detection limits of 0.004-0.2 vg 1-1 (2246).Hahn e t a l . (1122) 4.8.4 Comparison of MethodsTable 4.8 FOODS AND BEVERAGES Technique, Analyte Form Concentration Atomization, Sample treatment Ref. Element h/nm Matrix As - Foods - A, Hydride, G Dry ash with Mg(NO,),-MgO, dissolve in 6M HCl, arsenate converted to arsenite by addition of KI. Hydride generation into silica-tube furnace Sample shaken with 1% ammonium carbonate solution, diluted with aq. 15% methanol Zeeman background correction 5 g sample ashed with 6 ml HISO,, residue treated with 3 ml HNO,, 1 ml30% H,O, and evaporated to dryness. Residue dissolved in 6 ml25% HNO,, filtered, diluted to 25 ml Homogenized sample digested with HNOJHC10, in Teflon beaker, fumed to dryness and dissolved in dil.HNO, Wine and beer mixed 1:l with 0.02NA1(N03),, urine diluted 1:4 with O.lNHN0, before A1,0, addition. Ash 450°C Samples treated with ammonium citrate, adjusted to pH 8 with NH,OH, mixed with saturated (h'H,),SO,. Cd and Cu extracted with Na diethyldithiocarbamate and MIBK Digest sample with 10-25 ml HNO,(32%), evaporate 3 times with 5 ml HCI and concentrate to 10 ml. Add 6 ml 10% citric acid, adjust pH to 8.8, add 5 ml DDC solution, 5 ml butylacetate, add H,O Ash, Cd-I complex formed in acidic medium, extracted MIBK Dry ash Dry ashing, pretreatment with HNO,/H,SO, ash acid increases variability of Pb determination, but eliminates Cd loss.Sensitivity increased by extraction with dithizone in CHC1, and back extraction with HCl 1670 1 I01 2020 909 1009 1114 1622 1704 1762 1786 C2340 1592 909 1622 1786 1983 2019 1009 As - Animal feed - A, ETA, L As - Cd - Seaweed Tea leaves 9.9-51.4 ppm A, -, - - A, F, -, L Cd - Cd - Fish A, ETA, -, L A, ETA, L Wine, beer, urine Cd - Milk products - A, ETA, L Cd 228.8 Protein feeds - A, F, Air/C,H,, L Cd 228.8 Cd Cd - - Foods Meat products Vegetables A, F, Air/C, H, , L A, -, L A, F, L c r 357.81 c u - c u - c u c u - - Animal feed Tea leaves Milk products Meat products Foods - A, F, Air/C,H,, L A, F, -, L - A, ETA, L A, -, L 1.020mg/100g A, -, - - A, ETA, L - A, ETA, L - - See Cd, ref. 909 See Cd, ref. 1622 Dry ash 5 g sample digested with 10 ml HCIO,, 20 ml HNO, in micro- wave oven Solid samples dissolved in HNO, in decomposition vessel See Cd, ref. 1009 Foods FishHg Hg Hg Hg Hg K Na Pb Pb Pb Pb Pb Pb b % x - Marine sediments - A, -, - Extraction with 1: 1 H,SO,/HNO, with a few drops of HCI 1168 6 Hg 1653 8’ 253.7 Fish - A, Cold vapour, G Pb Pb Pb Pb Pb - 283.3 Wheatbran - Biological materials - Fish - Fish Vegetables Vegetables Sugar beet, pulp molasses Tea leaves Fish Soft drinks Fish Protein feeds - < 10 mg/kg - Beer 0.1 mg/l - Wine - - Meat products - - Food - - Food - E, P, G A, Cold vapour, G A, F, L A, ETA, L A, ETA, L A, ETA, L A, F, AU/C,H,, L A, ETA, L Homogenized sample digested in 12.5 ml of 18MH2S0,-15M HN0,/4:1), 2 ml H,0,(30%) added, mixture heated in Technicon BD4O block digester, Hg determined by cold-vapout technique Wet ash in mixture, of H,SO,/HNO,/HClO, Samples digested with HNO, and acidified KMnO, and detected by cold-vdpour technique Solvent extraction as MeHgI, methyl mercury detected using Hitachi model 501 Hg analyzer with Zeeman background correction Sample digested with 20ml HNO,/H,SO,(2:1) in presence of 10 mg V,O,, diluted to 100 ml with 0.02% K,Cr,O, in 5% HNO,/10% H,SO,. Sample injected into 3% SnC1,-5% hydroxylammonium sulphate in special apparatus, liberated Hg determined by ICP or cold-vapour cell Recovery investigation using various dry-ashing techniques See K, ref. 684 Collaborative study See Cd, ref. 909 See Cd, ref. 1009 Sample wet ashed, ash mixed with ZrOC1, and 18% NaOH to pH 7-9, Pb co-precipitated with Zr(OH),. Precipitate dissolved in HCl. Matrix modified with NH,H,PO, Digest sample with 10-25 ml HN0,(32%), evaporate 3 times with 5 ml HCI. Solution mixed with 10 ml 50% ammonium citrate, pH adjusted to 9.2 with NH,OH, extracted with 5 ml portions of dithizone, organic extracts shaken with 5-10ml 0.5MHCl.See Cd, ref. 1704 Dry ashing procedure Collaborative study Dry ash Round-robin study of carbon rod AA, and chelation-solvent extraction AA Digest in HNO,/HF/HClO,, matrix modified with 1% (NH, )z HPO, 3 1734 1879 1938 2254 6 84 6 84 685 686 737 909 1009 1028 1113 1704 1709 1761 1786 1841 1843Table 4.8 FOODS AND BEVERAGES-continued Element h/nm Matrix Concentration Atomization, Sample treatment Ref.Technique, Analyte Form Pb - Pb - Pb - Pb - Se 196.0 Se 196.0 Se - Se - Se Se Si - - - Sn 286.3 Sn 233.5 Zn - Zn - Food Vegetables Infant food Foods Foods Canned milk Vegetables Wines Cereals, lettuce, potatoes Fish muscle, liver Biological materials Foods Tea, bovine liver Biological materials Juices.beer Fruit, tea Canned foods Wine EtOH liquid diet Tea leaves - A, ETA, L - A, ETA, - 1-1000 ng/g A, ETA, - - A, F, L A, ETA, L A, ETA, L A, F, -, L A, F, Air/C,H,, L - A, F, Hydride, G A, ETA, L, G - A, F, Air/C,H,, L - - < 0.5 ng - A, F, N, G A, ETA, Hydride, G A, F, Air/C,H,, G A, F, N,O/C,H,, L - A, ETA, Ar, L A, F, Air/C,H,, L 200-500 ppm - A, -, L - Comparison of wet and dry ashing mcthods Comparison of ETA and anodic stripping voltammetry Solvent extraction technique preceeded by HNO,/HCIO, digestion; collaborative study See Cu, ref. 2019 Collaborative study See Cd, ref. 2340 Decomposed with H,O,, sample diluted with 5MHC1, (NH,),Mo,O,, added, extracted with MIBK at pH 1 to 2, solution analysed for Mo Digested in HNO,/HC1O,/H,S0,(3:2:1) and NH,VO, catalyst before hydride generation Comparison of ETA with hydride generator, three different digestion systems compared Na diethyldithiocarbamate treatment and extraction with MIBK See As, ref. 1670 Combination of ETA and hydride generation Heated quartz tube furnace after gas chromatography Sample absorbed onto Florisil, dried, extracted with CHCl,, extract evaporated to dryness, dimethylpolysiloxane determined after dissolution in MIBK Tricyclohexyltin hydroxide and related compounds extracted from sample with hexane in the presence of acetic acid, extract separated on alumina column, cyclohexylstannoic acid and dicyclohexyl tin oxide remain on the column Digested with HNO, then with HCI, 1 ml 1.91% KI solution added SO:- in wine precipitated with BaCI, and excess Ba” determined in filtrate Nutritional study See Cd, ref. 909 1844 1845 1846 1887 2019 C2161 C2340 1611 600 1367 1620 1670 1784 c2101 797 495 1641 1824 336 909Zn Zn Various (20) Various (7) Various (5) Various (6) Various (5) Various (1 2) Various (5) Various (6) Various (6) Various (20) Various (14) Various (16) Various (1 1) Various (8) Various (6) Various (5) Various (7) Various (14) Vsrious (5) Various (16) Various (8) Meat products Foods 1 7 7 0 mE/l Fish - Wine Food Fish Liver and kidney Milk-base feeds - Animal tissue Natural food dyes 3-240 @g/g Foods - Fish - Foods - Foods Food Shellfish Animal feed - Meat additivies Beer - Raw agricultural products Wheat Food Wine A, ETA, L A, -, - A, ETA, E, P, L E, P, L o r G A, tTA, L A, -, L E, P, L E, A, D.c., L A, 1: or ETA, L E, ETA, L Dry ash See Cu, ref. 1983 Carrier precipitation method discussed - (Al, Ca, Cu, Fe, K, Mg, Na) Digestion in special apparatus in HNO,/IICIO,, extracted into CHCI,, complexed with DDC (As, Cd, Hg, Pb, Se) For Hg, digested in H,SO,, other metals sample ashed with Mg(NO,),.(Cd, Cr, Cu, Hg, Ph, Zn) - (Cd, Cu, Mn, Ph, Zn) Incineration at 360°C in a kiln furnace preferred to mineralization in an autoclave (Cd, Cr, Cu, Fe, Ga, K , Mg, Mn, Na, Ni, Zn).Separate determination of Hg Dry oxidation followed by acid ash dissolution, (Cd, Co, Cr, Ni, Pb) Pretreatment with H,SO,/H,O, (Cd, Cr, Cu, Mn, Ni, Zn) Hydride generator interfaced t o ICP, (As, B, Ge, Sh, Se, Sn) Investigation into carrier precipitation method 14 elements including trace levels of Mo and Ni Development of SIMAAC (simultaneous multi-element AA continuum source) (Ca, Co, Cr, Cu, Fe, K, Me, Mn, Ni, Zn) Evaluation of ARL137 ICP (As, Cd, Co, Cr, Cu, Fe, Mn, Li, Pb, Sr, Zn) Comparison of ICP and AA results (Cd, Co, Cu, Fe, Mn, Ni, Sr, Zn) Samples digested in HNO,/H,S0,(2:3) in the presence of 4-5% V,O,, 10% SnCI, added and Hg determined by cold vapour AA, As, Se determined by hydride generation, Ca, Cu, Zn determined by low-temperature ashing and analysis of the ash dissolved in dilute H,SO, Polyphosphates analysed for As, Cd, Cu, Hg, Pb -- (As, Cd, Cu, Hg, Pb, Se, TI) HCI pressure dissolution of sample in closed polyethylene bottles (Be, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn.Mo, Ni, P, Pb, Zn) Sample ashed for 48 h at 600 " C , dissolved in 5 ml HCI(1 : l ) , 1 ml VCI (12.5% s o h ) added (As, Cd, Cu, Pb, Zn) Scc rcf. C1427 50ml sample, boil down to f volume, add 5 ml HNO,, boil down to 5 ml, add 5 ml H,O, (30%), reboil, dilute to volume (Ca, Cu, Fe. K, Mr. Na, Pb. Zn) 1983 g. c211 2 345 564 677 687 844 1010 1025 1122 C1321 C1426 C1427 1543 1621 1640 1826 1885 2018 2246 C2292 2319222 Analytical Atomic Spectroscopy An interlaboratory comparison (1841) of the determination of Pb in foods, over an 8 year period, indicated t h a t three techniques (ETA-AAS; solvent extraction- FAAS; and ASV) gave comparable data.Generally the interlaboratory RSDs were c 20% a t levels of 0.1-0.3 ppm Pb. Pb i n sugar beet pulp and molasses by FAAS and ETA-AAS methods gave good i n t e r - laboratory agreement, good agreements w i t h the c e r t i f i e d value f o r the analysis of NBS orchard leaves, and quantitative (97-109%) recoveries o f added Pb (685, 686, 737). A workshop on the analysis of Pb i n foods (1887) showed control of contamination t o be a major f a c t o r i n obtaining good analytical agreement between the 7 participants. the standard deviation being 0.3 ng g-l when o u t l i e r s were excluded and 0.6 ng g-l f o r a l l data. 107%. A collaborative study of the determination o f The data f o r milk analysis gave a mean of 2.2 ng Pb g - l , The average recovery o f Pb added t o milk samples a t 10 ng g-l was

ISSN:0306-1353    

DOI:10.1039/AA9821200216

出版商:RSC    

年代:1982

数据来源: RSC

摘要:

Applications 223 4.9 BODY TISSUES AND FLUIDS 4.9.1 SamDle PreDaration The c o l l e c t i o n by f i n g e r - p r i c k o f blood samples f o r trace element determination i s beset by problems of contamination, and i t i s therefore o f i n t e r e s t t h a t a technique has been reported (C94) which avoids such contamination by using a portable laminar-flow clean bench. Even when venepuncture i s used t o c o l l e c t blood the type of c o l l e c t i o n vessel may o f t e n be a source o f contamination.A recent example o f t h i s i s the considerable contamination o f blood w i t h A1 from evacuated blood-collection tubes and the need t o use s f o r t h i s analysis (1972). 4.9.1.1 Methods i n v o l v i n g Minimal Sample Preparation The most promising new methods f o r the d i r e c t analysis those i n v o l v i n g F I techniques and FAAS.Rocks e t a l . e c i a l l y prepared tubes o f b i o l o g i c a l f l u i d s are 942) determined L i by i n j e c t i n g 10 p1 volumes o f serum i n t o a flowing stream o f deionized water t h a t was pumped t o the nebulizer o f a FAAS instrument. The a d d i t i o n o f physiological concentrations o f K and Na t o the aqueous standards overcame matrix interferences , and the r e s u l t s agreed w e l l w i t h those obtained by analysis of p r e - d i l u t e d spec- imens.nebulization o f 50 p1 volumes o f the supernatant from serum f o l l o w i n g TCA p r e c i p i t a t i o n o f proteins was used (755) t o determine serum Fe by FAAS w i t h a day-to-day precision o f 2 4 % .The d i r e c t analysis o f Pb i n u r i n e by FAAS was achieved by using an e l e c t r i c a l l y heated P t o r Ir loop t o vaporize m i c r o l i t r e volumes i n t o a flame (537). The d i r e c t electrothermal atomization-AAS analysis o f b i o l o g i c a l samples usually requires a d i l u t i o n step. However, Nash e t a l . (C2461) determined K and Na d i r e c t l y i n n a n o l i t r e volumes o f b i o l o g i c a l f l u i d s using graphite microboats.A systematic study of the interferences present w i t h t h i s method was reported. The small volumes allowed an extremely r a p i d analysis time o f 15 s w i t h RSDs o f 3% o r less. Another r a p i d ETA-AAS procedure w i t h an analysis time o f 30 s was achieved by eliminating the need f o r drying and ashing stages (1183).A simple d i l u t i o n o f serum, o r whole blood, w i t h T r i t o n X l O O was s u f f i c i e n t preparation f o r the determination o f Cu by ETA-AAS w i t h an RSD o f 2% (1650). For the determination o f B i by ETA-AAS, Berthole and Renoe (1588) d i l u t e d serum 1 + 1 w i t h 1mM EDTA and achieved a detection l i m i t o f 0.05 ug 1 - l .Homogen- i z a t i o n o f r a t tissues i n 0.25% T r i t o n X l O O enabled P t t o be determined d i r e c t l y a t concentrations of 0.1-10 pg m l " i n the f i n a l s o l u t i o n (790). Rains (C2294) has r e c e n t l y reviewed various techniques o f matrix modification used t o overcome interferences i n d i r e c t ETA-AAS methods including those using the L'vov platform. Holcombe and Eaton (C2097) have also reviewed matrix modi- f i c a t i o n and have discussed the use o f O2 ashing during electrothermal pre- The recovery o f added L i was 98.5101% w i t h an RSD o f 2%.Discrete7-24 Analytical Atomic Spectroscopy treatment, as a means o f eliminating the accumulation o f carbonaceous residues from blood during the determination o f Pb.determined Pb i n blood w i t h RSDs o f 2.1-2.7%. For c a l i b r a t i o n they used aqueous standards which contained 0.2% NH4H2P04 i n 0.5% T r i t o n X l O O as matrix modifier. The a d d i t i o n o f 25 p1 o f 20% !!/! H3P04 t o 250 p1 u r i n e allowed the d i r e c t deter- mination o f Pb by ETA-AAS using a Mo-coated graphite tube (1630).The determin- a t i o n o f Au i n b i o l o g i c a l f l u i d s required the c a r e f u l control o f NaCl concent- r a t i o n s i n samples and standards t o overcome the depressive e f f e c t o f C1 on Au (1728). Fernandez and H i l l i g r o s s (1976) 4.9.1.2 Multi-stage Methods Various procedures used f o r wet digestion o f b i o l o g i c a l samples have been reviewed (338, 1476).reagent f o r digestion o f l i v e r t i s s u e f o r the FAAS determination o f Cu, Fey Mn and Zn. Verlinden (1384) evaluated various procedures f o r the decomposition o f blood and plasma f o r Se determination by hydride generation-AAS and recommended wet ashing w i t h HN03/HC104 using a f i n a l heating stage a t 210 OC. application o f p r o t e o l y t i c d i s s o l u t i o n was the use o f f i c i n t o dissolve lung tissues t o allow the separation and subsequent analysis o f insoluble dust p a r t i c l e s (1116).The accumulated dust contained s i g n i f i c a n t amounts o f Coy C r y Sb and Sc. It was noted (338) t h a t HN03 was the most e f f e c t i v e An i n t e r e s t i n g Dry-ashing procedures f o r the determination o f C r i n b i o l o g i c a l samples have been reviewed and i t was claimed t h a t these are preferable t o those i n v o l v i n g wet digestion (C2100).Cr(V1) i n r a t tissues under d i f f e r e n t drying conditions, i t was noted (2268) t h a t oven drying a t 120 OC gave s i g n i f i c a n t losses o f C r ( I I 1 ) b u t much lower losses o f Cr(V1).blood f o r the analysis o f 8 trace elements by FAAS and ETA-AAS. took less than 30 min and gave resul-is t h a t agreed well w i t h those obtained a f t e r wet-digestion o r d i l u t i o n o f samples. laboratories f o r t r a c e element analyses. H u l l e t a l . (491) however, determined P t i n serum by ETA-AAS a t concentrations o f 25-250 pg 1-1 f o l l o w i n g digestion w i t h However, i n a study o f the r e t e n t i o n o f C r ( I I 1 ) and Sakla e t a l .(950) used oxygen-flask combustion t o prepare 0.1 m l volumes of The procedure Solvent e x t r a c t i o n procedures are now used r e l a t i v e l y i n f r e q u e n t l y i n c l i n i c a l HN03 and e x t r a c t i o n w i t h APDC/MIBK. 5&200 pg 1-1 ranged from 94.2 t o 97.5%.samples from p a t i e n t s treated w i t h the drug ( < l o ppb) i n bone were determined (2263) by a two-stage solvent e x t r a c t i o n me both stages i n v o l v i n g back-extraction i n t o an aqueous phase from dithizone/CC This procedure separated Cd from the matrix and also from Zn which interfered w i t h the ETA-AAS analysis. The o v e r a l l RSD ranged from 610%.The recovery o f P t added t o samples a t The method was s u i t a b l e f o r monitor C i s p l a t i n . Low l e v e l s o f Cd hod, 4'Applications 225 4.9.2 Atomic Absorption Methods 4.9.2.1 Flame Methods Sequential measurements of Ca, C u , K , Mg and Na i n a reference serum were made using d i s c r e t e nebulization and FAAS o r FAES (1729). Integrated absorbances were obtained using an automatically triggered d i g i t a l i n t e g r a t o r and the analytical accuracies were w i t h i n +3% of the c e r t i f i e d values of the elemental concentrations.Discrete nebulization FAAS has a l s o been used t o measure Au, Cu, Fe, P t and Zn i n serum (C2363). concentrations of 5CL1200 pg 1-1 (1011) and i n 5 ml volumes of blood a t levels of 100-800 pg 1-1 (144).FAAS analysis o f Pb i n deciduous teeth a f t e r ashing and dissolution i n HC1 (2274). The observed concentration range f o r urban children was 0.1 - 30.0 pg g-l and the RSD f o r internal q u a l i t y control material was 2.9% a t 16.7 pg g-l and 7.4% a t 6.1 pg g-’. Solvent extraction and FAAS have been used t o measure Pb i n urine a t high Solvent extraction w i t h APDC/MIBK was a l s o used in the Other references of i n t e r e s t - Li in plasma and erythrocytes : 654.Measurement of Ca in t i s s u e s following solution containing La( 111) : 485. homogenization i n a butanol/HCl 4.9.2.2 Electrothermal Atomization Methods __ Zinc i n small volumes of serum i s usually measured by FAAS, b u t with studies involving neonates and very young children i t i s desirable t o use the minimum sample volume possible.Shaw e t a l . (1014) determined Zn i n sera by ETA-AAS using <2@ 111 volumes which were diluted 1t199 f o r analysis. For c a l i b r a t i o n , i t was necessary t o use matrix matching by adding aqueous standards t o a control serum, which had been depleted of Zn by treatment w i t h Chelex 100.ment was obtained with analyses by FAAS, and the w i t h i n and between batch RSDs were 2.5 and 5.6% respectively. The recovery of added Zn was 95%. These authors did not observe any s i g n i f i c a n t differences i n the Zn concentrations of plasma o r serum from the same individual. Foote and Delves (1521) avoided the problems of contamination w i t h Zn t h a t can occur a t these high dilutions by using a high internal gas flow r a t e during atomization and determined Zn i n sera diluted 1+24.Matrix interferences were overcome by incorporating albumin and NaCl i n t o the aqueous standards. T h i s procedure worked well f o r standard graphite tubes, although not f o r pyrolytically coated tubes, good agreement ( r = 0.94) was obtained w i t h analyses by FAAS.and the detection l i m i t was 0.36 umol 1 - l . ation i n the reference concentrations observed f o r heal thy controls in d i f f e r e n t countries. Good agree- The RSD a t 12.6 pmol 1-1 Zn i n serum was 3.6% Analyses of blood and serum samples f o r manganese showed a s i g n i f i c a n t vari- In China the observed levels of Mn i n whole blood ranged from 4-19226 Analytical A tomic Spectroscopy ug 1-1 (2234), and comparably high mean values o f 17.4 pg 1-1 (blood) and 2.3 pg 1-1 (serum) were observed by Japanese workers (1065).are higher than those o f 1.14 pg 1-1 observed i n Europe (2015). methods had detection l i m i t s o f <0.1 ug 1-’ so i t i s u n l i k e l y t h a t a n a l y t i c a l s e n s i t i v i t y i s responsible f o r these v a r i a t i o n s i n reference l e v e l s . vanadium i n u r i n e a t concentrations down t o 0.5 pg 1 - l .The RSDs ranged from 46% a t concentrations o f 10-20 pg 1 - l and recovery o f V added t o u r i n e was 96100%. A d i r e c t determination o f V i n serum (524) t h a t involved only a 1+1 d i l u t i o n w i t h 0.5% !/! H2S04 gave a detection l i m i t w i t h p y r o l y t i c a l l y coated tubes o f 30 pg (1.2 pg l - ’ ) , and an RSD o f 3.5% a t 12.4 pg 1 - l .important p a r t i c u l a r l y f o r c o n t r o l o f p a t i e n t s on t o t a l parenteral n u t r i t i o n . Hal 1s and F e l l (C274) overcame the problem o f background emission interferences i n the analysis o f C r i n u r i n e by lowering the atomization temperature from 2700 t o 2400 OC.They were able t o measure 2-12 pg 1-1 o f C r i n u r i n e from p a t i e n t s on t o t a l parenteral n u t r i t i o n , using continuum source background correction, and could detect 0.2 pg 1 - I . echelle monochromator and a wavelength modulated background correction system i n t h e i r studies (1185, 2275, C2463) and could detect down t o 0.03 pg 1-1 o f C r i n urine.They observed ’normal’ l e v e l s i n the region 0.1-0.5 pg 1-’. Considerable a t t e n t i o n has been focussed on the determination o f selenium These concentrations Most o f the Buchet e t a l . (1582) used solvent e x t r a c t i o n w i t h cupferron/MIBK t o measure The analysis o f chromium i n b i o l o g i c a l f l u i d s i s becoming increasingly V e i l l o n e t a l .used a continuum source, i n whole-blood and plasma by ETA-AAS. the Se resonance l i n e a t 196 nm i s reported t o cause background problems t h a t necessitate the use o f a Zeeman background correction system (C58). - a1 . (386) , however, successfully used D2 continuum source correction f o r the d i r e c t determination o f Se i n blood d i l u t e d 1+1 w i t h T r i t o n X100.bias was observed between analyses by ETA-AAS and by spectrofluorimetry. RSD was 9.8% a t 160 pg 1 - l . Pleban e t a l . (1016) measured Se i n plasma and i n erythrocytes using Zeeman background correction , and achieved RSDs o f 6.4% a t 93 pg 1-1 and 5.6% a t 150 pg l-l, respectively. For example, the use o f Ag was found t o give b e t t e r s e n s i t i v i t y f o r Se than e i t h e r N i o r Cu (2215).The samples o f serum o r seminal plasma were treated w i t h TCA t o p r e c i p i t a t e proteins p r i o r t o the analysis, and the RSD a t 1.3 pmol 1-1 (103 pg 1-’) was 3%. Alfthan and Kumpalainen (1524) d i l u t e d serum 1 t 9 w i t h 0.072 M HN03, containing N i ( I I ) , f o r the determination o f Se i n serum o r plasma, b u t the precision was only 12% a t 71.8 pg 1-1 and 15% a t 61.4 pg 1 - l . o f ashed blood by e x t r a c t i o n w i t h 2,3-diaminonaphthalene was used p r i o r t o ETA- AAS w i t h Cu( I I ) added t o the organic solvent i n the graphite tube (1942).This method gave an excellent recovery o f added Se w i t h a c h a r a c t e r i s t i c concentration P a r t i a l overlap o f nearby Fe l i n e s w i t h D i l l o n et No s i g n i f i c a n t The Matrix modifiers f o r selenium have been widely reported.Separation o f Se from solutionsApplications 227 of 5.3 pg 1-1 for an absorbance o f 0.0044. Me3Se+ from u r i n e by cation exchange on Dowex 50W-X8 p r i o r t o ETA-AAS w i t h the a d d i t i o n o f N i (11).and o f t o t a l Se were 82-102% and 96101% respectively. A small number o f hydride generation techniques have also been reported f o r Oyamada and I s h i z a k i (467) separated The RSDs ranged from 3.7-6.2% and the recoveries o f Me3Set Se (1513, 1548). Digestion w i t h HN04/H2S04 was s u f f i c i e n t f o r analysis o f whole- blood, red c e l l s and plasma (1548) w i t h concentrations ranging from 6-160 pg 1 - l . The RSDs ranged from 4.@-5.5% a t concentrations o f 120-144 pg 1 - l .and Meranger (1513) used HN03/HC104 digestion o f tissues p r i o r t o analysis o f As and Se by hydride generation AAS. X l O O d i r e c t l y by ETA-AAS w i t h RSDs o f 6.0% a t 40 pg 1-1 and o f 3% a t 123 pg 1 - l . The concentration range observed f o r healthy c o n t r o l subjects was much lower, 2-15 pg l-', and was almost i d e n t i c a l w i t h t h a t observed by Leung and Henderson (2276), b u t they also observed higher values o f 25-500 pg 1-' i n p a t i e n t s on heamodialysis.These l a t t e r workers used matrix modification w i t h M S ( N O ~ ) ~ and a L'vov platform technique t o obtain w i t h i n and between run RSDs o f ~ 3 . 5 % and <7.4% respectively. Although the discrimination between serum A1 l e v e l s f o r controls i s c l e a r i n both o f these studies, there i s evidence t o suggest t h a t the 'normal' l e v e l o f A1 i n serum may be less than 1 pg 1-1 ((2173). Monitoring changes of platinum l e v e l s i n serum i n response t o the therapeutic administration cis-dichlordiammine P t ( 11) ( ' C i s p l a t i n ' ) i s o f increasing import- ance i n cancer chemotherapy.serum (1875) and o f ' f r e e ' c i s p l a t i n i n blood f o l l o w i n g d i f f e r e n t modes o f admin- i s t r a t i o n (1059) were made using simple ETA-AAS a t r e l a t i v e l y high concentrations. Can0 e t a l . (1111) determined P t i n plasma by ETA-AAS f o l l o w i n g a 1 + 9 d i l u t i o n w i t h 0.5% HN03, and i n u r i n e a f t e r a 1 + 19 d i l u t i o n w i t h H20.l i m i t was 10 ng m l - 1 i n the d i l u t e d solutions and the RSDs f o r 0.3-2.6 pg m l - 1 o f P t i n plasma ranged from 2.9-4.7%. o f P t i n sera and i n u l t r a - f i l t r a t e s by ETA-AAS, f o l l o w i n g wet ashing and APDCI MIBK extraction. combination o f HPLC and ETA-AAS was used t o study various C i s p l a t i n ' f r a c t i o n s i n u r i n e (1730).i s t h a t RSDs of 3 4 % are often achieved w i t h methods t h a t employ a simple d i l u t i o n as sample preparation. 0.2% HN03 and 0.6% T r i t o n X l O O f o r Pb analysis and reported an RSD o f 2.7%. Subramanian e t a l .(1638) achieved w i t h i n and between run RSDs o f 3.9 and 4.0% respectively f o r blood Pb analyses. and 0.5% T r i t o n X l O O and the method could detect 2 pg 1-1 . blood w i t h NH4H2P04 f o r ETA-AAS, using a L'vov platform technique, gave a method Subramanian Parkinson e t a l . (2272) measured aluminium i n sera d i l u t e d 1 + 1 w i t h T r i t o n Parmaco-kinetic studies o f protein-bound-Pt i n The detection H u l l e t a l .(491) measured 25-250 pg 1-1 A The recoveries o f P t added a t 50 t o 200 p g / l were 94.2-97%. A notable feature o f papers dealing w i t h the determination o f lead i n blood Ikeda e t a l . (1062) d i l u t e d whole blood w i t h The samples were d i l u t e d w i t h 0.5% (NH4)2HP04 D i l u t i o n o f whole-228 Analytical Atomic Spectroscopy w i t h RSDs of 2.1-2.7% and which required only aqueous standards i n 0.5% HN03 and 0.2% NH4H2P04 f o r c a l i b r a t i o n (1976).have discussed methods o f blood Pb analysis by ETA-AAS t h a t included probe and platform techniques, w i t h simple d i l u t i o n as preparation, using samples deproteinized w i t h HN03 (C304, C305, C2075, 2490).use o f aqueous standards f o r c a l i b r a t i o n and the demonstration o f a n a l y t i c a l accuracy by the analysis o f known q u a l i t y c o n t r o l blood specimens. tissues and f l u i d s (C61, C308, 455, C2478). determined down t o 0.1 ug 1-1 o f Cd i n blood and i n u r i n e using matrix m o d i f i - cation w i t h (NH4)2HP04, together w i t h T r i t o n X l O O (blood) o r HN03 ( u r i n e ) .Shimizu e t a l . (455) achieved a s i m i l a r detection l i m i t f o r ETA-AAS measurement o f Cd i n solutions o f ashed u r i n e and obtained an RSD o f 1.76% a t 0.36 ug 1 - l . Determinations o f other t o x i c metals i n b i o l o g i c a l samples were: the deter- mination o f Sb i n u r i n e a t concentrations up t o 200 ug 1-1 (1537); analysis o f T1 down t o 20 ug 1-1 i n blood (791); and the measurement o f Sn i n plasma (1002).Iwai e t a l . (1008) determined mono-, d i - and t r i - b u t y l Sn and inorganic Sn i n r a t tissues and f l u i d s . Ottaway, F e l l and t h e i r col leagues The main features were the Sensitive ETA-AAS methods have been reported f o r measuring cadmium i n body Subramanian and Meranger (C2478) 4.9.3 Atomic Emission Methods Few publications were concerned w i t h FAES methods and almost a l l o f the reports received were concerned w i t h plasmas.I n t e r e s t i n g innovations i n applications o f OES t o the analysis o f b i o l o g i c a l f l u i d s were the measurement o f organic compounds. Heine e t a l . (679) analysed 100 111 volumes o f mixtures o f nucleotides by separation using HPLC and analysis using f l o w i n j e c t i o n and ICP-OES t o measure P a t 213.5 nm.RSD o f 4.5% and a detection l i m i t o f 750 ng. Phenolic constituents o f urine, such as catechol and 4-methylcatechol which may have a r o l e i n bladder cancer, were analysed by determination o f B by GC-MIP a f t e r conversion t o t h e i r c y c l i c - alkylboronate esters (C72).Hagen e t a l . (C168) used a He-MIP detector w i t h GC t o measure perfluoro-octanoate i n human blood plasma f o l l o w i n g i n d u s t r i a l expos- ure t o t h i s compound. isomer, compared w i t h more than 50 peaks using electron capture detection. form only a m i n o r i t y o f the applications reported b u t contain useful information. Minoia e t a l .(381) measured S i i n u r i n e down t o 100 ug 1-1 by ICP-OES and achieved an RSD of 4.7-5.8% a t the average l e v e l s found i n humans o f 10.5 mg 1 - l . The measurement of T i i n r a t and mouse tissues by ICP-OES was developed t o support a toxicology study o f 'titanocen d i c h o l o r i d e ' (C2303). The method could detect 40 ppb T i i n tissues, gave 94+6% recovery o f T i added a t 0.1-2.0 ppm and RSDs o f 611%.Camiera e t a l . (1633) determined Mn and N i i n whole blood by d i s s o l u t i o n The method had an This detector system gave only one peak from the suspected Single-element analyses o r measurements o f only a few elements by OES methodsApplications 229 w i t h TMAH and using ETA t o introduce the sample i n t o an I C P .by standard additions and the concentrations found f o r both elements ranged from 4-14 pg 1 - l . Gardiner and B r l t t e r (C175) used a DCP as the detector f o r measuring Cu, Fe and Zn i n proteins separated from human serum by gel f i l t r a t i o n chromatography. development. a t 215 ppb using isotope d i l u t i o n .e i t h e r DCP-OES (C15, C165, C207) o r ICP-OES (C209, C210, 1257, C1330, 1692, C2708). Barnes (C1330, 1692) used polydithiocarbamate chelating resins t o separate and concentrate Be, Coy C r y Fey Hg, Mn, T i , V and Zn from serum and u r i n e f o r analysis using pneumatic-nebulization i n t o an I C P , and also used hydride generation i n the determination o f As, B i , Sb, Se, Sn and Te.(C205) has reviewed the various modes o f sample i n t r o d u c t i o n f o r analysis by ICP-OES. Coy Cu, Fey Mn, N i and Pb. Calibration was The use o f an ICP o r M I P as i o n source f o r mass spectrometry i s an e x c i t i n g Douglas e t a l . (C22) used t h i s technique t o measure Pb i n blood Many mu1 ti-element analyses o f b i o l o g i c a l samples have been reported using K i r k b r i g h t Detection l i m i t s using ETA i n t r o d u c t i o n ranged from 6-64 pg f o r Cd, 4.9.4 CornParison o f Methods Oster and P r e l l u i t z (2271) compared hydride generation AAS f o r the determination of Se i n serum w i t h d i r e c t analysis by ETA-AAS using N i as matrix m o d i f i e r .The c o r r e l a t i o n c o e f f i c i e n t over the range 40-110 pg 1 - l was 0.94 and both techniques gave RSDs o f approximately 54%.Brown e t a l . (1610) c a r r i e d o u t a s i m i l a r study, b u t i n a d d i t i o n they evaluated a hydride-generation AFS method which showed the most promise b u t which was n o t commercially a v a i l a b l e . hydride generation AAS and f l u o r i m e t r y showed ETA-AAS t o be the best procedure w i t h an RSD o f 6% ( n = 4).the v a r i a t i o n between r e s u l t s by hydride generation was unacceptably higher w i t h an RSD o f 35% (n = 5 ) . I n two comparative studies o f hollow cathode-OES and ETA-AAS, the former technique was shown t o have b e t t e r precision and fewer matrix interferences f o r the determination o f Ca (1175) and A1 (1732).Excellent agreement has been obtained between ETA-AAS and c o l o r i m e t r i c analysis f o r the analysis o f serum f o r Fe (1624) and f o r Zn (2013). The analysis o f human bones f o r Cd a t 1MO ppb and f o r Pb a t 3-15 ppm was accomplished by ETA-AAS and by d i f f e r e n t i a l pulse- ASV w i t h both techniques g i v i n g comparable data (246). Both ETA-AAS and ETA-AES gave good agreement w i t h stable isotope d i l u t i o n GC-MS f o r the analysis o f C r i n u r i n e a t 0.5 pg 1 - l (C2175).An i n t e r - l a b o r a t o r y study (1623) o f Se measurements i n human serum by ETA-AAS, The f l u o r i m e t r i c data had an RSD o f 10% ( n = 4) b u tTable 4.9 BODY TISSUES AND FLUIDS Element A/nm Matrix Technique, Concentration Atomization, Analyte Form Sample treatment Ref.A1 Al A1 Al A1 A1 A1 A1 A1 A1 A1 A1 A1 A1 As As As As As - Serum, haemodialysate, 309.2 Hair water, bone Blood plasma Blood plasma - Hair - Serum, urine - Serum 396.2 Tetanus toxoids - Biological samples - Serum - Whole blood Whole blood, serum, plasma Serum, water 309.3 Serum, urine - Urine 193.7 Liver, kidney - Urine, faeces - Urine - Body fluids, tissue ’> 1.3 pg/l 0-1.5 ng > 0.5 pg/l 1 .o- 1000 fig11 < 0.15 mg/l - 9.2 pg/l 1 .I g/1 - MI1 > 1 .o pgll < 200 pg/l 2-500 pg/l > 30 ng - - A, ETA, L A, ETA, S A, ETA, - A, ETA, L A, ETA, L A, ETA, L A, ETA, L A, F, N,O/C,H,, L A, -, - E, Hollow cathode, - E, A, - A, -, - A, ETA, L A, ETA, L’vov platform, L A, ETA, L A, ETA, L’vov platform, L A, Hydride, G A, Hydride, G A, Hydride, G A, Hydride, G A, -, - E, P, ICP, - Liquid samples: dilute with aqueous solution of Triton X-100 Bone: ash in low temperature oxygen plasma circuit Wash with ether in soxhlet extractor, dry, cut into 1 cm length and weigh.Standards prepared by absorption of lop1 of standard solutions (0-0.5 ppm) onto Amberlite 1R- 120H beads Collect blood in EDTA-coated, Al-free plastic tubes; dilute with aqueous solution of Triton X-100 and NH,NO, Digest in acid No predigestion Automatic sample injection Digest with HNO,/H,SO, Comparison of methods; hollow cathode suffered least interference, atomic absorption was most sensitive and fastest Study of blood collection and storage procedures Comparison of D, arc and Zeeman background correction; nature of graphite furnace found to be an important variable Digest with HNO,; H, added to furnace inner gas flow Dilute serum (1 + 1) with 1% aqueous solution of Triton X-100; RSD - 5% Dilute serum (1 + 1) with 0.14% aqueous solution of Mg(NO,),; dilute urine (1 + 1) with H,O; within run RSD < 3.5%, between run RSD c 7.4% None Digest in HNOJHCIO, ; semi automatic hydride generation; interferences by transition elements overcome with LaOH Dry ash with Mg(NO,), -MgO, dissolve in 6M HCI, add NaBH, Automated hydride generation system C273 393 655 94 1 1115 1179 1186 C1261 1732 1972 C2096 C2173 2272 2276 833 1513 c2102 1617 1782 2043Au Au Au B Bi Ca Ca Ca Ca Ca Ca Ca Ca Ca Cd Cd Cd Cd Cd Cd Cd Cd 242.8 - 242.8 249.8 223.1 422.7 - - 442.7 - - - - 422.7 - 228.8 - - 228.8 - - - Synovial fluid Whole blood, plasma, red cell lysate Tissue, whole blood, serum Steroidal carboranes Serum, urine Serum Kidney Serum Serum Erythrocytes Hair Hair Dental enamel Polymorthonuclear leukocytes Urine Bone Whole blood Saliva, whole blood, plasma Urine Heart muscle, kidney Placenta Liver 0.04-1.99 mg/l A, ETA, L - A, ETA, - - E, P, MIP, G < 100 Irgll A, ETA, L <O.lg/l E, P, ICP, L A, F, Air/C,H, or N,O/C,H,, L - A, F, L - < 120 mg/l - 600 pg/l < 4.5 mg/g - - < 2 mgll > 0.2 rg/l 10-60 ng/g > 0.16 pg/l - A, -, - A, --, L A, F, - A, ETA, - A, -, -, Neutron activation A, F, - E, -, - A, F, Air/C,H,, L A, ETA, L’vov platform, L A, ETA, L A, ETA, Segmented rod atomizer, L A, ETA, - 0.5-1.22 pg/l 3 ng/g (Dry wt.) 50-70 ng/g (Dry wt.) A, ETA, Ta or W coated tube, L A, F, L A, ETA, - 395 Digest with H,SO,/HNO,, calibrate by standard addition.Proteins separated by gel filtration - Digest in conc. HNO, at 70°C for 4 h, cool, oxidize with 10% H,O,, dilute with H,O. Background correction and matched standards essential Separation by GC Dilute (1 + 1) with 1 mM EDTA, char in furnace under 0, atmosphere Dilute 50-100 fold; comparison of methods Homogenize ultrasonically with butanol/HCI/La solution, centrifuge and determine Ca in supernatant Examination of interference by phosphate and sulphate Dilute (1 + 49) with 10 mM LaC1,/50 mM HCI Investigation of method Remove adsorbed Ca by soaking in dil.HCI, ash in Pt crucible Comparison of methods Homogenize (1 + 4) with 49 mM La203/0.8M HCI Zeeman background correction, matrix modification Digest under pressure in 65% HNO, at raised temperature; calibrate by standard addition Dilute (1 + 19) with 0.1% solution of Triton XlOO at 30-37°C - Decompose organic material with HNO,/H,O, solution Digest with HNO,/HCIO, Comparison of methods for sampling, homogenization and decomposition Digest with HCIO,/HNO,/H,SO,, extract at pH 8.5-9.0 with dithizone in CCI,.evaporate. oxidize organic material 1178 1728 C72 1588 2, 839 485 681 756 1003 1076 1823 1884 2270 C6 1 246 C308 353 p55 54 1 6 04 704N w 13 Table 4.9 BODY TISSUES AND FLUIDS-continued Element h/nm Matrix ~ ~~ Technique, Concentration Atomization, Analyte Form Sample treatment Ref. Cd Cd Cd Cd Cd Cd Cd Cd Cd Cd Cd c o Cr Cr Cr Cr Cr Cr Cr Cr - 228.8 228.8 - 228.8 - - - - 228.8 228.8 - - 357.9 - - - - - - Liver metallothionein Kidney, liver, heart Hair Whole blood Whole blood Whole blood Whole blood, urine, hair Urine Hair, liver, kidney Bone Whole blood Heart muscle, kidney Urine Urine Heart muscle, kidney Urine Hair Whole blood Serum, urine Serum ~ Characterization of protein A, -, - A, F, L A, ETA, L MIBK 66-330 ng/g (Wet wt.) Digest with HNO,/H,O,, adjust pH, extract with CHC1, or - > 150 ng/l > 100 ng/l > 50 ng/l - - 0.8 pg/l 3 -3 8 pg/l > 8 ng/g (Dry wt.) < 1 wg/l 0.1 - 12 pg/l > 24 ng/g (Dry wt.) > 0.03 ,ugh - 16Ong/g < 60 ng < - 0.1 pg/l A, ETA, L A, ETA, L A, ETA, L A, ETA, L A, ETA, L A, ETA, L A, ETA, - A, ETA, L A, -, - A, F, - E, P, ICP, - A, ETA, L A, F, - A, ETA, - A, ETA, - A, -, - A, ETA, - A, ETA, - Studies of a separative column atomizer Add ammonium phosphate solution, ash in 0, atmosphere in furnace Dilute (1 + 4) with 0.5% solution of (NH,),HPO,/Triton x-100 Extraction Low temperature digestion in closed pressurized system Dilute with IMHCI, extract on column of Dowex 1-X2 in iodide form, elute with 1~ HNO, Metabolic study Remove lipid by ether extraction, digest with HNO,/HClO,, adjust to pH 3-3.5, extract with dithizone in CCI,, back extract into HCl/HEDTA at pH 8.5, re-extract with dithizone/ CCI,, back extract into HCI Review of analytical methods Digest with HNO,/HClO, Cr(II1) or Cr(V1) selectively preconcentrated on poly (dithiocarbamate) or poly (acrylamidoxime) resins according to pH Dilute (1 + 1) with distilled water Digest with HNO,/HCIO, Calibrate by standard addition Comparison of hair washing procedures prior to Cr determination Dilute (1 + 1) with HNO, and stand overnight, heat to 130°C.cool, mix with HCIO,, boil for 30 min, cool, centrifuge at 3000 rpm for 10 min, adjust to pH3, mix with 5% APDC and MIBK, determine Cr in MIBK layer None, calibrate by standard addition Freeze dry in siliconized quartz, dry ash in muffle furnace 836 945 1369 1475 1638 C2478 1840 1876 1977 2012 2263 2211 541 c210 C274 541 $ 1185 1941 $ a, 2099 $ c2100 gCr Cr Cr 357.9 <:r C U C U cu <'U 324.7 C U 242.8 CU c u Cu CU cu cu CU ('U Cu CU 324 7 ('U cu cu <'U ('U En?) nies (Ag) I Urine Rat tissue Urine Serum Biological fluds Blood.urine Blood Hair Synovial fluid Plasma. bile Breast milk Plasnia. livcr. spleen Plasma, bile Tissue Blood. p k e n t a , amnjotic fluid Liver. mctallot hionein Amniotic fluid Plasma Leucocytcs Whole blood, serum Biological mJtcridl Saliva Gallstone. renal calculus Blood. ~ e r u i n , urine. livcr Muscle fibers Blood plasma ~ 0 5 rg/l 0.1 2.5rg/l - 0.I rg/I > 5 rril < I 5ng 0.5 2mg/l . 0.6 mg/l 0.25 -2.2 ng/l0" cells 0 04--2.25 Iiip/g A. ETA, .- E, E'rA, - A. kTA, 1. A, ETA, - E. P. D.C., L A. -, - A. -, - A, ETA. S A, I T A , I. A. kXA. - A, -, - A, -, - A, ETA, L A. I-. - A. -. .- A , -. - A, ETA. - A. ETA. - A, I<TA, L A, ETA. - A, . - A. LTA. -. A:,- A, I.TA. - A:.- 1.:. Y. MIPS G Cornparison vf malytical methods Comparison of wrnple preparation procedures Dilute (100 t I ) with 1MHCI.calibratc by atandard additivn Separate nietalloproteins on a Sephdcryl S-300 column, determine Cu, I:e and Zn sirnultanc'ously in eftlucnt Comparison of colorimetric and AA determination vf Cu Comparison of methods for the determination of ceruloplasmin See Al, ref. 393 See Au, ref. 395 Dry ash. dlssolve residue in 5N HCI None InvcstiRation of nicthod Characterization ot proteins Separate nictalloproteins o n a Sephacryl S-300 column Separate nietalloproteins on DEAE Scpharose C L 6 B column Separate leucocytes by dettran sedimentation. digest cells u i t h IiNO, Add 1% of Triton X-100 Interlaboratory comparison Cornparison of sample preparation methods: ( I ) HNO, - l i 2 0 2 digestion. (2) svluhilizc u i t h Solucne X-350.(3) dilute with Triton X-100, (4) digest with IINO, I I ~ O ~ , e\tr;ict with APDC and DDC Dtssolvc o r n t r a c t with 109 DDC/MlHK Invcsri~!atrvn ( i f Iutses using '"Cu: uirh charring hclou. 700 'C and rapid ticating t o 2600 C locscs arc miniiniied Place fresh fro/.en section on photofraphic film. after ekpcisurc and film processing dctcrrnine Ag deposited in various area\ of Scparatc volatile fluorinated clilnpvUndS b) capillary GC thc photOgrJphlc film ('2175 s, 2268 2 2275 b C2463 C175 335 34 I 393 395 688 708 758 759 760 835 836 1022 1 l u 3 1551 1650 1819 1880 1974 1981 1012 <'I68 I d '4 'ATable 4.9 BODY TISSUES AND FLUIDS-confinued Technique, Andyte Form Element h/nm Matrix Concentration Atomization.Sample wabnent Ref. 248.3 287.6 253.7 253.7 Serum Breast milk Blood Plasma Plasma, liver, spleen Liver Amniotic fluid Serum Serum. tissue Tissue, body fluids Tissue Blood, urine Urine Hair Whole blood Urine, hair Blood, tissue, urine tfair Hair Blood, urine. liver > 5 re/! - 0.7 mg/l < 1.2mg/l > 0.1 2 ng > 0.5 pgll > 0.4 ng - 17 rg/l 0.1 -5O~g/g > 0 5 n g E, P.D.c. L A. -, - A. -. - A, F. L Discrete nebulization A, -, - A, -. - A, ETA, L A, ETA. L A, -. - A, ETA. L A, -.- I:, A, - E. Hollow cathode, - A, Cold vapour, G A, Cold vapour. G A, ETA, L A, Cold vapour. C A. -, - A, -, - A, ETA, L A, Cold vapour, G A, Cold vapour, G See Cu. ref. C175 Dilute ( 1 t 2) with H,O, centrifuge, separate on column of G3000SWX2-G2000SWX2, elute with 0.1M phosphate buffer (pH 7.3)-O.IM KCI.determine Fe in Hb lraction Separate with TCA-arcorbate See Cu. ref. 758 Wet ash See Cu. ref. 1022 Dilution with H,O, or addition of reducing agent and TCA followed by centrifugation. or addition of FeCI, and M O , followed by centrifugation Digest with HNO,, add f-DTA, calibrate by standard addition Comparison of methods; hollow cathode emission preferred Urine: no pretreatment, reduce with Sn(ONa),.Blood. mineralize, reduce with Sn(ONa), Mix with KMnO,/H,SO,. add hydroxylamine HCI, reduce with SnCI, Comparison of loss of Hg during drying stage. No losses detected from mixtures of HCl/fi,O,, HCI/HNO,/H,O, or atmosphere of H,S in tube before drying Dilute blood ( I + 4) with H,O. add KMnO,(wlid) and II,SO,.cool, dilute (3 + 2) with H,O. add NH,OH.HCI solution till colourless, reduce with SnCI, solution Disperse with 1.5M KOIi, oxidize with KMnO.. add H,SO, t o complete midation, reduce excess oxidant wlth oxalic acid Studies of a separative column atomizer Examination of sources of analytical errors (2175 708 734 755, 1064 75 8 838 1022 1624 1882 C2407 402 I175 603 132 792 795 963 1060 I369 1552 1781Urine Urine Hair Breath, saliva Nail tissue Plasma Plasma, serum Serum Urine Inner ear fluids Urine Renal tubular fluid Plasma Plasma, erythrocytes Serum Serum Serum Serum, urine.faeces Biological material Hair Serum Dental enamel Lcucocytes Plasma, bile Urine A, Cold vapour. G A. Cold vapour, G 0.28-4.4 mg/l A, Cold vapour, G A. -. - - 6 mg/g E, F, L E, F.L E. F, L t. F. L E, I-, L > 50 ng/l E, F, L E. F. L A, ETA, L E, F, - A. ,- A, -. - A, I:, L A. -. - E. F, N,O/C,H,. L < 0.3 mg/l A. -, - A, -. - A, -. - A. -, - A, I;, - < 1.2 mg/l A. F', Air/C,H,. L A, ETA. - A. -, - Automated vapour generation system Add ION NaOH/2'% DL-cysteine/defoaming agent (tri-Bu phosphate)/solution of (SnC12/2h'HCI/Cd SO,) Determination of inorganic Hg, phenyl Hg and alkyl Hg by adjustment of pH of digest Application of the graphite 'T' tube atomker Dry, defat with Et,O.extract with H20 on boiling water bath Comparison of flame photometry with potentiometry Comparison of flame photometry with ion-selective electrodes Comparison of flame photometry with potentiometry Spot urine onto filter paper, extract with aqueous solution containing Li as internal standard and a surfactant Micro method for simultaneous determination of K and Na Comparison of flame photometry with ion-selective electrodes Micro-analytical technique (0.1 nl); interference effects examined Comparison of methods; examination of stability of plasma specimens - Flow injection system; Na and K added t o standards Buffer with K (2000~~g/ml) add saponin solution in Triton x-100 No dilution.reparation or preconcentration; prepare standards in 21% glycerol Dilute serum ( 1 + 199) and urine ( I + 399) with 0.1% LaCI, solution Interlaboratory comparison Comparison with neutron activation and literature values Comparison with photometric methods; cloudy sera produced inaccurate results with the latter Dilute ( 1 + 9) with releasing agent (49mmol/l La,O, in in 0.8M tiC1) Nutritional studies Separate by ionsxchange chromatography on Spheron-Oxin 1000 1782 2 1972 '' 2, 1975 233 1 607 608 657 658 1018 1019 1822 C246 1 602 654 94 2 94 8 1184 1758 1819 1823 1881 1884 2270 688 73 1Table 4 9 HODY TISSUES AND I LUIDS cortrmued Element h/nm Mahh Technique, Concentration Atomization, Analvte Form Sample treatment Ref.Mn Mn Mn Mn Mn 257.5 Mn Mn Mn Mn Mn Mn N Na Na Ni Rcd cells Plasma. bile Tissue Whole blood. serum Whole blood, muscle Clinical wniples Saliva Serum Whole blood Serum Serum Biological material Nail tissue Clinical samples I'la~ma. serum Serum Milk Urine lnncr ear fluids Scruni Urine Renal tubular fluid Urine < 5 0 rg/l 2.3-17.4rgil 4 -- 14 #/I 0.1 --IOug/l 0.I - 10 ugh 4 - 19.3 rg/l - 6.5 rnglg - 400 mg/l > 0. I rg/l A. ETA, - A, ETA, - A, F, N,O/C,H,, - A,I<TA. - E. P, ICP with ETA. L A , - , - A, ETA. - A, ETA. - A, ETA (Zceman). - A. ETA, - A, ETA, ~ E - - . . E 1: A, I:TA. L A. ETA. L . . Wet digestion. dry over NaOH in desiccator. remove Fe by extraction Bu, phosphate. form ternary complex with dithirone and 6-phenanthrolinc Investigation of method Dilute blood ( I + I ) with aq. 2% Triton X-100, dispense onto graphite rod atomizer. add tetramethyl-ammonium h>droxide solution. ash, repeat solution addition. dtomize. Dissolve muscle in tetramethylammonium hydroxide Study of ashing conditions See Cu, ref. I880 Optimization of method See Al, ref. C2096 Separate N-containing compounds on ion-exchangc column 04-72) with ninhydrin at pH 5.4.concentrate. decompose with 2N HCI on hot water bath, oxidizewith H,O,. dccompose NH, with CuO CaO See K. ref. 607 See K. ref. 608 See K. ref. 657 See K. ref. 658 See K , ref. 1018 See K. ref. 1019 lhainination of Na binding by dialysis. NMR. and ion-selective electrode$ See K . ref. 1822 See K. ref ('2461 Ektraction proccdurc 154 759 760 1065 1633 1818 1880 2015 C2096 2334 C24 18 680 607 608 657 658 84 1 1018 1019 1020 1822 C246 I 157Ni Ni Ni Ni P P Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Serum.urine Whole blood, muscle Tissues, body fluids Serum Nucleotides Serum, muscle microsomal fraction Serum Bone Blood Blood Blood, urine Blood Urine Blood, liver Blood Blood Blood, urine Blood Blood Urine Blood Blood Blood A, ETA, L E, P, ICP with ETA, L A, -, - E, P, ICP, - A, ETA, - E, P, ICP, L A, ETA, - Mass spectrometry with ICP or MIP afomization A, ETA, L A, ETA with graphite probe, L A, ETA, L F, F, L A, ETA, L A, F with electrically heated metal loop, L A, F, L A, ETA or F, - A, -, - A, ETA, - A, -, - A, ETA, - A, -, ~ A, ETA, - A, ETA, - A, ETA, L Digest with HNO,/H,SO,/HClO,, adjust to pH7 with NH,OH, extract as bis(1-pyrrolidenecarbodithioate) nickel(I1) complex with MIBK See Mn, ref. 1633 - Separate mixtures of nucleotidcs on an anion-exchange column (Micro Pak AX-10) with acetate buffer Add equal vol. of 1% ammonium molybdate and 2 vols of IMHCl to the sample, extract molybdophosphoric acid with Et ether/2-pentanol, release Mo with ammonium buffer (PH 9.8) See Cd, ref. 246 Aqueous dilution Deproteinize with 2% HNO, Dilute (1 + 4) with H,O Add H,O,/HNO, to sample, centrifuge, analyse supernatant See Cd, ref. 704 - Extract with HCI, H,PO,, KI into MIBK Dilute with Triton X-100 React blood with Ca-EDTA and APDC Dilute with 0.2% HN0,/0.6% Triton X-100 Examination of effect of heparin, citrate and EDTA on whole blood lead standards - 946 3. 0 12 1633 2043 C2417 679 733 c 2 2 246 C304 C305 C306 C307 537 704 794 835 906 944 1001 1011 1062 1180 1181Table 4.9 BODY TISSUES AND FLUIDS-conrinued Element h/nm Matrix Technique, Concentration Atomization, Analyte Form Sample treatment Ref. Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pb Pt Pt Pt Pt Pt Pt Sb - Urine 283.3 Urine 283.3 Blood - Plasma, erythrocytes - Capillary blood 283.3 Blood - Blood ~ Blood Blood 283.3 283.3 265.9 - 217.6 Teeth Blood Serum, ultrafiltrate Plasma, urine, tissue Blood, bile, liver Plasma, urine Urine Serum Whole blood A, ETA, L A, ETA, L A, ETA, L A, ETA, L A, ETA, L A, -, - A, ETA with L’vov platform, L A, ETA with L’vov platform or probe, L, F, F, L A, ETA, - A, F, Air/C,H,, L A, ETA, - A, ETA, L A, ETA, - A, ETA, - A, ETA, - A, -, - A, -, - A, Hydride, C Either: wet oxidation with H,SO./H,O,, extract with APDC/MIBK at pH4-5 or: extract directly with APDCj MIBK at pH4-5 if amounts of coporphyrine and other complexants are negligible Add 20% H,PO, See Cd.ref. 1638 Complex with APDC, extract into MIBK; use of heparin anticoagulant led to lower plasma Pb values Hemolyse with Triton X-100 Dilute blood with 0.2% NH,H,PO,/O.5% Triton X-100, prepare standards in 0.2% NH,H,PO,/O.5% HNO, Review Examination of ashing procedures and matrix modifiers Clean teeth in H,O, followed by Decon 75; dry to constant weight, dissolve in HNO,, ash at 460°C dissolve in HC1, buffer to pH 4.5, complex with APDC and extract in MIBK Comparison of atomization from tube wall and L’vov platform Digest with equal vol.conc.HNO, in boiling water bath, dilute (1 + 5) with H,O, complex with aq. 1% solution of pyrrolidene-l-carbodithioate, extract into MIBK Homogenize tissue Plasma: dilute (1 + 9) with 0.5% HNO, Urine: dilute (1 + 19) with dist. H,O Separate Pt complexes by HPLC Precipitate Ptcontaining proteins Mineralize with HNO, for 3 h at 170”C, evaporate, dissolve residue in 1% HCI, reduce with KI-NH,OH in 10%HCI, decompose SbH, at 900°C in He 1537 1630 1638 C2478 1646 1878 1939 1976 C2075 C2097 C2462 2274 2490 491 790 1059 1111 1730 1875 793Sb Sb Se Se Se Se Se Se Se Se Se Se Se Se Se Se Se Se - - 196.0 196.0 196.0 - - 196.0 196.0 196.0 196.3 196.0 - - - - - 196 .O Urine Urine Blood, urine Blood Urine Urine Plasma, erythrocytes Blood, plasma Kidney, liver Serum, plasma Biological material Whole blood, plasma, erythrocytes Biological material Serum Whole blood Urine Kidney, liver Serum, seminal fluid < 200 pg/l 1-50 pg/l 50-200pg/l < 250 rg/l 26 - 104 &I > 4 rg/l 50 -200 pg/l - 50-500 ng/g < 800 pg/l - 6-160 pg/l 2.5-1OOng 10-6OOng - 90 > 5 ug/l 5-2OOpg/l - 0.3-0.8 pg/g > 1 rgP A, ETA, L A, Hydride, G A, ETA (Zeeman), - A, ETA, L A, ETA, L A, Hydride, G A, ETA (Zeeman), - A, Hydride, G A, Hydride, G A, ETA, L A, ETA, L A, Hydride, G A, Hydride, G F, Hydride, G A, ETA, L A, ETA, L A, Hydride, G, Fluorimetry A, ETA, L A, ETA (Zeeman), - A, Hydride, G A, ETA, L See Pb, ref. 1537 Generate SbH, by reduction with NaBH, Dilute blood ( 1 + 1 ) with 0.1% V/V Triton X-100, add equal vol. of I.Og/l Ni solution, calibrate by standard addition Total Se: digest under pressure.Trimethylselenium ion: separate on column of Dowex 50 W-XO, elute with 4N HCI and decompose complex under pressure See As, ref. 833 - Review of sample decomposition methods; mineralization with HNO,/HCIO, recommended Digest with HNO,/HCIO,; interference by transition elements overcome by separation with LaOH Dilute ( 1 + 9) with Ni”(0.25%)/HNO3(O.072M), calibrate by standard addition Examination of errors produced by digestion procedure, HNO,/HCIO,/H,SO, recommended Digest with HNO,/H,SO,, heat with 6M HC1 to convert to Comparison of atomic spectroscopic techniques Se (IV) lnterlaboratory comprison; ETA gave lowest coefficient of variation (6%) and hydride generation the highest (35%) Digest with HCIOJHNO,, reduce, neutralize, treat with 2,3-diaminonaphthalene, extract into PhMe, add equal vol.of aq. Ca(NO,),(l.Og/l) to sample in furnace; calibrate with blood based standard None See As, ref. 1513 Precipitate proteins with TCA, separate by centrifugation, dissolve precipitate in 10% NH, solution, add aq. solution of AgNO, (0.1%) to sample in furnace 1537 $ 1965 5 C5 8 386 46 7 833 1016 1384 1513 1524 1547 1548 1610 1623 1942 C2095 c2102 2213Table 4.9 BODY TISSUES AND FLUIDS-continued Element A/nm Matriv Technique, Concentration Atomization, Analyte Form Sample treatment Ref.Se 196.0 Serum Si Si Si Sn Sn Sr Sr Ti TI V V Zn Zn Zn Zn Zn Zn Zn Zn 25 1.6 - Urine Tissue Body fluids Plasma Biological material Whole blood. serum Serum Tissue Blood, tissue, urine - Serum, tissue, urine 318.4 Urine - Tissue - Biological fluids Metallothionein - Plasma, bile - Breast milk - Tissue - Plasma, bile ~ Tissue A, ETA, L or Hydride, G E, P, ICP, L A, -, - A, -, - A, ETA, L A, ETA, - E, P, ICP, - E, F, N,O/C,H,, - A, F, N,O/C,H,, - E, F, N,O/C,H,, - E, P, ICP, - A, F or ETA, L A, ETA, - A, ETA, L E, P, D.c., L E, P, D.c., L A, F, L A, ETA, - A, -, - A, -, - A, ETA, - A, F, - Comparison of techniques: (1) ETA: Dilute sample (1 + 1) with aq.Ni solution (4g/l), calibrate by standard addition (2) Hydride: Digest with HNO,/HCIO, at 1 8 0 ° C add H,SO,/HNO,, raise temp. to 3OO0C, cool, add H,O/CHCI, boil, cool, dilute, generate hydride. Good agreement between techniques Dilute (1 + 4) with H,O, calibrate by standard additon Ash at low temperature, dissolve in 6NHCI, extract into MIBK Separate organo-tin compounds on silica gel column Comparison of methods, ICP preferred See Li, ref. 1184 Wet digestion Blood and urine deproteinizcd with 5% CI,CCO,H, centrifuge, adjust to pH6, mix with NaDDc, extract with MIBK. Tissue digested with HNO,/HCl Direct determination of V in serum. Tissue: dry ash, dissolve ash in 0.5% H,SO, Wet ash with HNO,, chelate with cupferron, extract into MIBK Digest with HNO,/H,SO,/HCIO,.heat, boil to remove HNO, and HCLO,, add H,O,, boil off excess H,O,, dilute with H,O See Cu, ref. C175 Separate metallothionein on gel permeation column, elute with alkali buffer Nutritional studies - See Cu, ref. 758 Direct injection 2271 381 796 1023 1002 1008 C275 1184 C2303 791 5 24 1582 c122 C175 678 688 708 758 159 760Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Zn Various Various (4) Various (1 3) Various (7) Various (14) Various (13) Various- Various (6) Various - Liver metallothionein - - Milk - - Central nervous system - - Plasma, serum - 0.8 mg/l - Blood cells - - Amniotic fluid - - Plasma proteins - - Albumin - 213.9 Serum - 0.8 mg/l - Leucocytes 10 ng/106 cells - Biological material - - Whole blood - 7 mg/l - Gallstone, renal calculus 0.5-3 mg/g - Serum - 0.9 mg/l - Saliva - 213.9 Seminal fluid - 32mg/l 213.9 Leucocytes - 250 /.lg/l 213.9 Serum - 0.65 mg/l - Blood, tissue, bone - - Whole blood 0.05-10 mg/l - Serum, tissue, bone > lOpg - Tissue - - Tissue - Urine - Blood, tissue, bone - - Biological materials - Metalloproteins A, -, - A, -, - A, -, - A, ETA, L A, ETA, - A, ETA, - A, ETA, L A, ETA, L A, ETA, - A, F, Air/C,H,, L A, -, - A, F, Air/C,H,, L A, ETA, - A, -, - A, -, ~ A, F, Air/C,H,, L A, F, Air/C,H,, L A, ETA, L E, P, D.c., - A, ETA, L E, P, D.c., L E, P, ICP, S or L E, P, D.c., L E, P, ICP, L or G A, ETA, - E, A, - E, Hollow cathode, - A, -, - A, -, - Characterisation of protein - Calibrate using standards prepared in serum or plasma Digest with HNO,, standard solutions simulate sample matrix See Cu, ref. 1022 See Cu, ref. 11 83 Extract albumin from plasma by affinity chromatography on Reactive Blue 2-Sepharose Incorporate albumin and NaCl into standards See Cu, ref. 1551 Interlaboratory comparison Extraction See Cu, ref. 1880 See Cu, ref. 1974 Comparison of methods; colorimetric method adequate for routine use Solubiliie with aq.tetramethyl ammonium hydroxide Homogenize, aspirate undiluted Dilute (1 + 20) with H,O, incorporate albumin and NaCl into aqueous standards Investigation of suitability of d.c. plasma for biological trace element analysis Digest in HNO,/HClO,(Cu, Fe, Pb, Zn) LiNO, used as ionic buffer Sample placed on graphite rod and inserted directly into plasma (Cd, Co, Cu, Pe, Mn, Ni, Pb) Wet digestion, LiNO, added as ionic buffer Extract trace elements with poly (dithiocarbamate) chelating resin, digest resin, nebulize solution or generate hydride Review Comparison of methods (Al, As, Ca, Cu, Ga, Zn) Renew 836 841 ' 951 ' 1014 1017 1022 1183 1188 1521 1551 1819 1840 1880 1974 2013 2269 2270 c2273 c15 c94 C165 C205 C207 C209 C255 C272 33 7N P w Table 4.9 BODY TISSUES AND FLUIDS-continued Element Alnm Matrix ~~ Technique, Concentration Atomization, Analyte Form Sample treatment Ref.Various (4) Various (8) Various (6) Various (20) Various (6) Various (9) Various (7) Various (6) Various ( 5 ) Various (4) Various (4) Various (14) Various (4) Various (4) Various (4) Various (13) Various (8) Various (8) Various (4) Various (4) Various Tissue Urine Serum, tissue - Blood Meningiomas Blood, urine Hair Finger nail - Serum - Tissue - Hair - Finger nail, hair, water Teeth Tissue culture medium Tissue - Hair - Blood Blood, serum, ery throcy tcs - Cellular fluids - Teeth - Biological material A, F, - A, ETA, - E, P, ICP, L E,P, - A, F, - A, ETA, - A, -, - E, -, - A, -, - A, -, - - E, F, - A, F, - A, ETA, - 7-8000 rg/l E, F, L Comparison of ashing procedures (Cu, Fe, Mn, Zn) Comparison with XRF (As, Cu, Fe, K, Ni, Pb, Sr, Zn) Form trifluoroacetylacetone complexes on xylene (Al, Cr, Cu, Fe, Mn, Zn) Review - (Ca, Cr, Cu, Fe, Mg, Mn) - (Al, Cr, Cu, Fe, Mn, Ni, Pb, Si, Ti) Comparison with NAA (As, Cd, Cr, Hg, Mn, Pb, Se) Examination of effect of preparation procedures (Ca, Cu, Fe, Mg, Mn, Zn) - (Ca, Cu, Fe, Mg, Zn) Comparison of wet and dry ashing procedures (Cu, Fe, Mn, Zn) Dry ash at 500 "C for 5 h, dissolve in HCI (Cu, Fe, Mn, Zn) Study of variation in elemental concentrations in the population of Egypt - (Cd, Cu, Pb, Zn) Study of solubility of dental amalgams (Ag, Cu, Sn, Zn) Tissue supernatant fractions separated by gel permeation column (SW 3000) and high speed liquid chromatography (Ca, Cd, Fe, Zn) Survey of mining industry workers; NAA also used for analysis Survey of normal blood concenrations (Ca, Cd, Cu, Fe, Mg, Mn, Pb, Zn) Oxygen flash combustion with HNO,, or wet digestion with HNO,, or dilution with distilled water (Ca, Cu, Fe, K, Mg, Na, Pb, Zn) Investigation of alkaline cation flow across a cell membrane (K, Li, Na, Rb) Dissolve in 14NHNO,, dilute to 0.5N.separate on Dowex 50W-X8 column, elute with 2N HCI, and separate on Dowex I-XS, elute with 1N HNO, (Cd, Fe, Pb, Zn) Review, comparison with NAA 338 340 507 563 659 664 6 76 682 705 706 707 762 800 815 834 850 943 950 1013 1015 1021Various (9) Various Various (5) Various (20) Various (23) Various Various Various (5) Various (9) Various (6) Various Various Various Various (19) Various (5) Various (4) Various (20) Various (4) Various (7) Various Various (4) Various Various Various Various (5) Various Various - Bone - Body fluids, tissue - Whole blood - Hair - Lung tissue - Body fluids Biological samples Serum Whole blood, serum, hair, urine Body fluid, tissue Blood plasma Tissue Body tissues Urine Serum Whole blood, serum, urine Kidney, liver Body fluids Bone Semen Food.exreta - Whole blood. serum Tissue, bone Biological materials Plasma, erythrocytes Blood, serum, urine Tissue, urine ~~ A, -, - E, P, ICP, - E, P, ICP, - - A, -, - A or E, Electrically heated 11 loop, L E, P, ICP, - E, P, ICP, - E, P, ICP, - A, ETA (Zeeman), - E, P. High frequency, A, -, - E, P, ICP, - E, P, ICP, S or L or G A, F, L A, ETA, L E, P, ICP, - A, -, - A, ETA, - A, -, - E, P, D.c., - A, -. - A, ETA, - E, P, ICP, - E, P, ICP, - - (Ca, Cd, Cu, Li, Mg, Mn, Pb, Sr, Zn) Review Study of interferences (Al, Cd, Cr, Cu, P) Interlaboratory comparison of methods Review Examination of interelement effects Dilute (1 + 99) with H,O (Cu, Fe, Mg, Na, Zn) Extract trace elements with chelating resins (As, Be, Co, Cr, Fe, Mo, Se, Ti, V) - (Al, Au, Cd, Cr, Cu, Mn) Comparison of solution introduction techniques Investigation of contamination (Cd, Cu, Mn, Pb, Zn) Review Preconcentrate on chelating resin; either digest resin or vaporize resin in ETA; nebulize resin digest or generate hydrides Discrete nebulization of sample diluted with 1M HCI/l% La solution (Ca, Cu, K, Mg, Na) Dilute with 2% Triton X-100; calibrate by standard addition (Al, Cr, Mn, Pb) Digest with HNO,/HCIO, Optimization of methods (Cu, Fe, Mg, Zn) (Cu, Fe, K, Mg, Mn, Ni, Zn) Review Wet or dry ashing (Cd, Cu, Mn, Pb) Separate metal-containing compounds on columns of 1G4000 SW, 2G3000 SW, and 1G2000 SW Soft tissue: digest with HNO,/HCIO,/H,SO, Bone: digest with HNO,/HCIO, Review A, F or ETA (Zeeman), L Dilution (Cr, Cu, Mn, Se, Zn) Optimization of methods A, ETA, - A, ETA, - Review b 'p1 - 2 1024 1044 5' 1061 2 9 1063 1116 1118 1257 C1298 C1330 C1434 1631 1645 C1684 C1692 C2078 1729 1759 1821 1883 1943 1944 1980 1982 C2076 C2079 C2088 C2098 C2294 bJ P wh, P Table 4.9 BODY TISSUES AND FLUIDS-continued Technique, Analyte Form Element h/nm Matrix Concentration Atomization, Sample treatment Ref. Various (7) - Body fluids, tissue - A, ETA, (Zeeman), - Critical comparison with XRF and NAA (Al, Au, Cd, Cr, Cu, C2295 Various(4) - Tissue 0.5- 120 pg/g A, F, L Dry ash with Mg(NO,), , dissolve ash in 6M HC1 (Cd, Cu, 2321 - C2360 Various Biological material - A, -, - Review of analysis in chemistry Mn, Pb) Pb, Zn) Various(5) - Serum - A, F, L Flow injection (Au, Cu, Fe, Pt, Zn) C2363 Various(20) - Blood, tissue, urine - E, P, ICP Preconcentrate by either coprecipitation or liquid-liquid C2457 extraction Various - Biological materials - A, ETA, - Review C2492 F, F, -

ISSN:0306-1353    

DOI:10.1039/AA9821200223

出版商:RSC    

年代:1982

数据来源: RSC

摘要:

New Books NEW BOOKS 245 Trace Element A n a l y t i c a l Chemistry i n Medicine and Biology, Proceedings o f t h e F i r s t I n t e r n a t i o n a l Workshop on Trace Element A n a l y t i c a l Chemistry i n Medicine and Biology, Neuherberg, W. Germany, A p r i l 1980. E d i t e d by P. B r a e t t e r and P. Schramel, published by Walter de Gruyler, B e r l i n , 1980. (503) An I n t r o d u c t i o n t o AAS.A S e l f - t e a c h i n g Approach. L. Ebdon, published by Heyden & Son, London, 1982. (539) AA Determination of Noble Metals. I . G . Y u d e l i v i c h and E.A. Startseva, published by Nauka, Sib. Otd., Novosibirsk, USSR. (752) D i f f r a c t i o n Gratings. M.C. Hutley, published by Academic Press, New York, 1982. (822) The Theory o f Atomic S t r u c t u r e and Spectra.R.D. Cowan, published by Univ. o f C a l i f . Press, Berkeley, C a l i f o r n i a , USA, 1981 (969) AAS i n Analysis o f Mineral Raw M a t e r i a l . Stolyarova, I . A . and M.P. F i l a t o v a , published by Nedra, Lenengradskoe Otdelenie, Leningrad, USSR, 1981. (1004) Developments i n Atomic Plasma Spectrochemical Analysis. (Proceedings o f I n t e r - n a t i o n a l Winter Conference, San Juan , Puerto Rico, 7-11 January 1980).Edited by R.M. Barnes, published by Heyden & Son, London, England, 1981. (1056) Studies i n A n a l y t i c a l Chemistry, Vol. 4: Guide-Lines t o Planning o f Atomic Spectrometric Analysis. B. Magyar, published by E l s e v i e r , Amsterdam, The Netherlands, 1982. (1171) Annual Reports on A n a l y t i c a l Atomic Spectroscopy, Vol. 10 Reviewing 1980. Edited by M.S. Cresser and B.L. Sharp, published by The Royal Society of Chemistry, London, England. ( 1 491 ) A D i c t i o n a r y of Spectroscopy. Second Ed. R.C. Denney, published by Macmillan, London , 1982. ( 171 0) Absorption Spectra of Metal Vapours i n t h e Vacuum U l t r a - v i o l e t Region. M.G. Kozlov, published by Nauke, Moscow, USSR, 1981. (1741) Atomic-Absorption Spectrochemical Analysis. M.E. B r i t s k e , published by Khimiya, Moscow, USSR, 1982. (1839) Metal Vapours i n Flames. C.T. Alkemade, T. Hollander, W. Snelleman and P.J. Zeegers, published by Pergamon, New York & London, 1982. (2302)

ISSN:0306-1353    

DOI:10.1039/AA9821200245

出版商:RSC    

年代:1982

数据来源: RSC

摘要:

246 REVIONS Analytical Atomic Spectroscopy AAS, general AES, instrumentation f o r AFS A1 umi n i urn, analysis o f Arsenic, determination o f Arsenic, i n environmental samples Atmospheric p a r t i c u l a t e s , analysis o f Atomic spectroscopy o f b i o s i g n i f i c a n t t r a c e Atomic spectroscopy, recent advances i n Background correction, Zeeman B i o l o g i c a l materials, analysis o f Coal , coke and ash, analysis o f Con tami na ti on D.c.plasmas Drugs, AAS i n analysis o f E l e c t r o n i cs Exploding conductors Foods, analysis o f GC, atomic spectroscopic detectors i n HCLs Hydri de genera t i on ICP-OES, general elements i n analysis o f b i o l o g i c a l samples i n food analysis i n s t e e l analysis i n water analysis Interferences i n AAS w i t h ETA Isotope s h i f t s Laser-enhanced i o n i z a t i o n spectroscopy Lead, determi nation o f Loops i n AAS and OES Metalloproteins, analysis o f Metals, analysis o f Non-ferrous a1 1 oys , analysis o f OES, general 388, 971, 1142, 1911, 2037 1361 558, 623, 1911 86 7 1793 575 523, 916 454 2253 486, 552, 747, 1679 1182 51 3 1045, 1394, 1395 1042 46 3 1448 1994 709, 843, 1190 581 430, 773 1006 1909, 1912, 1956 11 82 843 1791 768 1910 1366 2222 1708 1118 337 1080, 1996 496 2221Reviews 247 Organic complexing agents, i n AAS Organic s o l v e n t enhancement e f f e c t Petroleum a n a l y s i s , by AAS Reagents, p u r i f i c a t i o n o f S i l i c o n i n a l l o y s , determination o f Sources, s p e c t r a l Speciation Spectrometers SRMs Toxic metals, determination o f Water analysis, by I C P OES Wines, a n a l y s i s o f Zeeman background c o r r e c t i o n 31 9 1083 801 1393 2038 430, 773, 1041 , 1995 581 866, 1361 505, 1396, 1452 563 768 345 486, 552, 747, 1679

ISSN:0306-1353    

DOI:10.1039/AA9821200246

出版商:RSC    

年代:1982

数据来源: RSC