CHAPTER 3 Methodology 3.1 NEW METHODS In this Section novel methods, developments of methods and studies of experi- mental conditions a r e discussed. b u t they are included here i f they a r e l i k e l y t o be more widely applicable and hence of general i n t e r e s t . detailed information i n the appropriate applications section of Chapter 4. Many references a r e t o s p e c i f i c applications, In such cases, the reader may often find more 3.1.1 Sample Destruction 3.1.1.1 Ashing, Digestion and Fusion Papers comparing ashing procedures continue t o appear.pared f o r e f f l u e n t s (854), s o i l s and sludges (C287, 1468, 1990, 2021), vegetation (1465, 1476, 1625) and biological t i s s u e s (338, 706, 1414). Un- fortunately, there seems t o be l i t t l e agreement about the best methods, and the often contradictory conclusions will do l i t t l e t o a s s i s t the reader i n selecting the optimum method f o r his own application.The determination of As by ETA-AAS i s prone t o interferences, but a novel -~ wet ashing procedure f o r s i l i c e o u s materials (C296) was claimed t o eliminate most of the interferences commonly encountered. of a two-stage procedure using aqua regia, HF and H3B03.matrix modification with Ni(N03)2 p r i o r t o AAS determination. fluoboric acid was a l s o needed, however, t o remove A1 and Na interferences. I t should a l s o be noted t h a t spectral interferences by A1 on As have been reported (see Section 1.4.3.2). devices f o r semi-automatic sample decomposition.samples i n 15 min, and a fusion device melted the sample (* ore, slag, dolomite, dust) and c a s t i t i n t o a p e l l e t . vegetation samples w i t h HC1 by pressure digestion i n polyethylene b o t t l e s , prior t o multielement analysis by ICP-OES. said t o be f a s t e r than conventional ashing. The sample was heated with NH41, the sub- Methods have been com- Samples were digested by means This was followed by Dilution w i t h Wagner e t a l .(628) described two useful new A wet asher dissolved s t e e l Kuennen e t a l . (2018) digested The digestion (duration only 30 min) was A fusion/sublimation procedure f o r determining B i , Sb and Sn i n a variety of sample types was described (1053). limed iodides were collected i n a cold t r a p , and they were then dissolved i n d i l u t e HC1 f o r ETA-AAS determination.When Several workers have warned of v o l a t i l i z a t i o n losses during ashing. 8384 Analytical Atomic Spectroscopy dry ashing f o r 24 h , loss of several elements (a As, Br, C1, Cry Hg, Sb and Se) was reported (342) a t temperatures as low as 20OoC. samples of r a t f u r was said t o occur even during freeze drying (2268), and when several tissues were oven dried a t 12OoC, s i g n i f i c a n t loss of Cr(II1) was recorded, though l i t t l e Cr(V1) was l o s t .Severe loss of Sb when organic matter was wet ashed w i t h HN03/HC104 was only prevented by f i r s t adding H2S04 (2346). The acid complexed Sb and so prevented insoluble compound formation and ad- sorption on the walls of the digestion vessel. of vegetation was avoided by adding HN03/H2S04 (C2340).Incomplete recovery of Se when digesting biological materials, u s i n g only HN03,was a t t r i b u t e d (1547) t o incomplete mineralization of organo-selenides. A cautionary note on the HN03 digestion of organic samples i n closed systems was published (1668). a PTFE-lined s t a i n l e s s - s t e e l vessel , an explosion occurred which forced the bottom of the vessel through 6 mm of A1 p l a t e and 25 mm of wood: the authors preferred digestion w i t h HN03/HC104 i n an open vessel, although t h i s i s hardly the s a f e s t of digestion procedures.Loss of Cr(II1) from Loss of Cd during the dry ashing When 1 g of dried grass was heated w i t h 5 ml of HN03 i n Thereafter Other references of i n t e r e s t - Comparison of decomposition procedures f o r Se i n blood : 1384.comparison of LiB02 fusion w i t h acid digestion f o r s o i l s and rocks : 392. Rapid digestion procedure f o r sludges : 1464, 1467. Review of sample preparation methods f o r foods : 709. The use of alkaline KMN04 f o r digestion of biological materials : 1060. 3.1.1.2 Combustion and Pyrolysis The use of a quartz oxidative combustion apparatus (398, 532) enabled l e s s than 1 g of organic material t o be incinerated in pure 02. Volatile t r a c e metals were condensed i n a liquid N p system mounted above the combustion chamber. Refluxing w i t h j u s t 2 ml of acid dissolved both the condensed v o l a t i l e species and the l e s s v o l a t i l e elements i n the residual ash.Combustion times were long (50-60 min per sample), but good recoveries and low blanks were claimed f o r several elements i n the ng-ug g-l range. oxygen f l a s k combustion procedure f o r the destruction of blood prior t o the determination of several t r a c e elements. A non-oxidative pyrolysis system f o r determining Hg i n coal (1518) used a stream of N2 t o sweep evolved Hg vapour i n t o a KMn04 trapping solution.Sakla e t a l . (950) described an 3.1.2 SeDaration and Preconcentration A review of mu1 tielement preconcentration procedures f o r water analysis was published by van Grieken (2214). techniques such as evaporation, freeze-drying, ion exchange, co-precipi t a t i o n , Although primarily directed towards XRF uses,Methodology 85 s o l v e n t e x t r a c t i o n , i m m o b i l i z a t i o n a f t e r c h e l a t i o n and e l e c t r o d e p o s i t i o n were s u rveyed . 3.1.2.1 Chelating and Ion-exchange Resins Barnes and co-workers described several appl i c a t i o n s t o ICP-OES o f t h e i r pre- concentration technique u s i n g polydithiocarbamate c h e l a t i n g r e s i n s (see ARAAS, 1980, 10, Ref.C1394; i n c l u d e d preconcentration o f t r a c e elements i n u r i n e (C209, C2078) , serum (C2078), seawater (C240) and coal and f u e l o i l (C2092), and s p e c i a t i o n o f C r ( I I 1 ) and Cr(V1) i n u r i n e and dextrose (C210). E l u t i o n and/or a c i d d i g e s t i o n were used f o r r e c o v e r i n g t h e metals from t h e column (C240).determined by d i r e c t ETA measurement o f t h e r e s i n . The b u f f e r e d sample s o l u t i o n was mixed w i t h the r e s i n ( l e s s than 400 mesh), which was then s t i r r e d , f i l t e r e d , and suspended i n water p r i o r t o i n j e c t i o n i n t o t h e g r a p h i t e furnace. S i m i l a r l y , Hg was determined (464) by preconcentration on dithiocarbamate bonded s i l i c a gel which was introduced d i r e c t l y i n t o a Zeeman ETA spectrometer.l i m i t f o r Hg o f 0.9 pg m l - 1 was claimed. Hirano e t a l . (921) compared several i o n exchange and c h e l a t i n g r e s i n s f o r use w i t h waste waters. Dowex A-1 , Epolas 10 and Ca-type UR50 adsorbed Cd, Pb and Zn w e l l , b u t Amberlite IRA-47 was p r e f e r r e d f o r s t a b l e complex-forming metals such as Cu, Fe, Mn and N i .commonly used Chelex-100. 31 8 ) by complexi ng w i t h 8-hydroxyqui no1 i ne and then adsorbing on C-18 bonded s i l i c a gel, enabling seawater samples t o be processed 10 times more q u i c k l y than w i t h Chelex-100. C o r s i n i e t a l . (2345) evaluated a m a c r o r e t i c u l a r a c r y l i c e s t e r r e s i n (SM-7) f o r preconcentrating f r e e and inorganically-bound t r a c e metals i n aqueous s o l u t i o n .mined by ETA-AAS, t h e SM-7 r e s i n gave lower blanks than Chelex-100. been r e p o r t e d (see Section 3.1.3). 1981, - 11, Ref. 154, C1155, 2158, 2200). A p p l i c a t i o n s Chelex-100 was used (2042) f o r t h e preconcentration o f Pb, which was then A d e t e c t i o n Two r e p o r t s have described t h e use o f m a t e r i a l s s a i d t o be p r e f e r a b l e t o t h e Trace metals were concentrated from seawater (C236, When t h e adsorbed metals were e l u t e d w i t h HN03 and deter- Speciation of As (312, 400, 1731) and Se (467) by separation on r e s i n s has Other references o f i n t e r e s t - Determination o f "methylmercury" i n seawater u s i n g c h e l a t i n g r e s i n s : 1132.Evaluation o f Amberlite XAD-1 and XAD-2 f o r t r a c e metals i n n a t u r a l waters : 923. Preconcentration o f Pb from t a p water by use o f a polystyrene supported poly(ma1eic anhydride) r e s i n : 2213. Preconcentration o f several metals from sea and t a p water by use of a d i thiocarbamate c e l l u l o s e d e r i v a t i v e : 2218.Size e x c l u s i o n chromatography f o r separating t r a c e metals i n n a t u r a l waters : 2224.86 Analytical Atomic Spectroscopy 3.1.2.2 Solvent Extraction One of the most v e r s a t i l e chelating agents i s APDC, because o f i t s wide complex- i n g a b i l i t y .Miyazaki e t a l . (2265) compared several chelating agents and found APDC t o be the most s u i t a b l e f o r multielement e x t r a c t i o n , and hence f o r ICP-OES. They also examined more than 30 organic solvents and suggested those o f low vapour pressure t o be the best, since they would have a smaller e f f e c t on gas pressure i n the I C P than high vapour pressure solvents.s u i t a b l e i n t h i s respect, b u t d i i s o b u t y l ketone was b e t t e r . a 100-fold concentration step, b u t i n p r a c t i c e , when samples might contain high concentrations o f some o f the extractable elements, t h i s can lead t o chelate p r e c i p i t a t i o n . A r a t h e r complicated procedure f o r overcoming such a chelate interference e f f e c t when determining Ag (380) required the a d d i t i o n o f EDTA, CaC12, FeC13, CuS04, s a l i c y l i c acid, dibutylamine and NH40H. masking agents are needed there seems l i t t l e advantage i n using FAAS compared w i t h molecular absorption spectrophotometry, which a l s o usually requires the a d d i t i o n o f masking agents because o f poor s e l e c t i v i t y .(2261) reported t h a t freon was the most s u i t a b l e solvent f o r e x t r a c t i n g APDC and DDC complexes from estuarine waters, because freon and water have very low mutual s o l u b i l i t y . m i s c i b i l i t y , which occurred w i t h many other solvents (see ARAAS, 1978, 8, Ref. 886). The use o f several unusual chelating agents has been reported. The extrac- t i o n o f Sb as i t s trioctylaminebromo-ion association complex i n t o MIBK was described (1167).Trioctylamine was also used (329) f o r e x t r a c t i n g Be from an NH4SCN medium i n t o MIBK. A detection l i m i t o f 0.004 ppm was obtained by FAAS using a N20/C2H2 flame. Ivanova e t a l . (1048) examined 1-phenyl-3-methyl-4- benzoyl-5-pyrazolone (PMBP) and i t s chloro-derivatives f o r chel a t i n g t r a n s i t i o n metals p r i o r t o e x t r a c t i o n i n t o o-xylene o r MIBK.PMBP i t s e l f was best b u t Cu and Fe were extracted s e l e c t i v e l y w i t h 4-chloro-PMBP and 2,4-dichloro-PMBP. Other uses o f unusual chelating agents included: Ag i n ores (889); Cd i n ores (933); Cu i n aluminium (893); Cu i n waters (460, 1831, 1900); Fe i n waters (460, 408, 1952); Mo i n s t e e l (1216); Pb i n high p u r i t y cadmium (1162); Se i n blood (1942), and i n s o i l (1123); Sn i n s o i l s and rocks (383); V i n water (582, 675, 1133),and airborne dust (675); several elements i n waters (744).The much used MIBK was The authors reported When so many Danielsson e t a l . Hence, varying s a l i n i t i e s d i d n o t lead t o varying phase For multielement e x t r a c t i o n Other reference o f i n t e r e s t - Review o f the use o f organic complexing agents i n FAAS and ETA-AAS : 319. 3.1.2.3 Co-precipitation Q u i t e remarkable concentration f a c t o r s (up t o 2400-fold) were claimed f o r f l o t a t i o n separation (1412) and i t i s perhaps s u r p r i s i n g t h a t t h i s technique i sMethodology 87 not more widely used.Trace metals were either co-precipitated or complexed t o form hydrophobic ions and the precipitated species were carried t o the surface by a i r o r N2 bubbles. The resulting "scum" was then sucked i n t o a sampling tube. mination of several elements by ICP-OES. The p r e c i p i t a t e was separated, washed and dissolved i n HN03 f o r deter- 3.1.2.4 Adsorption and electrodeposi tion Satake e t a l .adsorbed Cd (1923) and Mn (1924), both as the 5-chloro-7-iodo-8- quinolinol complex, on microcrystalline naphthalene p r i o r t o FAAS determination. Gold was determined i n i t s ores (500) by digestion and adsorption onto p l a s t i c foam, and P t group metals were determined (1052) a f t e r adsorption onto a thio- e t h e r polymer. heavy metals (as their DDTC complexes) in seawater (C104), Nb and Ta in natural waters (1036), Hg in waters (619), and t r a c e elements i n metals (1051, 1402) and NaC104 (123).ICP-OES determinations. Metals of i n t e r e s t were deposited from flowing streams onto a glassy C electrode, and were subsequently stripped back i n t o an electro- l y t e solution which was pumped t o the ICP nebulizer.The procedure was s a i d t o be useful f o r obtaining large preconcentration f a c t o r s from solutions of high s a l t content. Frick and Tallman (1129) described the use of a graphite tube as a flow-cell t o electrodeposit Hg. The c e l l was subsequently removed and used d i r e c t l y f o r ETA-AAS w i t h a claimed detection l i m i t f o r Hg o f 0.08 ppb. Reduction i n a c e l l w i t h a P t wire anode and amalgamated Au-wire cathode has been used (771) f o r preconcentrating Cd from lake water p r i o r t o ETA-AAS.Adsorption onto activated carbon was used t o preconcentrate Electrochemical preconcentration was used by Long and Snook (C297) p r i o r t o Additional references on the preceding topic - 501 , 1953. 3.1.2.5 Miscellaneous Methods Atom trapping, using a cooled c o l l e c t o r t u b e i n the flame (see ARAAS, 1979, 9, Z O ) , was used (2257) t o enhance the s e n s i t i v i t y of Se determination by FAAS. Vegetation samples were combusted i n an oxygen f l a s k and Se was collected f o r 2 min on the tube p r i o r t o allowing the Se t o atomize i n t o the air/C2H2 flame.Several types of c o l l e c t o r tube were examined, and Si02 was the most s a t i s f a c t o r y . The atom trapping technique i s prone t o severe interferences due t o deposition and/or attack on the c o l l e c t o r tube, b u t t h i s was minimized by coating the tube w i t h A1203. 1.3.3.1). procedure f o r Hg i n drinking water samples.was carried via an Ar stream, f o r 5 m i n , i n t o a KMn04 trapping solution. dition o f SnC12 t o this solution enabled Hg vapour t o pass t o an AFS c e l l . A detection l i m i t o f 0.03 ppm was obtained. (See a l s o Section Bertenshaw and Wagstaff (1554) described a simple and useful preconcentration After SnC12 reduction, Hg vapour Ad- A88 Analytical Atomic Spectroscopy detection l i m i t o f 1.6 ng 1-1 was obtained.Other reference o f i n t e r e s t - Heavy metal separation by b a c t e r i a l leaching : 727. 3.1.3. Speciation Coupled chromatography-atomi c spectrometric procedures are being used i ncreas- i n g l y f o r speciation. They are discussed i n Sections 1.1.1.2, 1.1.3.3, 1.1.1.4 Se 1 ec ti ve Inorganic Hg respectively ( 3 ) p r i o r t o Addi t i o n a Pu ttemans and 1.3.3.3, thus only a l t e r n a t i v e procedures are reviewed here.Yamamoto e t a l . (417) s e l e c t i v e l y reduced A s ( I I 1 ) i n the presence o f As(V), and S b ( I I 1 ) i n the presence o f Sb(V), by t r e a t i n g seawater samples w i t h 40% c i t r i c acid p r i o r t o a d d i t i o n o f NaBH4 f o r hydride generatiowAAS. concentrated HC1 t 40% K I were added.S i m i l a r procedures have been applied t o As determination i n r i v e r waters (1474) and s o i l e x t r a c t s (1659). Speciation i s o f p a r t i c u l a r i n t e r e s t i n the analysis o f environmental samples. For t o t a l As o r Sb, reduction was used by Oda and I n g l e (1614) f o r mercury speciation. compounds and organomercuri a1 s were reduced by SnCl and NaBH4 Preconcentration w i t h macroreticular chelating resins was used the ETA-AAS determination o f t o t a l and "methyl-Hg". and Massart (2256) s e l e c t i v e l y extracted A s ( I I 1 ) as i t s APDC o r references on the preceding t o p i c - 1132, 1938, 1975.diethyldithiophosphoric acid complex. i n order t o break down the As chelate before ETA-AAS determination.The deter- mination o f S b ( I I 1 ) i n the presence o f Sb(V) was accomplished (332) by chelating w i t h N-benzoyl-1-phenylhydroxylamine and e x t r a c t i n g i n t o CHC13. reduction w i t h K I was used. Antimony was determined i n the e x t r a c t s by ETA-AAS They back-extracted i n t o a Cu(I1) s o l u t i o n For t o t a l Sb, a f t e r adding Cu t o the sample solutions i n order t o prevent analyte loss during ashing.by ICP-OES (1163) involved i t s s e l e c t i v e chelation w i t h 2 - t h e n o y l t r i f l u o r o - acetone and e x t r a c t i o n i n t o xylene. Chromium was also speciated (C210) by separation on poly(dithiocarbamate) and poly(acry1amidoxime) resins. Speciation o f As was effected by passing solutions through a column o f Dowex AG5OW-XB (400).Inorganic As was eluted w i t h 0.1M H3P04, monomethylarsonic acid w i t h 0.02M NH3, and dimethylarsinic acid w i t h 1M NH3. l i m i t o f 0.5 ng m1-l. (322), and by Oyamada and I s h i z a k i f o r Se speciation (467). A method f o r the determination o f C r ( I I 1 ) i n chromate and dichromate matrices Determination by ETA-AAS gave a detection S i m i l a r procedures were used by Pacey and Ford f o r As 3.1.4 Sample Introduction 3.1.4.1 Gaseous Sample Introduction Several automated hydride generation systems have been described.A s i m p l i f i e d procedure f o r Ge determination (585) required no c a r r i e r gas. A sealed vesselMethodology 89 caused the generated hydride t o be forced under pressure,via a capillary, i n t o the spray chamber o f an AA spectrometer f o r determination i n a N20/C2H2 flame.A double nebulizer, consisting o f two concentric c a p i l l a r i e s (627) allowed KBH4 and sample s o l u t i o n t o be nebulized together i n t o a spray chamber which supported an air/C2H2 flame (see Section 1.3.3.1). system (1169) used two p e r i s t a l t i c pumps t o d e l i v e r NaBH4 and sample s o l u t i o n t o a gas/liquid separator.The evolved As o r Se hydride was swept t o a mini- ature A r / H 2 flame burning a t the end o f a b o r o s i l i c a t e glass tube f o r measurement by e i t h e r AAS o r AFS. the determination o f B i by hydride generation AAS (see ARAAS, 1981, 5. Refs. C772, C2060).Besides the obvious advantage o f automated analysis (throughput o f 180 samples h-’), the author claimed t h a t FI enabled interference f r e e B i determinations i n the presence o f f a r higher Cu and N i concentrations than can normally be t o l e r a t e d i n hydride methods. speed and low NaBHq concentration. used a combination o f hydride generation and ETA-AAS (1871).The B i was reduced i n s o l u t i o n by NaBH4, stripped w i t h He gas, and collected i n s i t u i n a modified carbon rod atomizer. Subsequent electrothermal vaporization from the rod gave a detection l i m i t o f 3 pg. closed Si02 tubes i n hydride generation AAS. when open tubes were used. Hydride generation procedures are frequently complicated by the need t o reduce chemical interferences.Crock and Lichte (673, 674, 2266) described an automated (AutoAnalyzer) system which they claimed eliminated interferences i n the hydride generatiodAS determination o f As and Sb. geological materials, the f o l l o w i n g reagents were sequentially added: K I , NH20H.HC1 t o x a l i c acid ( t o eliminate Fe interference), HC1 ( t o reduce N i i n t e r - ference) and NaBH4 f o r hydride formation.I n addition, two 40-foot delay c o i l s were said t o reduce interferences f u r t h e r by a1 lowing equi 1 ibrium conditions t o be reached p r i o r t o atomization. They reported no interference from Cu, Fey U o r V, and the small interferences from N i , Se and Sn were n o t s i g n i f i c a n t a t t y p i c a l concentrations i n geological samples.The i n t r o d u c t i o n o f a long delay time i n an AutoAnalyzer system i s undesirable, b u t perhaps i t i s worthwhile i f normally troublesome interferences are removed so e a s i l y . On a three-channel continuous-flow system f o r hydride generation, Carr e t a l . (C221) found t h a t s e n s i t i v i t i e s f o r Pb were improved when the acid concentration o f the samples was decreased.For As and Se, however, the reverse was true. I n general, i n t e r f e r - ences from t r a n s i t i o n metals were more severe a t low acid concentrations. When SnH4 was generated from an acid s o l u t i o n (534), Fe interference was reduced i n A simple and inexpensive automated Astrom (1450) has published h i s work on the use of FI f o r This was a t t r i b u t e d t o a high pump An i n t e r e s t i n g method f o r the determination o f B i i n environmental samples Verlinden (2217) warned o f the d e t e r i o r a t i o n (due t o d e v i t r i f i c a t i o n ) o f Such problems were n o t encountered A f t e r acid digestion o f90 Analytical Atomic Spectroscopy 0.3M compared t o 0.1M HC1.Ge was enhanced a t l e a s t 4040% in H3P04 rather than HC1. They reduced Au, Co and N i interference by masking w i t h EDTA or replacing the acid medium by malic acid. When Pb was determined by a hydride method (2250), i n t e r f e r i n g Ag, Au, Cd and Cu were removed w i t h a dithizone/CHC13 extraction s t e p followed by back extraction i n t o HN03. A continuous-flow system was described (2029) f o r the cold vapour AAS deter- mination of Hg i n waters.Digestion, reduction and extraction were performed continuously in small bore tubes. A gas-liquid separator removed the Hg vapour which was then dried by passing i t through an a i r condenser before i t entered the cold vapour c e l l . Compared w i t h conventional AutoAnalyzer methods, only about one tenth the amount of reagents was required. A continuous-flow apparatus f o r determining Hg i n coal digests (1518) used a windowless c e l l f o r AFS measure- ment, obviating the need f o r drying the Hg vapour (see ARAAS, 1981, 11, Ref. 1024). described. lowed by solvent evaporation and methylation of the residue w i t h MeLi t o form Me4Pb. a quartz-furnace atom c e l l .limited of only 5 ng ml-1 was claimed. carbonyl formation (1130) involved NaBH4 reduction t o the element, reaction w i t h CO and collection of the v o l a t i l e analyte i n a cold trap. atomizer was used f o r the f i n a l determination by AAS. Volatile elements (As, B i , Cd, Se and T1) have been separated from r e l a t i v e l y non-volatile matrices (1165) by heating s o l i d samples a t 1000-1300 OC i n a stream of H2/N2/02, which carried the analyte elements i n t o an ETA.a method and apparatus f o r converting metals t o v o l a t i l e complexes with DDC o r trifluoroacetylacetone, adsorbing them on s i l i c a g e l , and thermally desorbing the v o l a t i l e compounds f o r AAS o r ICP-OES. ment by ICP-OES (see ARAAS, 1978, 8, Ref. 1076) has been applied by Kirkbright and co-workers t o the analysis of biological (C271, 1633) and metallurgical (C271) samples. J i n e t a l . (670) reported t h a t the s e n s i t i v i t y of Several unusual procedures f o r vapour phase AAS determinations have been One f o r Pb (966) involved chelation and extraction i n t o CHC13, f o l - The analyte vapour was trapped on a Porapak Q column and then swept i n t o A1 though the procedure was complex, a detection The determination of Ni i n seawater by A heated quartz-tube A patent application (2010) described Vaporization of s o l i d samples from a graphite rod ETA and subsequent measure- A s i m i l a r procedure was described by Aziz e t a l .(1362). Other references of i n t e r e s t - Determination of Te by hydride generation AFS : 416.Review of methods f o r t r a c e As determination : 1793. 3.1.4.2. Liauid Sample Introduction In s p i t e of the considerable amount of past work on blood lead determination by ETA-AAS, the analysis i s s t i l l d i f f i c u l t , usually requiring chemical pretreatmentMethodology 91 t o reduce matrix e f f e c t s . required only d i l u t i o n w i t h water (C304).the sample on a graphite probe i n t o a preheated furnace atomizer. procedure f o r Se (386) required only d i l u t i o n of blood w i t h 0.1% Triton XlOO and addition of Ni(N03)2. determined by FI-FAAS (942). ously flowing aqueous stream containing Na and K a t physiological concentrations. gasoline. of the Mn-C bond by adding CC14/Br2. A simple procedure was described, however, which This was accomplished by introducing An ETA-AAS Therapeutic concentrations of L i i n serum have been Aliquots of serum were injected i n t o a continu- An emulsion-FAAS procedure (389) was applied t o the determination of Mn i n An anionic detergent was used as the emulsifying agent a f t e r cleavage 3.1.4.3 Solid Sample Introduction A major trend i n analytical atomic spectrometry i s towards instrument automation (see Section 2.4).w i t h considerable speed. I t i s not surprising, therefore, t h a t there i s a l s o increasing i n t e r e s t i n procedures which can shorten sample pretreatment time. Such procedures include the d i r e c t introduction of s o l i d samples i n t o flames, ETAs and ICPs. - 10, Refs. 475, C633, 1245; 1981, 11, Refs. C914, 1338). introduce weighed mg amounts of s o l i d material d i r e c t l y i n t o an ETA. are e i t h e r dropped i n t o a constant temperature induction furnace or placed onto a graphite platform which i s inserted i n t o a r e s i s t i v e l y heated graphite furn- ace. They have determined t r a c e elements i n glass (C63) and nickel alloys (C291, 1558, 1600).i n metals by ETA-AAS (559, 648, 1964). w i t h Perkin-Elmer AA spectrometers has been described (548). Hence, analytical measurements can frequently be performed Headridge and co-workers have been very a c t i v e i n this area (see ARAAS, 1980, Their procedure i s t o Samples Other workers used this approach f o r determining t r a c e elements An improved s o l i d sampling tool f o r use Additional references on the preceding topic - 554, 952.Although the d i r e c t weighing of s o l i d samples i n t o ETAs i s generally much simpler than prior sample digestion, precision may be poor due t o lack of sample homogeneity. When s o l i d samples can conveniently be ground i n t o a f i n e powder, the preparation and introduction of a s l u r r y may be preferred. enables b e t t e r sample homogeneity and a l s o r e p l i c a t e aliquots of s l u r r y can be micropipetted i n t o the ETA a f t e r only one weighing.Hutton (C1442) described his work on the determination of t r a c e metals i n titanium dioxide. S l u r r i e s were s t a b i l i z e d by adding a thixotropic thickening agent (see ARAAS 1981, 11, Ref. 1293). A s l u r r y procedure f o r determining t r a c e metals i n s o i l (C314) did not require s t a b i l i z a t i o n i n this way provided the s l u r r y was constantly s t i r r e d magneti cal l y w h i 1 e sample a1 iquots were p i petted from i t . P i petting reproduci b- i l i t y was good, enabling an overall analytical precision o f 8% RSD a t typical concentrations of Pb i n s o i l . This Slurry ETA-AAS was a l s o applied t o the determin-92 Andy tical A to inic Spectroscopy a t i o n o f As i n coal (1545) and Pb i n b i o l o g i c a l materials (1627).Ebdon (C267, C2089) used a slurry-ICP-OES procedure f o r the analysis o f coal and coal ash. A simple procedure f o r determining Fe i n airborne dust (2264) involved c o l l e c t i o n on a polystyrene f i l t e r , i t s d i s s o l u t i o n i n xylene, and formation o f a s l u r r y u l t r a s o n i c a l l y p r i o r t o ICP-OES.Stupar and A j l e c (1512) reported good precision ( 1 2 % RSD) f o r the d i r e c t nebulization o f s o i l s l u r r i e s i n t o a flame. w i t h ETA-AAS a smaller s l u r r y p a r t i c l e s i z e was required, however, and i t was f i r s t necessary t o g r i n d each sample f o r 30 min.good precision (see ARAAS, 1978, S, Ref. 233). kidney tissues w i t h butanol-HC1-La s o l u t i o n , centrifuged, and then determined Ca i n the supernatant by FAAS. A commercial s o l i d sampling device f o r ICP-OES (see ARAAS, 1981 , 2, Ref. C1156 and Sections 1.2.1.2 and 2.5.1) permits sampling o f cast metals and briquetted powders by generating a high voltage spark between the analyte and a counter electrode. The r e s u l t i n g d r y aerosol i s swept by an A r stream i n t o the I C P .plants and s o i l s (C2207). For e l e c t r i c a l l y vaporized t h i n f i l m AES (2230), s l u r r i e s were micropipetted onto t h i n f i l m s o f Ag on a polyethylene substrate.A plasma was then formed by e l e c t r i c a l discharge. Detection l i m i t s were i n the ppm range (see ARAAS, 1980, - 10, Refs. 315, 1230). Compared Tissue homogenization provides a sample which can also be micropipetted w i t h Tew e t a l . (485) homogenized The device was used f o r the analysis o f a l l o y s (C222, C1232, C2210), and Other references o f i n t e r e s t - Analysis o f r e f r a c t o r y carbides by nebulizing s l u r r i e s i n t o a d.c.plasma : C33, C2469. Comparison o f FAAS, ICP-OES and d.c. plasma-OES f o r s l u r r y atomization o f foods : C2307. 3.1.5 I n d i r e c t Methods An improvement i n the phosphomolybdate method (401) enabled P t o be determined i n d i r e c t l y , by ICP-OES o f Mo, i n n a t u r a l waters w i t h a detection l i m i t o f 5 pg m1-l.Following the usual "molybdenum blue" formation, the complex was extracted i n t o d i - i s o b u t y l ketone. Unlike most other solvents which have been used, t h i s has very low water s o l u b i l i t y , and so the need t o wash was removed (washing can p a r t i a l l y back-extract the heteropoly a c i d i n t o the aqueous phase).An i n d i r e c t FAAS method (644) used e x t r a c t i o n i n t o b u t y l acetate. An i n t e r e s t i n g application o f the method f o r P determination was t o the analysis o f semi- conductor f i l m s (1639). Anodic oxidation o r chemical etching was used t o remove t h i n layers ( l e s s than 0.5 um), which were then extracted i n t o e t h y l a c e t a t e l butanol p r i o r t o heteropoly acid formation ( A l , As, Ga and I n were also deter- mined by d i r e c t means).Methodology 93 Additional references on the preceding t o p i c - 733, 1611.Several applications were described o f the i n d i r e c t procedure f o r sulphate determination by Ba FAAS (981, 1458, 1824, 1857). It i s o f i n t e r e s t , however, t h a t Miles and Cook (C313) determined sulphate d i r e c t l y i n natural waters, by ICP-OES, w i t h a detection l i m i t d i f f i c u l t i e s associated w i t h the AAS determination o f selenium.reaction o f Se w i t h K I , the l i b e r a t e d I2 was extracted i n t o benzene and then back-extracted i n t o aqueous ascorbic acid s o l u t i o n t o react w i t h cadmium phen- anthroline sulphate.Cd determined by FAAS. 2% was claimed. reported. A Hg displacement method was used f o r CO determination (1224). A i r samples were passed through activated HgO, and the evolved Hg vapours were determined by AFS. technique f o r SO2 determination t o enable continuous monitoring i n ambient a i r a t much lower l e v e l s than commercial instruments allow (see ARAAS, 1981, 11, Refs. 1579, 1912). A method f o r determining H2S i n a i r (613) involved reaction w i t h CdS04 and p r e c i p i t a t i o n o f CdS. was determined by AAS. (SNR = 3) o f 0.08 mg 1 - l . Vijayakuma e t a l . (321) developed a r a t h e r complex procedure t o overcome the Following The r e s u l t i n g complex was extracted i n t o n i trobenzene and I n s p i t e o f the many manipulative steps, an RSD o f only Some i n t e r e s t i n g methods f o r the i n d i r e c t determination o f gases have been Marshall and Midgley (1788) adapted t h e i r Hg displacement This was f i l t e r e d , dissolved i n acid and Cd Kuldvere (1539) determined I i n seaweed by measuring the decrease i n absorb- ance, caused by the formation o f Hg(I1) iodide complexes, when Hg was determined by cold vapour AAS.I n d i r e c t methods were also reported f o r aldehydes and ketones (461 ) , a1 k a l o i ds (456), 2-ami no-2-deoxyhexoses (476), amygdal i n (1 978) , ascorbi c acid (355), chloride (1103, 1801), detergents (965, 1705, 1722) and S i (C316). Other reference o f i n t e r e s t - Determination of W by Ca atomization i n h i b i t i o n t i t r a t i o n : 588. 3.2 DETECTION LIMITS. PRECISION AND ACCURACY Few studies s p e c i f i c a l l y concerned w i t h detection 1 i m i t s have been reported compared t o previous years. featured i n a review (1413) which assessed the detection c a p a b i l i t i e s o f t r a c e a n a l y t i c a l techniques. Comparative tables l i s t i n g l i m i t s o f determination f o r over 70 elements were presented.were reported f o r an ICP-echelle spectrometer (1177) and a DCP-OES system (749). I n both cases the r e s u l t s were compared t o published values f o r ICP-OES. A low cost signal averager which could be coupled t o a v a r i e t y o f instruments was used (988) t o give increased s e n s i t i v i t y and r e p r o d u c i b i l i t y f o r ETA-AAS determinations of T i i n rock samples a t concentrations near the instrumental detection l i m i t .Techniques such as AAS, AFS and ICP-OES were I n two separate investigations detection l i m i t s94 Analytical Atomic Spectroscopy Signal averaging improved the SNR which was , wi thin certain 1 imi t s , proportional t o “, where 1 represents the number of repetitive measurements.A novel method for SNR enhancement in FAAS (C98), based on a reduction in analyte flicker noise, was achieved through electrostatic modulation of analyte droplets using a modified nebulizer. Detailed studies on the noise characteristics of ICPs referred t o i n a previous volume (see ARAAS, 1981, 11, Refs. C80, C502, C716) have been published (134, 1372).Various aspects of calibration were investigated with the aim of improving accuracy and precision. Mitchell and Garden (1338) considered RSD, detection limit and correlation coefficient t o be poor measures of data quality in routine analysis and they recommended t h e i r rep1 acement by more meaningful parameters based on confidence-band s t a t i s t i c s .The authors proposed a general scheme which incorporated mu1 tiple-curve calibration and weighted least squares techniques for measuring and maximizing precision in analyses based on the use of calibration graphs. The approach was illustrated by reference t o the determination of Fe i n water by FAAS over a very wide concentration range (0.05- 100 pg ml-’). chemical trace analysis was examined by Klockenkamper and Bubert (1374).In the f i r s t part of the study, a scheme t o determine the most appropriate calibration function according t o the method of analysis (%, AAS, ICP-OES) was developed assuming a constant standard deviation of the measured variable throughout the working range of the calibration curve. ranges in ICP-OES was c r i t i c a l l y examined by Maessen and Balke (549).authors made a systematic study of the relationship between concentration and the standard deviation of the net line intensity, based on simultaneous mu1 t i - element analysis of 20 standard solutions containing eight elements in the concentration range 1 ng ml” - 100 ug ml“. the standard deviation was constant over the lower analytical range and the RSD was constant over the upper range.therefore, a linear scale was required for the lower concentration range and a logarithmic one f o r the upper range. severe error may occur i f a l e a s t squares procedure, which gives equal weighting t o a l l calibration standards, i s used to cover the entire linear range in ICP-OES. software routines, for estimating the contribution of individual sources o f variance (a standardization) i n ICP calibration functions. As an alternative t o computing a least-squares f i t f o r calibration data in AAS, Andrews and Jowett (870) developed a numerical method which linearized the calibration data.method assumed an exponential relationship between absorption and concentration and required only that the concentrations of the calibration standards formed an arithmetic progression.When the method was applied t o calibration data for Cu, A s t a t i s t i c a l treatment o f calibration i n quantitative spectro- The use of extended linear working The The investigation revealed that In the preparation of calibration graphs, The implication of this finding i s that Watters (C1430) developed approaches, based on the use o f modified TheMe tho do logy 95 Pb and Zn, using a program developed f o r use w i t h a Hewlett-Packard HP67 pocket calculator, the exponential r e l a t i o n s h i p was v a l i d w i t h i n the l i m i t s o f r o u t i n e ex pe r i men t a 1 e r r o r .For r o u t i n e FAAS using microprocessor-controlled instrumentation, Sotera 5 a1 .(2488) claimed t h a t stored working curves could be re-used on subsequent days provided parameters which would a f f e c t the shape o f the working curve, e.g. wave- length and s l i t width ( r e s o l u t i o n ) were n o t varied. t e s t elements and small changes i n s e n s i t i v i t y r e s u l t i n g from v a r i a t i o n s i n lamp current, burner height and flame conditions were compensated f o r by use o f a s i n g l e standard s o l u t i o n and a r o u t i n e which re-adjusted the slope o f the c a l i b - r a t i o n curve.performed by Belchamber and H o r l i c k (1176). Based on c o r r e l a t i o n studies between f l u c t u a t i o n s i n the emission i n t e n s i t i e s o f analyte and i n t e r n a l standard elements, i t was possible t o eliminate some o f the e f f e c t s o f source f l i c k e r noise, and gains i n precision o f about a f a c t o r o f 2 were realized.I n a study o f the i n t e r n a l standard method i n FAAS (4231, the e f f e c t s o f flame temperature and composition on the degree o f atomization o f 25 elements were investigated using a s p e c i a l l y constructed dual-channel spectrometer.Curves expressing the r e l a t i o n s h i p between absorbance and sample i n t r o d u c t i o n r a t e were established experimentally f o r each element, and those elements which exhibited s i m i l a r behaviour were recognized as mutual i n t e r n a l standard elements. accurate r e s u l t s as ever lower concentrations are being determined.reading f o r anyone embarking upon u l t r a - t r a c e metal determinations should be papers by Currie (1406) and Tschdpel (1411), who discussed l i k e l y e r r o r s and means o f m i nimi z i ng them when analyzing "real I' samples . from a special e d i t i o n o f Talanta, e n t i t l e d "Gains and Losses - Errors i n Trace Analysis", are also recommended.Kosta (1394) evaluated the r e l a t i v e e f f e c t s o f sources of contamination. M i t c h e l l (1393) c r i t i c a l l y compared methods f o r p u r i f y i n g chemical reagents, and 10 years o f experience a t the NBS i n the prod- uction o f high p u r i t y reagents was reviewed (1392). showed how disparate r e s u l t s i n t r a c e element analysis o f b i o l o g i c a l materials can frequently be a t t r i b u t e d t o contamination during sample c o l l e c t i o n and manip- u l a t i o n .ene containers were discussed (1398). suppress the signal i n the determination o f Hg by cold-vapour AAS b u t only i f the i n t e r f e r i n g element i s present i n the reducing s o l u t i o n p r i o r t o analysis. Kuldvere (1516) warned t h a t care should be exercised i f polypropylene reaction flasks are used f o r Hg reduction. These f l a s k s can absorb SnC12 which can remove Hg from solutions subsequently stored i n them unless the determination i s c a r r i e d - They used Cay Cu and Zn as An i n t e r e s t i n g study using the i n t e r n a l standard p r i n c i p l e i n ICP-OES was A n a l y t i c a l chemists are facing increasing d i f f i c u l t y i n reportinq precise and Essential -- The f o l 1 owi ng papers Yersieck and Barbier (1395) F i n a l l y , gains and losses o f u l t r a - t r a c e elements stored i n polyethyl- Suddendorf (601) cautioned t h a t Se and Te96 Analytical Atomic Spectroscopy out within two days.Thompson (C258) reported d i f f e r i n g FAAS chemical interferences which were dependent on the type of instrument used, e .~ . , when Cry Fe and Mn were deter- mined i n sewage sludge a f t e r acid digestion, e r r o r s greater than 40% were some- times observed when an air/C2H2 flame was used. These errors varied according t o the p a r t i c u l a r sludge sample, flame conditions and instrumental system. When sample preparation involves separating the analyte solution from a p r e c i p i t a t e or undissolved residue, f i l t r a t i o n should be avoided i f a t a l l possible.losses of Cd on the f i l t e r papers and the container walls (499). F i l t r a t i o n of CdS04 solutions (about 1-2 ppm) demonstrated severe Other references of i n t e r e s t - Coefficients f o r polynomial least-squares regression : 519.Correction f o r double-valued calibration curves i n Zeeman-effect AAS : 1149. Internal standardization i n ICP-OES : C52, C2107, C2474. Novel standard addition procedures f o r FAAS : 366, 1664. Quality assurance methods f o r ICP-OES : C1428, C1429. Software developments i n AAS calibration : 868. State-of-the-art contamination control techniques f o r ul t r a - t r a c e element analysis : 1045. 3.3 STANDARDS AND STANDARDIZATION 3.3.1 Reference Materials Several reports have been published on the a v a i l a b i l i t y and development of new reference materials. the CRM programme of the NBS, reported a t o t a l of 870 RMs i n the inventory. The review considered topics such as the c e r t i f i c a t i o n process and international progress and co-operation.Future programmes were outlined w i t h some emphasis given t o recently produced CRMs. The National I n s t i t u t e f o r Environmental Studies, Japan, has issued a booklet, the second i n the s e r i e s , describing the preparation, analysis and c e r t i f i c a t i o n of “Pond Sediment” CRM (see ARMS, 1981 , - 11 , Ref. 1616). New RMs under development ( c h l o r e l l a , freeze-dried human serum, human h a i r and mussel) were also discussed.analysis have been reviewed (1483) and special mention must be given t o the f i r s t seawater reference (NASS-1) prepared by the National Research Counci 1 of Canada; r e l i a b l e values a t the ng 1-1 level were established f o r As, Cd, Coy Cry C u , Fey Mn, Mo, N i , Pb and Zn.Such a standard has been long-awaited by marine s c i e n t i s t s and should do much t o reconcile the inconsistencies of t r a c e element data f o r seawater reported n the l i t e r a t u r e . The analytical methods and s t a t i s t i c a l techniques used i n the analysis and c e r t i f i c a t i o n of zinc ore concentrates (BCR No. 108, 109 and 1 0 ) f o r Cd, C u , F, Fey Hg, Mn and Pb were evaluated (510).Alvarez e t a l . (1452), i n reviewing the current s t a t u s of Standards and RMs f o r marine t r a c eMe tho do logy 97 The proceedings o f the i n t e r n a t i o n a l meeting on RMs sponsored by the A n a l y t i c a l D i v i s i o n o f the Royal Society o f Chemistry (see ARAAS, 1981, 11, 88) have been published (506, 508, 510, 512, 514). 3.3.2 Standardization Studies The importance o f collaborative i n t e r l a b o r a t o r y studies i n a l l f i e l d s o f chemical analysis was r e f l e c t e d i n an i n t e r n a t i o n a l symposium held i n H e l s i n k i i n 1981 and e n t i t l e d "Harmonization o f Collaborative A n a l y t i c a l Studies" (1675). symposium was organized by the A n a l y t i c a l , Applied, and C l i n i c a l Chemistry Divisions o f IUPAC and some 25 papers were delivered on subject matter ranging from the r o l e and philosophy o f a u t h o r i t a t i v e bodies such as IUPAC and IS0 t o p r a c t i c a l aspects including programme design, data q u a l i t y evaluation, and method intercomparison.Case studies i n d i c a t i v e o f c l i n i c a l , environmental and i n d u s t r i a l s i t u a t i o n s were presented.Elkins (1841) assessed, through i n t e r - laboratory experiments, a n a l y t i c a l methods used by the food i n d u s t r y f o r the determination of Pb i n processed foods. Procedures based on carbon rod-AAS, chelation-solvent e x t r a c t i o n AAS and ASY were comparable i n performance, y i e l d i n g <20% RSD a t concentrations o f 0.1-0.3 ppm.mination of Cd and Pb i n grass, l i v e r and human blood by FAAS a f t e r digestion i n HC1O4--HNO3-4i2SO4 and e x t r a c t i o n w i t h d i thizone i n CC14 was published (704). The RSDs f o r Pb were: and f o r Cd: grass 10-23% and beef l i v e r 5-17%. The reports "Workshop on the determination o f Pb i n foods" by Dabeka (693) and " I n t e r l a b o r a t o r y analysis o f sewage sludge" by Adelman e t a1 .(1887) have been published (see ARAAS, 1981 , 11, Refs. C1092, C126). o r a t o r i e s using ETA-AAS, hydride generation AAS and spectrofluorimetry (1623). Average values f o r Se ranged from 47 t o 118 pg 1-1 w i t h a mean o f 89 pg 1 - l . The most r e l i a b l e method was considered t o be ETA-AAS which gave an RSD o f 6%, compared t o 10% f o r spectrofluorimetry and 35% f o r hydride generation AAS.l i m i n a r y digestion o f the serum sample was n o t required f o r ETA-AAS and sample volumes <0.1 m l could be used. The concentrations o f As, Au, B r , Ca, Cd, C1, Coy C r , Cu, Fe, Hg, Mg, Mn, Na, Pb, S, Sb, Se, S r and Zn i n human h a i r RM (HH-1) o f the I n t e r n a t i o n a l Atomic Energy Authority, Vienna, were c e r t i f i e d on the basis o f the r e s u l t s o f an i n t e r l a b o r a t o r y study (1063).The powdered material was d i s t r i b u t e d t o over 100 laboratories o f which 66 reported data f o r more than 40 elements. S t a t i s t i c a l evaluation o f the data enabled c e r t i f i c a t i o n o f the 20 elements l i s t e d above and, i n addition, inter-comparisons o f d i f f e r e n t methods and laboratories were made w i t h special reference t o As, Cd, Hg, Pb and Sb.A number o f i n t e r l a b o r a t o r y studies have been reported on the determination o f trace metals i n n a t u r a l waters. For the determination o f Cd, Cu, Pb and Zn by AAS, polarography, NAA and proton-induced X-ray emission spectrometry (1740) , RSDs ranged from 3-47%, Pb and Zn having the poorest RSDs.Inter-method devi- The A collaborative study on the deter- grass 7-lo%, beef l i v e r 8-17% and blood 5-20%; Selenium was determined i n pooled human serum by 9 Finnish and 2 US lab- Pre-98 Analytical Atomic Spectroscopy ations f o r Cd, Cu and Pb were 36-71%, 14-55%, and 32-73% respectively.laboratories p a r t i c i p a t e d i n a study on the determination o f t o t a l Fe i n d r i n k i n g water using c o l o r i m e t r i c procedures and FAAS (2288). Disagreement was noted between the mean values f o r colorimetry (71.2 f 2.5 pg 1-’) and FAAS (84.5 ? Twenty 3.6 pg 1-’) and i t was considered s i l i c a t e .The National I n s t i t u t e the r e s u l t s o f an i n t e r l a b o r a t o r y i n water (1469). Reproducibility Hg, Mn, Se and Zn, b u t u n r e l i a b l e t h a t the l a t t e r was subject t o interference by f o r Water Research, South A f r i c a , published study on the determination o f 10 heavy metals was considered s a t i s f a c t o r y f o r As, Cd, C r y Cu, data were obtained f o r Fe and Pb.A l l the p a r t i c i p a t i n g laboratories analysed the samples by AAS except one where ICP-OES was used. C r y Cu and Pb i n standard solutions by ETA-AAS was c a r r i e d out i n 1979 (991). The exercise, which involved the use o f 11 models o f spectrometer and 6 types o f furnace, was c a r r i e d out on s i n g l e and mu1 tielement standard solutions having concentrations i n the range 1-50 ug 1 - l .age d i d n o t influence detection performance, modern instruments which were equipped w i t h automatic sample i n j e c t i o n gave improved precision. f o r the determination o f Cd, Cu, Hg, Mn, Mo, N i , V and Zn i n open-ocean water was undertaken i n Bermuda i n 1980 (1644). f i e d Niskin and unmodified Hydro-Bios sampling b o t t l e s , each f i t t e d w i t h 3 commonly used hydrowires, were compared using a n a l y t i c a l methods based on ETA-AAS, ICP-OES and ASV.laboratories f o r several metals than has been the case i n previous i n t e r - c a l i b r a t i o n s . and hydrowires were n o t as large as has been claimed i n the past (except f o r Cu and Zn).series 22) may be obtained from UNESCO, 7 Place de Fontenoy, 75700 Paris. Olaf- son (1486) described an i n t e r n a t i o n a l c a l i b r a t i o n experiment f o r Hg i n sea water i n v o l v i n g 32 laboratories. spiked w i t h HgC12, b u t serious e r r o r s occurred f o r determinations a t natural Hg concentrations. An extensive i n t e r l a b o r a t o r y comparison on the determination o f Cd, It was found t h a t , although equipment An ambitious i n t e r c a l i b r a t i o n experiment designed t o compare sampling devices Modified and unmodified Go-Flo, modi- The study revealed b e t t e r agreement between experienced marine Differences i n data caused by the use o f d i f f e r e n t sampling methods A complete account o f the i n t e r c a l i b r a t i o n exercise (IOC Technical Good accuracy and precision were obtained f o r samples An extensive study on the r e l i a b i l i t y of environmental analyses was undertaken by the Environment Agency of Japan (1742).Soil and sediment samples were analysed by government, municipal and commercial laboratories (200 laboratories i n t o t a l ) f o r As, Cd, Cu, Pb, Zn, t o t a l N and t o t a l P.a t the 100 pg g - l l e v e l i n s o i l were determined d i r e c t l y by FAA, but preconcent- r a t i o n by solvent e x t r a c t i o n was necessary f o r Cd a t the 1 pg g - l l e v e l . d i s t r i b u t i o n o f data gave a negative skew which indicated t h a t complete decom- p o s i t i o n and e x t r a c t i o n were key factors f o r obtaining r e l i a b l e r e s u l t s .RSD f o r As determination (20%) was a factor o f 2 greater than t h a t f o r the other Copper, Pb and Zn present The TheMethodology 99 heavy metals. Other references o f interest - Collaborative study f o r the determination o f Pb in dried sugar beet, pulp and molasses : 585, 686, 737. Comparison o f AAS procedures for Pb in wine : 1761.100 Analytical Atomic Spectroscopy TABLES 3.3A.1-3.3A.8: CERTIFIED REFERENCE MATERIALS Explanation: a b i l i t y o f RMs c e r t i f i e d f o r elemental composition. i n c l u d e d i n the l i s t i n g s .I n t e r n a t i o n a l Organisation f o r Standardization (ISO). The i n f o r m a t i o n g i v e n i n t h e Tables represents t h e c u r r e n t a v a i l - Categories o f RMs a r e based on those proposed by t h e U n c e r t i f i e d RMs a r e n o t Table 3.3A.1 CHEMICALS AND INDUSTRIAL PRODUCTS S u p p l i e r M a t e r i a1 Bureau National de Metrologies (BNM), Fuel O i l 8-10 r u e C r i l l o n , 75194 P a r i s Cedex 04, France Commission o f t h e European Communities, Comrnuni ty Bureau o f Reference (BCR) , 200 rue de l a L o i , B-1049 Brussels, Be1 g i um Organometallic compounds Carbone L o r r a i n e , 45 r u e des Acacias, BP 164, 75017 Paris, France Reagents Commissariat a 1 'Energie Atomique, C r i s t a l Tec, BP 85 Centre de tri, 38041 Grenoble Cedex, Francs Reagents I n d u s t r i a1 Manufacturing I n s p e c t i on Primary standards 6-1 5-1 Ginza , Chuoku , Tokyo, Japan National Bureau o f Standards, Primary standards , f e r t i 1 i zers , f u e l O f f i c e o f Standard Reference M a t e r i a l s , Washington, DC 20234, U.S.A.I n s t i t u t e , o i l , organometallic compounds Na ti ona 1 Phys i c a l Laboratory, O f f i c e o f Reference M a t e r i a l s , Teddi ngton , Middlesex, TW17 OLW, England P r o d u i t s Chimiques Ugine Kuhlmann, l e Rubis Synthetique des Alpes, 185fin ,la rri P - Fuel o i 1 , organometall i c compounds ReagentsMethodology 101 Table 3.3A.1 CHEMICALS AND INDUSTRIAL PRODUCTS - continued Supplier Material Pro1 abo , 12 rue Pelee, BP 200, 75526 Paris Cedex 11, France Rhone-Poulenc Chimie Fine, 21 rue Jean Goujon, 75008 Paris, France Reagents Reagents Service des Materiaux de Reference (SMR), Fuel o i l 1 rue Gaston Boissier, 75015 Paris, France Table 3.3A.2 FERROUS METALS AND ALLOYS Supplier Finely divided form Solid form A m t f u r Standardisierung und WarenprUfung (ASMW) , 102 Berlin, Wallstrasse 16, D.D.R. Bundesanstal t fUr Material- 1 Berlin 45, Unter den Eichen 87, Ge many Bureau of Analysed Samples Ltd., Newham Hal 1 , Newby, Middlesbrough , Cleveland, TS8 9EA, England prUfung (BAM), Bureau National de Metrologie 8-10 rue Crillon, 75194 Paris Cedex 04, France (BNM) 3 Centre Technique des Industries 44 Avenue de l a Division Leclerc, 9231 O-Sevre , France de l a Fonderie (CTIF), h a l l oyed and a1 1 oyed s t e e l s , c a s t irons, s l a g s , f e r r o alloys Unal 1 oyed and a1 1 oyed s t e e l s , s l a g s , c a s t irons, f e r r o alloys High purity irons, unalloyed and alloyed s t e e l s , s l a g s , c a s t irons, f e r r o a1 loys Unalloyed and alloyed s t e e l s , c a s t irons High purity irons C s t e e l s C s t e e l s102 Analytical Atomic Spectroscopy Table 3.3A.2 FERROUS METALS AND ALLOYS - continued ~~ Supplier Finely divided form Solid form Centro Naci onal de Investi gaci ones Cui dad Uni versi t a r i a , Madrid 3 , Spain Gosstandard of the USSR, 9 Leninsky Prospekt, 11704 Moskow, U.S.S.R.Metal urgi cas , I n s t i t u t de Recherches de l a BP 129, 78100-Saint Germain en Laye, France Siderurgie Francaise , I n s t i t u t o de Pesquisas Divisao de Quimica e Engenharia NuCleo de Padroes Anal t t i c o s , Caixa Postal 7141, 01000-Sao Paulo - SPY Brazi 1 Tecnoldgicas do Estado de Sao Paulo S/A-IPT, Qu i m i ca , Iron and Steel I n s t i t u t e of 9-4, 1-Chome, Otemachi Chiyoda-ku , Tokyo, Japan Japan , MBH Analytical Limited, Holl and House , Queens Road , Barnet , Herts.EN5 4DJ, England Metal impex POB 330, H-1376 Budapest, Hung a ry National Bureau of Standards, Office of Standard Reference Washington, DC 20234, U.S.A.Prolabo, 12 rue Pelee, BP 200, 75526- Paris Cedex 11 , France Materi a1 s , Spex Industries Inc. , 3880 Park Avenue, Metuchen, NJ 08840, U.S.A. Unalloyed and alloyed s t e e l s Unalloyed and alloyed s t e e l s , c a s t irons Unalloyed and a1 loyed s t e e l s , f e r r o alloys, c a s t irons, slags Unal 1 oyed and a1 1 oyed s t e e l s Unalloyed and alloyed s t e e l s , c a s t irons Unal 1 oyed and s t e e l s Unal 1 oyed and s t e e l s , c a s t f e r r o a1 loys Steels a1 1 oyed a1 1 oyed rons , Unalloyed and alloyed s t e e l s Unalloyed and a1 loyed s teel s Unalloyed and alloyed s t e e l s , c a s t irons Unal 1 oyed and a1 loyed s t e e l s , c a s t irons Unal 1 oyed and s t e e l s , c a s t a1 loyed rons Unal loyed and a1 1 oyed s teel s , c a s t i ronsMethodology 103 Table 3.3A.2 FERROUS METALS AND ALLOYS - continued Suppl i e r Finely divided form S o l i d form ~~ ~~ Swedish I n s t i t u t e f o r Metal Drottning K r i s t i n a s vag 48, slags S-11428 Stockholm, Sweden Unalloyed and alloyed Research , steels, f e r r o alloys, South African Bureau of Standards, Private Bag X191 , Pretoria, Transvaal 0001 , South A f r i c a Ferro a1 loys Table 3.3A.3 NON-FERROUS METALS AND ALLOYS Supplier Finely divided form S o l i d form A i r Products Ltd., Special Prods. Dept. , Weston Road, Crewe , Cheshire, CWl lDF, England A1 umi n i um Company o f America , A1 con Techni cal Center , A1 con Center , PA 15069, U.S.A. A1 umi n i um Pechi ney , 23 bis, rue Balzac, 75360 Paris Cedex 08, France Amt fur Standardisierung und WarenprOf ung (ASMW) , 102 B e r l i n , Wallstrasse 16, D.D.R.B r i t i s h Aluminium Co. Ltd. Chal f o n t Park , Gerrards Cross, Bucks, SL9 OQB, England Bundesanstal t ftlr Material- Unter den Eichen 87, Germany prtlfung (BAM) , Cu, Mo, Pb, T i , Z r base A1 base Sn, A1 , Mg base Cu , N i , A1 , Mg base High-purity metals, A l , Mg base A1 , Cu A1 base104 Analytical Atomic Spectroscopy Table 3.3A.3 NON-FERROUS METALS AND ALLOYS - continued Supplier Finely divided form S o l i d form Bureau o f Analysed Samples Ltd., Newham H a l l , Newby, Middlesbrough , Pb base Cleveland, TS8 9EA, England High-purity metals , A l , Mg, Cu, N i , Sn, High-purity metals, A1 , Cu, N i base BNF Metals Technology Centre, Grove Laboratories , Denchworth Road, Wan tage , Oxfordshi r e , England Canada Centre f o r Mineral Energy c/o Coordinator, CANMET, 555 Booth Street, Ottawa, Ontario K1A OG1, Canada Techno1 ogy , Commissariat a 1 ' Energi e Atom- ique (CEA) , C r i s t a l Tec, BP 85 Centre de tri, 38041 -Grenoble Cedex, France Centre Technique des Industries 44 Avenue de l a D i v i s i o n Leclerc, 92310-SWres, France de l a Fonderie (CTIF), Centre Techniques du Zinc, 34 rue Col 1 ange, 92300-Levallois Perret, France Chemicals Inspection & Testing 1-1 , 4-ChomeY Higashi-Mukojima, Sumida-Ku , Tokyo , Japan I n s t i t u t e , Gosstandard o f the USSR, A1 , Cu, N i base 9 Leninsky Prospekt, 11704 Moscow, U.S.S.R. Inco Europe Limited European Research & Development Commercial Development Department , Birmingham, B16 OAJ, England Centre, A1 , Cu, N i base Cu base A l , Mg base Cu base High-purity metals, Zn base A1 , Cu, N i base A1 , Cu, N i base A1 , Cu, N i baseMethodology 105 Table 3.3A.3 NON-FERROUS METALS AND ALLOYS - continued Supplier Finely divided form S o l i d form I n s t i t u t o de Pesquisas Tecndlogicas do Estado de Sao Paulo S/A-IPT, Divisao de Quimica de Engenharia Qulmi ca , NuCleo de Padroes Anal I t i c o s , Caixa Postal 7141, 01 000-Sao Paul 0-SP , Brazi 1 Japan A1 umi n i urn Federati on , Nihonbashi M e i j i Building, 1-3, 2-Chome, N i honbashi , Japan Japan Brass Makers Association, 12-22, 1-Chome, T s u k i j i , Japan A1 , Cu, Mg base Chuo-Ku , Tokyo , Chuo-Ku , Tokyo, Japan L i g h t Metal Association, 1-3,2-Chome, Nihonbashi, Japan Johnson Matthey Chemicals Ltd., Orchard Road, Roys ton , Herts, SG8 5HE, England MBH Analytical L i m i ted , Holland House, Queens Road, Barnet, Herts, EN5 4DJ, England Chuo-Ku , Tokyo , High-purity metals Mercu r e I ndu s t r i e , 13 rue Saulnier, 92800-Pu teaux , France Metal impex, POB 330, H-1376 Budapest, Hungary High-purity metals Cu base A1 , Cu, Mg base A1 Cu, Mg base High-purity metals A l p Cu, N i , Zn, Co base A1 base National Bureau o f Standards , High-puri ty metals , O f f i c e o f Standard Reference A l , Coy Cu, N i , Pb, Mg, Sn, T i , Zn, Z r Washington, DC 20234, base U.S.A. A l , Cu, Pb, N i , T i , Zn, Z r base Materials,106 A naly tical A tomic Spectroscopy Table 3.3A.3 NON-FERROUS METALS AND ALLOYS - continued Supplier Finely divided form Solid form P1 anet-Wattohm, 05310-la Roche de Rame, France H i gh-puri t y metals Pro1 abo , 1 2 rue Pelee, BP 200, 75526-Paris Cedex 11 , France Rhone-A1 pes Mercure, 4 rue des Fauvettes, Mons V i l e t t e D'Authon, 38230 Pont de Cheruy, France Spex Industries Inc., 3880 Park Avenue, Metuchen, NJ 08840, U.S.A. High-purity metals High-puri t y metals C u , P b , Sn base Tab1 e 3.3A. 4 GEOLOGICAL MATERIALS Supplier Finely divided form A m t f u r Standardi sierung und Warenprdfung (ASMW) , 102 Berlin, Wallstrasse 16, D.D.R. Bundesanstal t fur MaterialprUfung 1 Berlin 45, Unter den Eichen 87, Germany (BAM)? Bureau of Analysed Samples Ltd., Newham Hal 1 , Newby, Middlesbrough, Cleveland, TS8 9EA, England Canada Centre f o r Mineral and Energy c/o Coordi nator , CANMET, 555 Booth S t r e e t , Ottawa, Ontario K1A O G 1 , Canada Technology, Mn, Cry Sn ores Fe ores Fey Mn, Cry A1 ores, fluorspar, s i l l i m a n i t e , Na & K feldspar, magnesi t e , dolomite, 1 imestone Sb, Co-Mo, Au, Fey Mo ores syenite, gabbro, ultramafic rocks, s o i l sMethodology 107 Table 3.3A.4 GEOLOGICAL MATERIALS - continued Suppl i e r Finely divided form National Bureau o f Standards, Office o f Standard Reference Materials, Washington, DC 20234, U.S.A.National Chemical Lab. f o r Industry, River and estuarine sediments, coal, 1 H i gashi 1 -Chome, Yatabemachi , Tsukuba-Gun , Ibaragi , Japan National I n s t i t u t e f o r Environmental Pond sediment D i v i s i o n o f Chemistry & Physics , Yatabemachi , Tsukuba, Ibaraki , Japan Fe, A l , Cu, Mo, L i , Zn, W ores, fluorspar, Na and K feldspar, clays feldspar, clays, granodiori t e , basalt Studies, South African Bureau o f Standards, Private Bag X191, Pretoria, Transvaal 0001 , South A f r i c a US Geological Survey, National Center 972, Res ton, Va. 22092, U.S.A. Rocks, Fey C r y P t and Z r ores Diverse Table 3.3A.5 GLASSES, CERAMICS AND REFRACTORIES ~~ ~ Suppl i e r Finely divided form Bureau o f Analysed Samples Ltd., Newham Hall, Newby, Middlesbrough, p u r i t y s i l i c a Cleveland TS8 9EA, England Centre d'Etudes e t de Recherches de Cement 23 rue de Cronstadt, 75015 Paris, France S i l i c a b r i c k , f i r e b r i c k , magnesite- chrome, Portland cement, zircon, high L ' I n d u s t r i e des Liants Hydrauliques, Centre National de l a Recherche Scienti f i que, Centre de Recherche Petrographiques e t Geochimiques (CNRS/CRPG) , 15 rue Notre Dame des Pauvres, Case O f f i c i e l l e No. 1, 54500 Vandoeuvre-1 ez-Nancy, France Glasses ( 2 a v a i l a b l e )108 Analytical Atomic Spectroscopy Table 3.3A.4 GEOLOGICAL MATERIALS - continued Supplier Finely divided form Centre National de l a Recherche Scient- Bauxite, granite, i r o n ores i f i q u e , Centre de Recherche Petrographiques e t Geochimiques (CNRS/CRPG) , 15 rue Notre Dame des Pauvres, Case O f f i c i e l l e No. 1, 54500 Vandocuvre-lez-Nancy, France Commission o f European Communities, Communi ty Bureau o f Reference (BCR) 200 rue de l a L o i , B- 1049 Brussel s , Be1 gium Geological Survey o f Japan 1-3 H i gashi 1 -Chome , Yatebemachi , Tsukuba-Gun , Ibaragi , Japan Zn, Sn, Cu, Pb ores, coke Fel dspar , clays , granodi o r i t e basal t Gosstandart o f the USSR, 9 Leninsky Prospekt, 11704 Moscow, U.S.S.R.U ores, lake sediment and s o i l I n s t i t u t o de Pesquisas Tecnoldgicas do Divisao de Quimica de Engenharia 0100 Sao Paulo-SPY Brazi 1 Phosphate rocks and clays Estado de Sao Paulo S/A-IPT, Qu-lmi ca , I n t e r n a t i o n a l Atomic Energy Agency, U ores Analytical Qua1 i ty Control Services , Laboratory Sei bersdorf , PO Box 590, A-1011 Vienna, Austria Junta de Energia Nuclear, Cuidad Universi t a r i a , Madrid-3, Spain L.R.M., BP 3013, 54000 Nancy Cedex, France L i g n i t e Rocks Marine A n a l y t i c a l Chemistry Standards Marine sediments Chemistry D i v i s i o n , National Research Council , Montreal Road , Ottawa, K1A ORGY Canada Program,Methodology Table 3.3A.5 GLASSES, CERAMICS AND REFRACTORIES - continued 109 Suppl i e r F i n e l y d i v i d e d form Federation Europeenne des Fabricants 44 r u e Copernic, 75016 P a r i s France de Produi t s R e f r a c t a i r e s (PRE) , L.R.M., B.P. 3013, 54000 Nancy Cedex, France National Bureau o f Standards, O f f i c e o f Standard Reference M a t e r i a l s , Washington, DC 20234, U.S.A. National Chemical Lab. f o r I n d u s t r y , 1 Higashi 1-Chome, Yatabemachi , Tsukuba-Gun, I b a r a g i , Japan Pro1 abo , 12 r u e Pelee, B.P. 200, 75526 P a r i s Cedex 11 , France S h e f f i e l d U n i v e r s i t y , Dept.o f Ceramics. Glasses & Polymers, Northumberl and Road, S h e f f i e l d S10 2TZ, England S o c i e t y o f Glass Technology, 20 Hallam Gate Road, S h e f f i e l d S10 5BT, England R e f r a c t o r y m a t e r i a1 s R e f r a c t o r y m a t e r i a l s Lead/barium, opal, h i g h and low boron, soda l i m e glasses, s i l i c a , alumino- s i l i c a t e and chrome r e f r a c t o r i e s , P o r t l a n d cements Sodalime s i l i c a , s i l i c a , h i g h s i l i c i c acid-high b o r i c a c i d glass R e f r a c t o r y m a t e r i a l s G1 asses G1 asses ( 3 avai 1 able) Table 3.3A.6 BIOLOGICAL, BOTANICAL AND FOOD MATERIALS S u p p l i e r M a t e r i a l Laboratoi r e National D ' Essai s (LNE) , P1 ants 1 r u e Gaston B o i s s i e r , 75015 P a r i s , France National Bureau o f Standards , O f f i c e of Standard Reference M a t e r i a l s , Washington, DC 20234, U.S.A.Bovine l i v e r , brewers yeast, c i t r u s leaves, orchard 1 eaves, o y s t e r t i s s u e s , p i n e needles, r i c e f l o u r , tomato 1 eaves , wheat f 1 our110 Analytical Atomic Spectroscopy Table 3.3A.6 BIOLOGICAL, BOTANICAL AND FOOD MATERIALS - continued Supplier Material National I n s t i t u t e f o r Environmental Pe pperbu s h Division of Chemi s t r y and Physics , Yatabemachi , Tsukuba, Ibaraki , Japan Studies , Table 3.3A.7 CLINICAL MATERIALS ~~ ~ ~~~ Suppl i e r Ma t e r i a1 Biomerieux, Chemin, de L'Orme, Marcy L ' Etoi l e , 69260 Charbonnieres Les Bains, France Various 1 iquid preparations National Bureau of Standards , Freeze-dried urine and serum Office of Standard Reference Materials, Washington, DC 20234, U.S.A.Table 3.3A.8 ENVIRONMENTAL MATERIALS Supplier Finely divided form Bureau of Analysed Samples Ltd. , Newham Hal 1 , Newby, Middlesbrough , Cleveland TS8 9EA, England I n s t i t u t de Recherches de l a Siderurgie BP 129, 78104 Saint Germain en Laye, France Furnace dust ( L D ) Furnace dust ( e l e c t r i c ) Francai s e , Marine Analytical Chemistry Standards Seawater A t 1 an t i c Research Laboratory , National Research Counci 1 , Halifax, N.S.B3H 321, Canada National Bureau of Standards , Urban p a r t i c u l a t e , coal f l y ash, f i l t e r Office o f Standard Reference Materials , Washington, DC 20234 , U.S.A.Program , media, watersMethodology 111 TABLES 3.3B.1-3.38.8: REFERENCE METHODS OF ANALYSIS Ex lanation: The information given in the Tables i s a compilation of reference + met o s o analysis which have been published and approved by various organiz- ations. In the present context no d i s t i n c t i o n i s made between the terms refer- ence method, standard method, recommended method and o f f i c i a l method as used i n the l i t e r a t u r e .but flame atomic emission spectrometry, emission spectrography and inductively- coupled plasma optical emission spectrometry a l s o feature i n the l i s t i n g s . entry i n the Table, f o r the appropriate body, represents e i t h e r the page number i n the standard t e x t o r the code number of the reference method.for each entry s i g n i f i e s the analytical technique as follows: ( 1 ) Flame atomic absorption spectrometry (2) Electrothermal atomization - atomic absorption spectrometry ( 3 ) Cold vapour - atomic absorption spectrometry ( 4 ) Hydride generation - atomic absorption spectrometry ( 5 ) Flame atomic emission spectrometry ( 6 ) Inductively-coupled plasma - optical emission spectrometry ( 7 ) Emission spectrography The names and addresses of the o f f i c i a l bodies are given below.Most of the methods are based on atomic absorption spectrometry Each The superscript Reference Methods of Analysis - Official Bodies 1 . 2. 3 . 4. 5. 6 . AMC : AOAC : APHA: ASTM : BS : EPA: Analytical Methods Comnittee, Analytical Division, The Royal Society of Chemistry, Burl ington House, London W1 V OBN, U.K. Association of Official Analytical Chemists, Official Methods of Analysis (13th Ed.), 1111 N . 19th S t r e e t - Suite 210, Arl i ngton , VA 22209, U.S.A. American Public Health Association, Standard Methods f o r the Examination of Water and Wastewater (14th Ed., 1975), 1015 15th S t r e e t N W , Washington, DC 20005 , U.S.A.American Society f o r Testing and Materials, 1916 Race S t r e e t , Phi 1 adel p h i a , PA 191 03 , U.S.A. British Standards I n s t i t u t i o n , 2 Park S t r e e t , London, W1A ZBS, U . K . US Environmental Protection Agency, Methods f o r Chemical Analysis of Water and Wastes, Office of Research and Development, Environmental Moni t o r i ng Sys tems Laboratory, Research Triangle Park , NC 27711, U.S.A.112 Analytical Atomic Spectroscopy 7.I P : I n s t i t u t e o f Petroleum, 61 New Cavendish Street, London , W1M 8AR, U.K. 8. ISO: I n t e r n a t i o n a l Organization f o r Standardization, Case Postale 56, 1211 Geneva 20, S w i t z e r l and. 9. IUPAC: I n t e r n a t i o n a l Union o f Pure and Applied Chemistry, Bank Court Chambers , 2-3 Pound Way, Cowl ey Centre, Oxford OX4 3YF, U.K. 10. NBS: National Bureau o f Standards, O f f i c e o f Standard Reference Materi a1 s , Was h i ngton , DC 20234 , U.S.A. 11. NWC: National Water Counci 1 Standing Committee o f Analysts , Dept. o f the Environment, Room A416, Romney House, 43 Marsham Street, London SWlP 3PY, U.K. 12. SABS: South African Bureau o f Standards, Private Bag X191m, P r e t o r i a 0001 , South A f ri ca . 13. USGS: US Geological Survey, Methods f o r Determination o f Inorganic Substances i n Water and F1 u v i a l Sediments , Book 5, Chapter A1 , 12201 Sunri se Val 1 ey Drive , Reston, VA 22092, U.S.A.Table 3.38.1 CHEMICALS AND INDUSTRIAL PRODUCTS AOAC ASTM BS IP IS0 IUPAC SABS Matrix Anal y t e Acimoni urn bicarbonate Pb DP711 O(l) Baking powders Mg ,K,Na Calcium chloride Hg E506(3) 5050(l) Caustic soda A1 ,F,Fe,Na,Si Cryol i t e Na P DIS6374(l) Drugs Ca , K ,Na 36.05 (’I Ferti 1 i zers Ca , Cu , Fe , Mg ,Mn , Zn D3684 (3) D3682(l) coal /coke ash Major/minor elements Trace elements D3683(l) ashes Inorgani c constituents gas turbine Trace metals D2788(l1 Trace metals D3605(l) gasol i ne Mn 03831 ( ) Pb gas (natural ) A1 8.023(l) DP6918(’ Borates Ca,Mg Boric acid Ca ,Mg 20.043(1) E449(l) ~ 5 3 8 ( ~ ) DP2366(l) 2.1 09 71 Fuels, coal Hg D3237(’ Greases, lubricating L? ,Wa D 3 d 5 Oil, e l e c t r i c a l insulating Cu D3635(l) fuel (residual) Na D131 8 ( 5 ) fuel and crude Na ,Ni ,V lubricating (unused) waterborne Ni ,V D3327(l) (proposed(3) ’81 ) D3717(l) Cr (low conc.) D3718(l) Pb,Cd,Co (low conc.) D3335(l) Hg (low conc.) D3624( 3, (1) urani um oxide H S u20 $ 3 7 1 Ba ,Ca ,Mg ,Zn Ba,Ca ,Mg,Zn Organic chemicals H9 Paint Sb (low conc.) 122.1 /75(7) 288/74(l) 308/74(’) 187/66( DIS3856/1( ) DIS3856/V(l)Table 3.3B.1 CHEMICALS AND INDUSTRIAL PRODUCTS - continued Analyte AOAC ASTM BS IP IS0 IUPAC SABS Matrix Paint (cont.) Paper boards, pulp Paper, highly opaque Phosphates (condensed) Phosphoric acid Pigments Pol yo1 s Rubber pigments Sodium hydroxide Sodium phosphate Sodium sulphate Timber preservatives Urea Pb Cd Ca cu Fe Mn Cd ,Zn Ca Ca Cd , Zn Na,K Pb cu Mn Pb , Zn Hg Hg Ca As,Cr,Cu Copper naphthenate Sn Biuret 5.001 D1224(1) D4004(l) 6075/11 (3) 5666/4(’ ) 5666/7(l) DIS3856(l) DIS385f(j(’ ) DIS777 DIS778(l) DIS779(l) DIS1830(1) DIS5373 D IS3707 ( DIS6678 DP6101 / Z 1 1 DP61 DP6101 O V ) ,.,, DIS5993 DP7102‘ DIS5994(l) 673-1976(l)Methodology 115 Table 3.3B.2 FERROUS METALS AND ALLOYS M a t r i x Analyte ASTM BS I so Cast i r o n Pb,Mg E351(l) K2/20:64(l)* F e r r o n i c k e l co DP7520(l) I r o n ore A1 E507(’) DIS4688(l) Ca,Mg E508(l) DIS469 ( l ) cu DP4693?l) Na,K DP6831( Iron/Cr/Ni a l l o y Pb B i ,Pb Steel Ni DP4940( DP4943 ( S i l i c o n s t e e l & i n g o t / cu carbon/low-alloy s t e e l / wrought i r o n Pb E350(l) Too 1 s tee 1 /medi um- h i g h a l l o y s t e e l Pb E352(l) * A u s t r a l i a n Standard.Table 3.38.3 NON-FERROUS METALS AND ALLOYS ~~ M a t r i x Analyte ASTM BS I so A1 umi na Mn E34(’ ) Zn Aluminium ores Cd Hg Pb a1 1 oys Cd C r cu Na Pb Zn Aluminium oxide Ca ,Na ,V ,Zn Cadmi urn Ag ,Cu ,Pb , Copper & copper a l l o y s A1 B i Cd C r Cu ,Te Fe Ni Pb,Zn E478( ) Pb Sb Te Zn A1 umi n i urn & a1 umi n i urn Mg Zn E396(l) 41 40/22(‘) DIS3390(l) DIS2071(1) DIS5961(’ DIS5666( j r 3 ( 3 ) DIS6061 1728/19 ( 1728/23(l 1728/24(l 1728/20\ 1 1728/21 41 40/AD2( DIS595 ( l ) DP5959I1 DIS5960(l) DIS47441( ) DP7602 DP7603(l) DP7604(l) DIS474 ( l ) DP7601T1 DP7605(l) DP4740(l) Magnesi urn & magnesi urn a1 l o y s Pb 3907/15(l)116 Analytical Atomic Spectroscopy Table 3.3B.3 NON-FERROUS METALS AND ALLOYS - continued Matrix Analyte ASTM BS IS0 Magnesium/chromium ores Al,Cu,Pb,Zn Nickel & nickel alloys Ag,Bi ,Cd,Co Cu ,Fe ,Mn , Pb Zn A1 ,Si co Cr .cu Fe Mn Nickel ( e l e c t r o n i c grade) P i g lead Powder metals Zinc & zinc alloys 3727/21(’ 3727/20(7) Trace metals Zn 3727/22(l) Ag,Bi ,Cu,Zn E37(l) Ca , K , Mg , Na Co , Fe , Mn , Ni Mo,Ti ,V Co ,Fe ,Mn ,Mo Cr A1 ,Cd,Cu,Fe A1 Cd cu Mg 3630/5(l) Sn Metals 1225(7) Mg Ni ,Ti ,V Pb ,Mg E536(l) DI S 5889 ( ) DP6351 ( l ) DIS7627/6 ( ) DP4812(l) DP481 O( ) DP4811 ( l ) DP7155(l) Table 3.3B.4 GEOLOGICAL MATERIALS Matrix Anal yte ASTM USGS Gypsum & gypsum products Na A1 As Ba Be Ca Cd co Cr cu Fe Hg K Mg Mn Sediment Ag c471 C5)M e tho do logy 1 Table 3.38.4 GEOLOGICAL MATERIALS - continued M a t r i x Anal y t e ASTM USGS Mo Na N i Pb Sb Se Sn S r Zn Table 3.3B.5 GLASSES, CERAMICS AND REFRACTORIES M a t r i x Ana 1 y t e ASTM IS0 SABS ~ ~~~ Cement Na,K DP4813(l) 551(l y 5 ) Cement , b l ended Glazed ceramic surfaces Pb,Cd Glazed ceramic t i l e Porcel a i n enamel hydraul i c Na,K C114(l y 5 ) surfaces Pb,Cd C895( surfaces Pb,Cd C87d1 ) C738(’ ) Table 3.38.6 BIOLOGICAL, BOTANICAL AND FOODS N a t r i x Analyte AMC AOAC IS0 IUPAC MAFF Foods cu Hg Pb Sn Zn F i s h Pb F r u i t & vegetables Zn M i 1 k Pb Organic m a t t e r Cd Ni Se Sb Zn Cd Ca co cu Pb P1 ants Animal feeds Ca , Cu ,Fe 7.091 ( ) D i s t i l l e d l i q u o r s Cu,Fe 9.O29( ) Ref.G(l) 25.083 ( ) Ref .H(3) 25.044(l) 25.136(l) 25.150(l) 25.068( 25.063(’) Mg ,Mn ,Zn TC/34/SClO(l) D I S6636( R e f .A ( $ \ l ) Ref. C Ref.D(4) Ref. E(4) Ref. F ( l ) 3.006( 3.006( ) 1 7118 Analytical Atomic Spectroscopy Table 3.3B.6 BIOLOGICAL, BOTANICAL AND FOODS - continued Matrix Analyte AMC AOAC IS0 IUPAC MAFF Tea Wines 1: Ni K Na Zn Hg Cd,Ni Cu ,Fe 3.006( 3 . 0 0 6 ( l ) 3.006( ) 3.006( 25.031 (’ ) 11.021 ( 1 ) A. Analyst, 1969, 9 4 , 1153 E. Analyst,1980, 105, 66 B. Analyst, 1975, n o , 761 F. Analyst, 1973, 98, 458 c. Analyst, 1979, 104, 1070 G. Pure A p p l . Chem., 1979, 51 , 385 D. Analyst, 1979, 104, 778 H. Pure A p p l . Chem., 1979, 51, 2527 Table 3.3B.7 CLINICAL MATERIALS Mat ri x Analyte BCR IUPAC NBS Blood serum Ca Ref.A(l) 260-36(l) K 260-63( 5, L i 260-69(l) Na 260-60(5) Blood serum, urine Ni Ref.B ( * A. B. Pure Appl.Chem., 1981 , 53, 773 J.Clin.Chem.Clin.Biochem., 1981 , 19, 413i? .-b !? APHA ASTM BS E PA I so NWC USGS 5 3- Table 3.3B.8 ENVIRONMENTAL MATERIALS Matrix Anal yte Air particulates Atmosphere, workplace Waters & wastes Pb Pb Pb Pb Pb Ag A1 As Au Ba Be Ca Cd co Cr cu Fe Ir K K,Na Li Mg Mn Mo Na Ni 0s Pb Pd Pt Re Hg D3372(l) D2791 (5) D1886(l) 40FR46258(l) EQL-0380-043(’ EQL-0380-044(2) EQL-0380-045 (6) DIS5961 (l) DIS5666(3) DP6061 159(l)- N 0 Table 3.38.8 ENVIRONMENTAL MATERIALS - continued Ciatri x Analyte APHA ASTM BS E PA I so NWC USGS Rh Ru Sb SiO, Se Sn Sr T i 7 , D3697 ( 159(l) D3859 I I V 1 5 2 ( l ) Zn 148( ) D1691(' Trace elements D3919 ( Major/trace el emen ts Ba Sr Sea water, brines K,Li,Na 273(l) bMethodology 121 Table 3.3C SUPPLIERS OF SPECTROGRAPHIC GRAPHITE ELECTRODES 1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Baird Corporation Inc., 125 Middlesex Turnpike, Bedford, MA 01730, U.S.A.Carbon Products Division, Union Carbide Corp., 270 Park Avenue, New York, NY 10017, U.S.A.(ARL Ltd., Wingate Road, Luton, Beds, England). Labtest Equipment Co.,11828 La Grange Avenue, Los Angeles, CA 90025, U.S.A. Johnson Matthey Chemicals Ltd., Orchard Road, Royston, Herts, SG8 5HE, England. Le Carbone ( G B ) Ltd., Portslade, Sussex, England. Le Carbone Lorraine, 37-41 Rue Jean-Jaures, 92231 Gennevi 11 i e r s , France.Jarrell-Ash, 590 Lincoln S t r e e t , Waltham, MA 02154, U.S.A. Zebac Inc., P.O. Box 345, Bevea, OH 44017, U.S.A. Ringsdorffe-Werke GmbH, 53 Bonn-Bad Godesberg, West Germany (Fining & Chemical Products Ltd., Alperton, Wembley, Middlesex, HA0 4PE, England). Spex Industries Inc., 3880 Park Avenue, Metuchen, NJ 08840, U.S.A. (Glen Creston, 16 Dalston Gardens, Stanmore, Middlesex, HA7 IDA, England). Ultra Carbon Corp., P.O. Box 747, Bay City, MI 48706, U.S.A. (Heyden & Son Ltd., Spectrum House, Alderton Crescent, London N.W.4., England). Table 3.3D SUPPLIERS OF STANDARD METAL SOLUTIONS (MS) AND REAGENTS ( R ) FOR AAS Aldrich Chemical Co. Inc., 940 W . S t . Paul Avenue, Milwaukee, WI 53233, U.S.A. ( R ) J . T. Baker Chemical Co., 222 Red School Lane, Phillipsburg, NJ 08865, U.S.A. (MS, R ) Barnes Engineering Co., 30 Commerce Road, Stamford, CO 06902, U.S.A. (MS) BDH Chemicals Ltd., Poole, Dorset, BH12 4NN, England (MS, R ) Bio-Rad Laboratories, 2200 Wright Avenue, Richmond, CA 94804, U.S.A. (MS) Carlo Erba, Divisione Chimica Industriale, Via C . Imbonati 24, 20159 Milano, I t a l y (MS) Eastman Organic Chemicals, Eastman Kodak Co., 343 State S t r e e t , Rochester, NY 14650, U.S.A. ( R ) Fisons S c i e n t i f i c Apparatus Ltd., Bishop Meadow Road, Loughborough, Leics. LEll ORG, England (MS, R ) Harleco, Div. o f American Hospital Supply Corp., 60th and Woodland Avenues, Philadelphia, PA 19143, U.S.A. (MS) Hopkin & Williams Ltd., P.O. Box 1 , Romford, Essex, RM1 lHA, England (MS, V . A. Howe & Co. Ltd., 88 Peterborough Road, London, SW6 3EP, England (MS) Instrumentation Laboratory Inc., 113 Hartwell Avenue, Lexington, MA 02173, U.S.A. (MS) Johnson Matthey Chemicals Ltd., Orchard Road, Royston, Herts, SG8 5HE, England ( R ) Koch-Light Laboratories Ltd., Colnbrook, Bucks, England (R) (Anderman & Co. Ltd., Central Avenue, East Molesey, Surrey, KT8 OQZ, England) R )122 15 16 17 18 1 2 3. 4 5 6 7 8 9 10 11 12 13 14 15 16 17 AnaIyticaI A tomic Spectroscopy May & Baker Ltd., Dagenham, Essex, RMlO 7XS, England (R) E. Merck, D 61 Darmstadt, West Germany (R) Spex Industries Inc., 3880 Park Avenue, Metuchen, NJ 08840, U.S.A. (MS) ALFA Division, Ventron Corp., 152 Andover Street, Danvers, MA 01923, U.S.A. (MS) (G1 en Cres ton , 16 Dal s ton Gardens , Stanmore , M i ddl esex , HA7 1 DA , England) Table 3.3E SUPPLIERS OF ORGANOMETALLIC STANDARDS Angstrom Inc., P.O. Box 248, B e l l e v i l l e , M I 48111, U.S.A. Baird Corporation Inc. , 125 Middlesex Turnpike, Bedford, MA 01730, U.S.A. J. T . Baker Chemical Co. , 222 Red School Lane, Phi l l i p s b u r g , NJ 08865, U.S.A. BDH Chemicals Ltd., Poole, Dorset, BH12 4NN, England. Burt and Harvey Ltd., Brettenham House, Lancaster Place, Strand, London, W.C.2, England. Carlo Erba, Divisione Chimica I n d u s t r i a l e , Via C. Imbonati 24, 20159 Milano, I t a l y . Conostan Div., Continental O i l Co., P.O. Drawer 1267, Ponca City, OK 7460 U.S.A. Durham Raw Materials Ltd., 1-4 Great Tower Street, London, EC3R 5AB, England. Eastman Organic Chemicals, Eastman Kodak Co. , 343 State Street, Rochester NY 14650, U.S.A. Hopkin and Williams Ltd. , P.O. Box 1 , Romford, Essex, RM1 lHA, England. E. Merck, D 61, Darmstadt, West Germany. MBH A n a l y t i c a l Ltd., Station House, Potters Bar, Herts, EN6 lAL, England. D i v i s i o n o f Chemical Standards, National Physical Laboratory, Teddington , Middlesex, TWll OLW, England. National Spectrographic Laboratories Inc. , 19500 South Miles Road, Cleve- land, OH 44128, U.S.A. National Bureau of Standards , O f f i c e o f Standard Reference Materials , Washington, DC 20234, U.S.A. Research OrganidInorganic Chemical Corp. , 11686 Sheldon Street, Sun Valley, CA 91352, U.S.A. ALFA Division, Ventron Corp., 152 Andover Street, Danvers, N4 01923, U.S.A. (Glen Creston, 16 Dalston Gardens , Stanmore, Middlesex, HA7 lDA, England)