Industrial analysis: metals, chemicals and advanced materials

Industrial analysis: metals, chemicals and advanced materials

Ben Fairman,*a Michael W. Hinds,b Simon M. Nelms,c Denise M. Pennyd and Phill Goodalle

aLaboratory of the Government Chemist, Queens Road, Teddington, Middlesex, UKTW11 0LY

bRoyal Canadian Mint, 320 Sussex Drive, Ottawa, Ontario, Canada K1A 0G8cIRMM, Reteiseweg, Geel, Belgium B-2440dShell Research and Technology Centre, Thornton, PO Box 1 Chester, UK CH1 3SHeBNFL, Sella®eld, Seascale, Cumbria, UK CA20 1PG

Received 14th September 2000First published as an Advance Article on the web 28th November 2000

1 Metals1.1 Ferrous metals1.2 Non-ferrous metalsTable 1 Summary of analyses of metals2 Chemicals2.1 Petroleum and petroleum products2.1.1 Petroleum products2.1.2 Fuels2.1.3 Oils2.2 Organic chemicals and solvents2.2.1 Organic chemicals2.2.2. Solvents2.3 Inorganic chemicals and acids2.4 Nuclear materialsTable 2 Summary of analyses of chemicals3 Advanced materials3.1 Polymeric materials and composites3.2 Semiconductor and conducting materials3.3 Glasses3.4 Ceramics and refractories3.5 CatalystsTable 3 Summary of analysis of advanced materials4 References

This Atomic Spectrometry Update is the latest in an annualseries appearing under the title `Industrial Analysis'. Thisyear's review has followed the changed format introduced lastyear. Further changes may be made in the near future tore¯ect the growing interest in certain areas such assemiconductor materials and a continuing decrease intechnical advances being reported under other traditionalheadings.

There has been considerable interest in XRF as a tool forthe non-destructive analysis of metallic art and historicalobjects. Laser ablation continues to be explored for metalanalysis. Laser ablation ICP-AES was used to differentiatebetween coins from different countries based on the elementalcomposition pro®les (or ®ngerprints).

Improvements to XRF instrumentation and methodologyhave meant that analysis of used oil reported via thistechnique is on the increase. The analysis of coal and its by-products once again dominates the Fuels section. Varioussample preparation procedures and a host of differentanalytical techniques have been used for its analysis. Pre-concentration using on-line column techniques coupled withatomic spectrometry is very important for trace metaldetermination. 8-Hydroxyquinoline (8HQ) has beenthoroughly investigated and reported by many as an excellentchelating agent for organic based solutions.

There have been some interesting developments this year

which impact on inorganic chemicals analysis in industrialapplications, particularly in ICP-MS. Elimination andreduction of spectral interferences using collision celltechnology in ICP-MS is becoming a commercial reality, asevidenced by an increasing number of papers dealing with thetechnique.

Materials Control and Accountancy (MC&A) is of utmostimportance in the nuclear industry. Analysis, undertaken forthe purposes of MC&A, provides a `Gold Standard' for anylaboratory in terms of accuracy, precision and reliability.This crucial area has seen some development in the periodcovered by this review for nuclear materials analysis.

This year, coupling to a variety of detectors has proved tobe a popular use of ETV for the analysis of refractorysamples. Finally, one major disappointment and surprise thisyear has been the lack of high quality papers and articleswhich could be selected to grace our Catalysts section.

1 Metals

The analysis of ferrous, non-ferrous metals, and their alloys byanalytical atomic spectrometry is covered in this section. Asummary of the analytical methods reported for metals in thetime period under review is given in Table 1.

1.1 Ferrous metals

X-ray ¯uorescence spectrometry (XRF) was mainly used forqualitative investigations such as: the formation of Fe±Alintermetallic compounds by energy dispersive spectrometry(EDS);1 the investigation of the oxidation process in steels byX-ray diffraction and EDS;2 and scale formation of lowcarbon, low alloy steel by scanning electron microscopy(SEM)-EDS.3

An overview of the application of micro-beam techniques in thesteel industry was written4 which emphasised micro-analysis ofsurfaces and precipitates. A method for obtaining multi-layeredthickness pro®les by micro-proton induced X-ray emission(PIXE) spectrometry was reported using TiN-coated steels.5

A spark ablation source was coupled to an ICP-MS for thedetermination of minor and trace elements in various steelsamples.6 Major component matrix elements of 57Fe and 55Mnwere used as internal standards for a wide range of elements(Al, B, Co, Cu, Mn, Nb, P, Si and V). A restrictive path wasdesigned to minimise skimmer cone blockage from thequantities of spark eroded material. Detection limits werereported to be below 1 mg g21.

There were a number of reports concerning solid sampleatomic emission spectrometry. An overview of the application

*Review co-ordinator, to whom correspondence should be addressedand from whom reprints may be obtained.

1606 J. Anal. At. Spectrom., 2000, 15, 1606±1631 DOI: 10.1039/b007460h

This journal is # The Royal Society of Chemistry 2000

Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

. View Article Online / Journal Homepage / Table of Contents for this issue

http://dx.doi.org/10.1039/B007460H

http://pubs.rsc.org/en/journals/journal/JA

http://pubs.rsc.org/en/journals/journal/JA?issueid=JA015012

Table 1 Summary of analyses of metals

Element Matrix

Technique;atomization;presentationa Sample treatment/comments Ref.

Al Aluminum alloys AA;F;L Samples dissolved on-line with a high current density anodic electro-dissolution unit

34

Al Steel AA;F;L A 0.5 g sample was dissolved in 20 ml HNO3 (1 : 1), cooled, and 20 ml of40 g l21 NaOH were added. The resulting precipitate was ®ltered andre-dissolved in 20 ml HCl (1 : 1), 6 g ammonium acetate, 10 mltriethanolamine and water to dilute to 100 ml. An 8-fold sensitivityenhancement was reported with an air±acetylene ¯ame

35

As Steel AA;ETA;L Dissolved samples were treated with ascorbic acid and potassium iodideto reduce analytes to the trivalent state. Analytes were complexed byammonium dithiophosphoric acid O,O-diethyl ester and adsorbed ontoactivated carbon. They were then eluted by a small volume of nitricacid

36

As Steel MS;ICP;L Sample dissolved in HCl±HF and passed through a desolvatingmicroconcentric nebulizer to the ICP-MS. Rh added as an internalstandard

37

B Steel MS;ICP;L Boron nitride in the dissolved sample was decomposed by treatment withH2SO4±H3PO4 fuming at 290 ³C for 30 min. Iron was masked by theaddition of CyDTA and was adjusted to pH 8 by NH4OH. The samplewas passed through a column (Amberlite IRA-743) where B wasretained on the column. Iron and acids were washed out then B waseluted with 2 M HCL. Detection limit was 0.06 mg g21

38

Bi Steel andaluminium

AA;FI-ETA;L Bismuth is separated from metal matrices by complexation withammonium dithiophosphoric acid O,O-diethyl ester and adsorbed ontoa mini-column of activated carbon. The Bi complex was eluted withethanol and was collected in an autosampler cup for determination byETAAS. Limit of detection was 0.048 mg l21

39

C Steel XRF;Ð;S Sample was collected and polished under low pressure (6 Pa). Calibrationlinear up to 1% C and limit of detection 0.018%

40

Cr Metal alloys AA;ETA;L Dissolved and diluted sample introduced onto a boron coated pyrolyticgraphite tube

41

Cu Brass and bronze AA;F;L Samples dissolved on-line with a high current density anodic electro-dissolution unit

34

Deuter-ium

Titanium MS;SIMS;S None 42

In Aluminum alloy AA;ETA;L Sample (0.5 g) was dissolved in 10 ml HCl (left overnight), heated andHNO3 added. Sample diluted to volume with water and determined byETAAS with a tungsten coated L'vov platform. Limit of detection 8 pg

43

Ni Aluminum alloysand steel

AA;F;L After sample dissolution nickel is retained quantitatively on 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol±ammonium tetraphenylborate withmicrocrystalline naphthalene. After ®ltration, the nickel complex isdissolved in dimethylformamide and determined by FAAS. Precision is1.5% RSD for 5 mg g21 Ni. A column version is also described

44

P Cast iron XRF;Ð;S Sample was ground to 300 mesh and 2.4 g was mixed with a binder ofmethylcellulose in a 5 : 1 ratio, then compacted at 30 kN to form a disc(25 mm id)

45

Pb Copper alloys AA;F;G Dissolved samples (1±100 mg) in HNO3±HCl and evaporated. Residuesre-dissolved in 1 M HCl and 1 ml aliquot introduced into a metal vapourelution column (Mo), then heated to generate metal vapours (gas)

46

Pb Tin plate AE;ICP;L Sample (565 cm) was heated with 5 ml 0.5 M NaOH and 2 ml 30% H2O2

for 5 min to dissolve the plating layer. The digest was further boiledwith 5 ml HCl (1 : 1) to remove the remaining H2O2 and diluted to25 ml

47

Pt Palladium±platinum alloys

XRF;Ð;S None 19

S Steel AE;ICP;L Sample dissolved in a ¯ow through electrolytic dissolution system againsta graphite counter electrode in 6 M HCl. Precision: 3.5% RSD for25 mg g21 S

17

Sb Brass AF;HG-F;L Dissolved sample neutralized then NaOH added to 8 g l21. Interferingelements Cu, Fe, Co, and Ni are removed by precipitation

48

Sb Steel AA;ETA;L Dissolved samples were treated with ascorbic acid and potassium iodideto reduce analytes to the trivalent state. Analytes complexed byammonium dithiophosphoric acid O,O-diethyl ester and sorbed ontoactivated carbon. Eluted by a small volume of nitric acid

36

Th Thallium±ironslags

AA;F;L Sample (0.1±0.3 g) was dissolved in 15 ml 30% HNO3 and evaporated tonear dryness. The residue was dissolved in 5 ml 50% HCl and diluted to50 ml with water

49

V Metal alloys AA;ETA;L Dissolved and diluted sample introduced onto a boron coated pyrolyticgraphite tube

41

Zn Brass and bronze AA;F;L Samples dissolved on-line with a high current density anodic electro-dissolution unit

34

Zn Copper alloys AA;F;G Dissolved samples (1±100 mg) in HNO3±HCl and evaporated. Residuesre-dissolved in 1 M HCl and a 1 ml aliquot introduced into a metalvapour elution column (Mo), then heated to generate metal vapours(gas)

46

J. Anal. At. Spectrom., 2000, 15, 1606±1631 1607

Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


of lasers to analysis problems with emphasis on the steelindustry appeared in the literature.7 A study of the effect ofhigh temperatures (up to 1200 ³C) on steel analysis by LIBS,indicated that analytical signals were temperature dependent.8

A slag layer of variable thickness formed at temperatures above600 ³C. This was composed mainly of oxides of chromium,iron, and manganese. In another study,9 LIBS was used for thedetermination of carbon, silicon and chromium. The lens tosample distance was observed to be a relevant parameter in the

LIBS experiment. A study of the saturation effects and theamounts of material ablated10 indicated that ablation ef®ciencydecreased at lower laser energies due to plasma shielding andthe energy required for air breakdown. A more ef®cientablation rate can be obtained by focusing the beam inside thematerial free expansion zone of the created plasma.

A spark ablation device was interfaced to a microwave plasmaatomic emission spectrometer and applied to the analysis of steeland brass.11 Detection limits were in the mg g21 range but

Table 1 Summary of analyses of metals (continued)

Element Matrix


Zn Zinc based metalcoatings

AE;GD;S None; depth pro®ling 50

Various Antimony MS;GD;S None; relative sensitivity factors derived from steel reference materials 51Various

(8)Bullet leads MS;ICP;L Samples (25 mg) were dissolved in 2 ml 25% HNO3 and 0.5% HF. Lead

was precipitated with 8 ml H2SO4. Supernatant (1 ml) was mixed with1 ml 1250 mg l21 In (internal standard), 1 ml 0.5% HF and diluted to25 ml with 1% HNO3

52

Various Cadmium MS;ICP andGD;L and S

Analytes were adsorbed on Dowex-50X8 from 0.2 M HNO3z0.25 M HClsample solutions. Matrix separation was carried out by eluting analyteswith 6 M HCl. GD-MS of solid samples was also described and goodagreement was reported between the two methods

53

Various(8)

Cadmium MS;ICP;L Sample (0.05 g) was dissolved in 5 ml 10% HNO3 at low temperature,treated with 0.5 mg Y and 0.5 mg Bi (internal standards) and diluted to50 ml with water. Detection limits 0.005±0.052 mg l21 for As, Co, Ga,Mn, Pb, Sr, Tl and V

54

Various(7)

Copper alloystatuettes

MS;ICP;L Small samples (1±10 mg) were taken and dissolved in HNO3±HCl anddiluted to 100 ml with water

33

Various Copper MS;ICP;S and L Dissolved samples were analysed by continous and ¯ow injection ICP-MS. Solid alloys were also analysed by laser ablation ICP-MS. Methodswere compared

29

Various(4)

Copper alloys MS;ICP;L Dissolved samples (HCl±HNO3) were mixed with In as an internalstandard. Time of ¯ight mass spectrometric detection. Detection limits:0.7, 2.5, 11, 15 mg g21, for Pb, Sn, As and Zn, respectively

32

Various Copper±nickel,neodymium±aluminumalloys, ironpowders

XRF;Ð;S Powders were ground and sieved to 400 mesh. The powders were mixedwith cellulose and pressed into 30 mm diameter pellets at 236.25 MPa

55

Various(5)

Gold alloys AE;ICP;L Sample (20 mg) dissolved in 20 ml aqua regia (3 : 1 HCl±HNO3) with heat.Internal standards Y (20 mg l21) or In (200 mg l21) added upon dilution

56

Various(20)

High puritytungsten

AE;spark;S Sample ignited to form WO3, then 500 mg mixed with 250 mg bufferagent containing 5% Li2CO3 and 0.03% Ga2O3, and packed into anelectrode

57

Various(8) Iron MS;ICP;L

Iron was separated from the analytes using Chrome Azurol B (CAB) toform an insoluble chelate with Fe. A membrane ®lter was used forseparation and a surfactant was added for solubilization of the othermetal±CAB chelates

58

Various(9)

Iron MS;ICP;L Sample (0.1 g) was dissolved with 1.5 ml HCl, 1.5 ml HNO3, and 3 mlwater with heat. The solution was cooled, diluted with 4 ml HCl and10 ppb Y was added as a marker for recovery. The solution wasextracted twice with 10 ml portions of MIBK. The aqueous phase wasevaporated to near dryness and additions of 0.1 ml H2SO4, 5 ml HNO3,5 ml water and 10 ppb In (internal standard)

59

Various(3)

Iron and steel MS or AE;HG-ICP;L

Dissolved samples were put through a continuous hydride generator toeither an ICP-MS or ICP-AES. Detection limits: for As, Bi and Sb 0.5,0.8, 0.5 ng ml21 for ICP-AES; and 0.03, 0.02, 0.03 ng ml21 for ICP-MS

60

Various(2)

Coated steel plates AE;ICP;L Samples (50640 mm) of the aluminium±zinc coated steel were stripped ofthe coating with 60 ml 30% HCL. The solution was mixed with 3 ml of5% HCl and diluted to 100 ml with water

61

Various(9)

Steel MS;spark ablationICP;S

Samples were ®nished with a surface grinder using a 60 grit abrasivezirconium oxide belt

6

Various(4)

Steel AE;laser;S None; detection limits: 6, 50, 80, and 80 mg g21 for Cr, Ni, C and Si,respectively

9

Various Steel MS;FI-ICP;L The matrix elements were removed from the dissolved solution using amicro-electrolytic cell within the ¯ow injection system

62

Various(11)

Tantalum MS;ICP;L The dissolved sample was passed through an on-line ion exchangecolumn. Different groups of analytes were selectively eluted by: (1) 2 M

HCl±0.1 M HF (Be, Al, Ti); and (2) 1 M HNO3±0.1 M HF (Cr, Ni, Nb,Mo, Sn, W, Th, U)

63

aHy indicates hydride and S, L, G and Sl signify solid, liquid, gaseous or slurry atomization, respectively. Other abbreviations are listedelsewhere.

1608 J. Anal. At. Spectrom., 2000, 15, 1606±1631

Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


unfortunately these were 20 times higher than those obtainedwith a spark ablation-ICP-AES high resolution, sequentialspectrometer. A glow discharge-atomic emission spectrometerwith a specially designed glove box for the analysis of steelsamples was tested with steel samples.12 This preliminary studyshowed that carbon, oxygen and nitrogen can be determinedwith detection limits of 10, 20, and 40 mg g21, respectively.

A recent patent was issued related to AAS wherebycomponents in molten metal can be determined from theabsorption of speci®c wavelength light by vapour above themelt.13

Solution based methods are mainly summarized in Table 1for ferrous samples. However, some work warrants specialmention. Low energy electron induced X-ray spectrometry andSEM were used to characterize residues from dissolvedtitanium stabilized steels.14 Compounds TiN and TiC wereidenti®ed from the shape and structure of the X-ray peak (Ltransitions). Quanti®cation was also possible by comparing thespectra of known mixtures.

A review article of the application of high resolution ICP-MS tothe steel industry15 presented theviewthatdetection limitswere notgoverned by the spectrometer but by sampling and samplepreparation (i.e., reagents, dissolution procedures, environment).Another review focused on sample preparation, pre-treatment andseparation methods for steel analysis by ICP-MS.16

Sulfur in steel was determined via on-line electrolyticdissolution against a graphite counter electrode in an acidicmedium, followed by introduction into an ICP-AES.17 Theanalysis time was reported to be only sixty seconds per sample.

1.2 Non-ferrous metals

A method for the analysis of precious metals in conventionalcoloured and white karat jewellery alloys by XRF wasreported.18 Good results were obtained with calibration froma set of reference materials especially produced for this type ofanalysis. In another paper, binary alloys of platinum andpalladium were analysed by XRF.19 The micro-¯uorescencespectrometer was useful in establishing the homogeneity levelof element distribution in the alloys.

There has been considerable interest in XRF as a tool for thenon-destructive analysis of art and historical objects. Anoverview of this XRF application described a range of devicesfrom synchrotron beam lines to a transportable spectrometer.20

The use of a small XRF instrument for in-situ analysis ofobjects was described.21 The small active excitation window(8 mm2) was focused reproducibly by aligning two sightinglasers attached to beam exit and entrance components. Thesmall beam diameter permits elemental mapping and speci®csite analysis of these valuable samples.

The analysis of alloy nano-particles (v100 nm diameter) ofPt±Rh and Pt±Re by X-ray emission spectrometry wasdescribed.22 Quantitative and phase separation informationwas obtained from this technique, which was coupled with anelectron microscope. Proton induced X-ray emission (PIXE)has also been actively used in the analysis of rare materials suchas: ancient coins;23,24 and gold artefacts.25,26 The small beamdiameter permits elemental mapping and speci®c site analysisof these valuable samples.

Laser ablation continues to be explored for metal analysis.Laser ablation (LA)ICP-AES was used to differentiate betweencoins from different countries based on the elemental composi-tion pro®les (or ®ngerprints) and the depth pro®les.27 Similarly,binary Cu±Zn alloys were studied using LA-ICP-MS.28

Different ablation rates were observed for various alloycompositions. Linear calibration curves were made by normal-izing the Zn intensity to that of Cu or to the crater volume.Trace impurities in high purity copper were determined by thistechnique with standards made from high purity copperpowder mixed and pressed with solution standards.29 This

approach gave results that were within 15% of solution basedICP-MS values. This shows promise as a semi-quantitativescreening method and the method of standard production hascreated possibilities for situations where no reference materialsexist.

Methods involving dissolved metal samples continue to be arelevant part of metal analysis. The majority of papersinvolving AAS, ICP-AES and ICP-MS focus mainly on thesample preparation (see Table 1); however, some papers areworth mentioning.

There were two reports of isotope ratio measurements ofmetallic historical objects. In one study, 207Pb : 206Pb ratioswere determined in bronze objects30 by ICP-MS. In another,thermal ionization mass spectrometry was applied to thedetermination of magnesium isotope ratios in magnesiummetal reference material.31 An improvement in the uncertaintyby a factor of 3±4 times over ICP-MS was reported.

The use of different detection systems were reported. Time of¯ight mass spectrometry was used to the determine a variety ofelements in copper alloys.32 Lead isotopic and elementalanalysis of copper alloy statuettes were obtained by doublefocusing sector ®eld ICP-MS.33 Uncertainty estimates for Pbisotope ratio measurements were lower than for those obtainedby quadrupole-based ICP-MS.

An automated system was reported for the determination ofaluminum, copper, and zinc in non-ferrous alloys by FAASfollowing on-line sample dissolution with an electro-dissolu-tion unit.34 The system was reported to analyse 50 samples perhour (on average).

2 Chemicals

2.1 Petroleum and petroleum products

2.1.1 Petroleum products. Petroleum additives such astetraethyllead (the use of which is on the decline) and one ofits main replacements, methylcyclopentadienylmanganese tri-carbonyl (MMT), maintain a high pro®le because of theirpotential environmental impact. Three papers,64±66 of whichthe ®rst two make use of isotope ratio information via ICP-MSand the last low pressure ICP-MS, have described methods toassess the environmental impact of tetraethyllead. Likewise,two papers67,68 report the use of various speci®c techniques toquantify and speciate manganese compounds in gasoline.

Sun Xiao-Juan et al.69 discuss alternative sample preparationto determine Pb in gasoline instead of the traditional methods,e.g., the iodine monochloride method. The use of microwaveextraction±nitric acid to convert organic Pb into inorganic Pb isreported. The results compare very well with traditionalmethods and offer an accurate, simple and quick procedure,which does, however, rely on investment in microwavedigestion equipment.

The environmental impact of petroleum products is furtherinvestigated via the use of in-situ laser induced ¯uorescence(LIF), which has been applied to contaminated land.70 Variouscalibration sets were prepared using laboratory reference oil,fuel oil, gas oil, diesel fuel, Brent and German crude oil, all ofwhich were extensively characterized with regard to theirphotophysical properties. All standards were prepared in a wellcharacterized soil. Although of 30 soils analysed 23 of themwere deemed to be contaminated, quantitative in-situ analysisof petroleum products contaminated soil encounters manydif®culties attributed to the fact that petroleum products per seare very complex, ill de®ned analytes in a complex soil matrix.Hence, the limited variation in contaminants and a single soilmatrix for standard preparation must add to the uncertainty.However, for the work carried out thus far comparative datawith IR was very encouraging.

A review with 13 references of metal microanalysis inpetroleum fractions by ICP-MS has been reported.71 Four


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


different sample routes are compared and contrasted and theadvantages and disadvantages of the methods described.

2.1.2 Fuels. The analysis of coal and its by-products onceagain dominated the Fuels section. Various sample preparationprocedures and a host of different analytical techniques havebeen used for its analysis.

As previously discussed in the 1999 review alternativemethods that preclude the need for sample dissolutionprocedures are favoured by many for coal/¯y ash analysis. Inthis review period several techniques have been used to analysecoal/¯y ash in the solid state, although it is fair to say that acertain amount of sample preparation is still required. Zhanget al.72 have developed a method for the determination of Ge incoal ash using WDXRF. The sample was presented to theinstrument as a glass bead, and the Compton peak was used formatrix correction. Using synthetic coal ash standards acalibration line with 0.999 coef®cient was established, andthe method was applicable in the range 10±12 000 mg kg21 Gein coal ash. The accuracy of the method was evaluated bycomparison with results attained by ICP-MS, relative differ-ences between the two methods being v10%. The study foundthat, after combustion, Ge was enriched in the ¯y ash ratherthan the bottom ash, so much so that the ¯y ash may well beconsidered as an economical source of Ge.

Two other papers73,74 report the use of XRF for coal and ¯yash analysis, the latter reporting on the use of on-line XRF forS, Ca, Fe and Ti determination and the former detailing the useof EDXRF and WDXRF for assessing the environmentalimpact of coal and ash. This required the samples to becrushed, dried, ground and pressed, further pelletization withboric acid being required for WDXRF. Both papers reportexcellent accuracy and precision.

Laser ablation ICP-MS has been employed as a rapidmethod75 for the determination of various elements present atlow (ppb) concentrations in bituminous coals. Uncerti®ed coalswere used for the calibration standards (representativestandards being one of the major drawbacks of LA-ICP-MS); these were subsequently veri®ed using the South Africancerti®ed coals Sarm 18,19 and 20. A critical analysis of the datashowed that, for many of the elements, the results were bothaccurate and precise.

Pelletization of ashed coal samples was also used in thesuccessful use of rf GD-AES in trace metal analysis.76

However, the evaluation of plasma stability showed that thetemporal pro®le of aluminium decreased with time; this wasattributed to water molecules trapped in the ash. To overcomethis the samples were prepared as a glass bead, similar to thatused in WDXRF analysis.

Silva et al.77 report on the extension of the method reportedin 1999, Pb in coal by slurry sampling GF-AAS, to include Cdand Cu. The particle size was reduced from 45 to 37 mm and thediluent remained as 5% (v/v) HNO3, 0.05% Triton X-100 and10% ethanol. Homogenization was via manual stirring or viathe use of ultrasonic agitation. Reference coals used to evaluatethe method showed a better correlation when the sampleparticle size was reduced to 37 mm.

Three papers discuss various aspects of coal analysis afterpreparing the sample solution via microwave digestion: they aredetailed as follows. Richaud et al.78 found that microwavedigestion in HNO3 of liquefaction extracts prepared fromArgonne Premium Coals and coal pitch tar was a suitablemethod for determining trace metals in the said extractionsolutions by ICP-MS. Sample sizes as small as 3±20 mg wereanalysed. They reported that the trace element distributionfound in the extracts bore little relationship to the correspond-ing distributions in the starting materials. Mossbauer spectro-scopy of the extracts indicated that the high Fe concentrationscorresponded to the presence of organometallic Fe compoundsand not to pyritic Fe. A sequential microwave digestion

method for the determination of sulfate S, pyritic S and organicS in bituminous and sub-bituminous coals with the use of ICP -AES has been reported;79 full details were given. Finallymicrowave digestion was employed in the determination of Hgin coal. FI-CV-AAS gave a detection limit of 20 ng g21 and forFI-CV-ICP-MS the detection limit was 4 ng g21.80

Shiowatana et al.81 report on the use of carbon adsorption andslurry sampling ET-AAS to determine Hg in natural gas liquidand condensate. A 500 ml volume of natural gas liquid wasstirred for 10 min with 0.5 g of activated carbon, which isremoved via ®ltration. After drying in air an accurately weighedmass of carbon was introduced into a pre-weighed amount ofeither 2% boiled tapioca ¯our or 75% glycerol containing 5 mgml21 of Triton X-100, then a homogenized suspension wasprepared using a vortex mixer. From this a 15 ml portion ofslurry was injected into a pyrolytically coated graphite furnacetogether with 5 ml of matrix modi®er (1 mg l21 of Pd). This wasdried at 120 ³C for 10 s, pyrolysed at 250 ³C for 20 s and stepatomized at 1300 ³C. The absorbance was measured at253.7 nm with deuterium background correction. The limitof detection achieved for natural gas liquid was 2 ng ml21,spike recovery of Hg (added as diphenylmercury) was w90%.Comparative results using acid digestion ETAAS and CV-AASwere in good agreement.

2.1.3 Oils. Although trace metal analysis in used oil as usualdominates this section, some papers have concentrated on theanalysis of single elements and have extended much more toalternative techniques to the normally dominant ICP-AES.

Jose Luis Burguera et al.,82 describe the use of an on-lineemulsi®cation FI-ET AAS system to determine Cr in lubricatingoils. A simple quick procedure for the on-line preparation of aone phase emulsion in an FI-ETAAS system is detailed. Theentire system was computer controlled and independent of thespectrometer. A 1 ml plug of sample solution was injected intoa carrier stream of hexane and was subsequently mixed withstreams of 3.8% (m/v) NaCl, 5.0% (v/v) Na dodecylsulfate and5.0% (v/v) sec-butanol. The ¯owing solutions were subject tosoni®cation, which improved the emulsion's stability. TheETAAS programme parameters were also detailed. Thereporter claims that to the best of his knowledge the literaturehas not reported work on w-o-w emulsions for ETAASdeterminations. Good agreement between the certi®ed andfound results for two NIST certi®ed materials was attained.

Sn determination in used oil was also reported;83 here theapplication of fractionary factorial design to the determinationof Sn in lubricating oils by continuous ¯ow HG-AAS isdescribed. Microwave digestion was used to prepare thesample, which included a 4 stage programme. The level ofSn studied was in the range 33±108 mg l21, and in all cases theresults were higher than those obtained by a simple dilution inkerosene.

Langer et al.84 interestingly detail a method for the directanalysis of new and used lubricating oils using ETV-ICP-MS. The sample was introduced into the ETV without dilution,and quanti®cation was carried out via aqueous standards. Theyreport this methodology as being reproducible and reliable.The `frozen drop method', where a drop of oil sample falls ontoa pellet of dry ice, is solidi®ed and then transferred manuallyinto a modi®ed GF, was investigated as an alternative toconventional acid digestion.

Microwave digestion was once again used for the samplepreparation stage for the determination of wear metals in marinelubricating oils.85 A four-stage procedure using nitric acid andhydrogen peroxide is detailed and the reporters claim to havesuccessfully totally digested a larger sample mass than thatrecommended by the manufacturers. They suggest that thisprocedure could be an interesting alternative to classical ashingprocedures. Comparative data with an alternative technique isgiven. The reviewer, however, wonders if this is a viable


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


alternative since the cost of advanced microwave systems is notinsigni®cant and systems are still limited to a relatively lowsample throughput.

A study to determine a possible link between toxic elementspresent in jet engine lubricating oils and two hydraulic ¯uidswith the symptoms (dizziness, nausea, lethargy, etc.) of ¯ightcrews was undertaken.86 ICP-MS was used to determine theelemental concentrations of Mg, Ti, Cr, Mn, Co, Sr, Zn and Win the oils after they were prepared for analysis by one of thefollowing two routes: (1) dissolution in HNO3 in a closed Parrbomb reaction vessel; (2) dissolution in 60% IPA, 1% Triton-100 and USN-membrane desolvation. Differences between theoils and hydraulic ¯uids were observed; however, none of thetoxic elements, which could be related to the symptoms, werefound.

Improvements to XRF instrumentation and methodologyhas meant that used oil analysis reported via this technique ison the increase.

One paper87 reports the work carried out to improve theASTM D4927 (WDXRF) method to extend its coverage to 13elements. The determination of empirical alphas are reportedand subsequently compared to the calculated alphas.

The use of EDXRF to monitor the oil condition of the F404engine on board the F18 weapon system is detailed andcompared with the results of a rotrode atomic emissionsystem;88 the bene®ts of such as system are given.

Pt reforming catalysts are easily poisoned by increased levelsof Pb, hence sensitive analytical procedures are required for Pbin crude oils. In preparation for the analysis by ETAAS, thepyrolysis and atomization characteristics of lead alkylsulfon-ate, lead 4-cyclohexane butyrate, tetraethyllead and lead in fueloil were studied.89 The best procedure is detailed in the paper.The limit of detection from a 20 ml injection was 0.25 ng g21

with a recovery of 85±106%.The disposal of combustion products from waste oils can

have a detrimental impact on the environment. Concerns areraised over the metal and non-metal content of such oils andalso the distribution of metals versus particle size. In this reviewperiod three papers have covered various aspects of wasteanalysis: Study of the distribution of Pb, V, Cr, Ni, Cd, Cu andFe in particles formed from combustion;90 Low leveldetermination of non-metals (e.g., chlorine, bromine, etc.) byICP-AES;91 and Determination of heavy metals and S in wasteoils by EDXRF.92

This year, the papers submitted in this section have shown awider coverage in applications and techniques employed incomparison with the last two review periods.

2.2 Organic chemicals and solvents

2.2.1 Organic chemicals. Electrothermal atomic absorption(ETAAS) has developed into one of the most ef®cienttechniques for the determination of trace elements inbiological, environmental, geological and industrial analysis.Electrothermal vaporization (ETV) is also a useful tool forsample introduction in ICP-AES and ICP-MS, offeringadvantages such as lower sample consumption, high sampletransport ef®ciency and direct analysis of solid samples.However, the formation of refractory carbides in this process,which leads to a suppression of signal, is a signi®cantdisadvantage. The reported comparative studies on chemicalmodi®cation of polytetra¯uoroethylene (PTFE) slurry inconjunction with ETV-ICP-AES and ETAAS93 gave aninteresting insight to the different in¯uences resulting from¯uorination. The addition of PTFE had previously beenreported by the authors; this had con®rmed that ¯uorinationwas an ef®cient method for determining trace refractoryelements, in which the PTFE converted the oxides of analytesinto their volatile ¯uorides at high temperature. The differentin¯uences observed in ETV-ICP-AES and ETAAS were

assigned to the different functions of the graphite furnace inthe two techniques. The formation of ¯uorides enhancedemission signals of the refractory elements, Mo, Cr and Ybsigni®cantly in ETV-ICP-AES, but only Cr in ETAAS. In bothETV-ICP-AAS and ETAAS the addition of PTFE increasedthe ashing maximum temperature of volatile analytes, espe-cially Cd. It can be concluded that the addition of PTFE hasmany bene®ts and the reviewer expects more work to bereported in this area in the future.

Pre-concentration using on-line column techniques coupledwith atomic spectrometry is very important for trace metaldetermination. 8-Hydroxyquinoline (8HQ) has been thoroughlyinvestigated and reported by many as an excellent chelatingagent, showing the best selectivity of the commercial resins.This coupled with the amount of literature available made it agood choice for Howard et al.94 to use as the comparative basefor a new chelating agent, poly-(L-cysteine) (PLC). PLC and8HQ were immobilized on controlled pore glass and used in a¯ow injection system for the separation of Cd, Pb and Cu fromsynthetic sea-water, Co and Ni matrices and CRM sea-water.They reported that both resins quantitatively recovered50 mg l21 Cd and Pb in synthetic sea-water. However, 8HQshowed low recoveries, 2±4% and 40±50% for the separation of50 mg l21 of Cd and Pb, respectively, from a 10 000 ppm excessof Ni and Co. PLC maintained quantitative recoveries. Neither8HQ nor PLC maintained quantitative recoveries for Cu2z.Much more information is detailed in the paper regardingfurther experiments which illustrate the limitations of thesystems plus the extra information available, e.g., stabilityconstants.

A plethora of papers were received during this review period forthe analysis of traditional Chinese medicines (TCMs). Threepapers95±97 detail the determination of arsenic by ICP-MS, twoillustrating the coupling with FI. Two papers98,99 employedsuspension-sampling FAAS for the determination of Mn, andFe, Zn and Ca, respectively. Two further papers100,101 havereported the studies carried out on 10 and 11 different TCMs,respectively, using FAAS.

Atomic spectrometric techniques have been traditionallyused to determine various trace metals in all types of drugs;however, in this review period the metal content has been usedto determine the mechanisms of certain drugs. The simulta-neous determination of Pt and iodine by ICP-MS has been usedto study the mechanism of reaction of diiodoplatinum anti-cancer complexes.102 Samples were diluted in KOH with Te asan internal standard. Improved sensitivity (two-fold) wasattained by the use of the S-option on the ICP-MS system. Theresults indicated that iodide release and different kinetics wereobserved for reactions of diiodo-PtIV and -PtII complexes in lowmolecular weight fractions of reaction mixtures of diiodo-Ptcomplexes and human albumin.

Further work investigated metallodrug±protein interactionsvia the use of size exclusion chromatography coupled with ICP-MS.103 Two Pt and three Ru based drugs were included in thestudy to assess their binding potentials with human serumproteins. Mixtures containing 1.6 mm of Pt based drug or0.1 mM of Ru based drug and serum were incubated at 37 ³C. Atregular intervals sub-samples were taken and diluted 100 foldwith 30 mM Tris hydrochloride buffer of pH 7 and analysed. ASupelco Progel TSK column, with the previously mentionedbuffer as the mobile phase, was used to monitor the proteinbound drug fraction. The column ef¯uent was fed directly intothe ICP-MS instrument and the following isotopes weremonitored: 194Pt, 195Pt, 196Pt and 100Ru, 101Ru, 102Ru. Themethod allowed the kinetics of drug binding to be successfullyinvestigated.

Doped heavy metals as well as those from contaminationhave a signi®cant effect on the sensitivity of ®lm andphotographic papers. The photosensitive layer of ®lms andpapers consists of microscopic grains of silver halide suspended


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


in gelatine; to improve the photographic process the silverhalide emulsions are usually doped with trace amounts of Ptgroup elements. Therefore, extremely sensitive techniques arerequired to determine the low level concentrations of theseelements. Krytek and Heumann104 have used several techni-ques to aid the determination of Ir and Rh. Different sampletreatment procedures were coupled with ICP-MS for thedetermination of Rh and Ir. For Ir, negative thermal ionizationisotope dilution mass spectrometry (NTI-IDMS) and ICP-IDMS were explored, using enriched 191Ir spiked solution. Forall analysis the removal of the silver matrix proved to beessential and for NTI-MS the gelatine matrix was alsoremoved. Because of the similar chemical and physicalnature of Ru and Rh, Ru was used as an internal standardduring matrix separation for the determination of traceamounts of Rh. By determining the 103Rh : 99Ru ratio of theseparated sample reliable results were attained. It wasconcluded that ICP-MS procedures could be used routinelyand Ir and Rh in photographic emulsions were determined inthe 0.5±650 ng g21 range. NTI-IDMS can be applied as anaccurate reference method.

Several papers report the analysis of cosmetics and shampoosfor various trace metals.105±107 The most elaborate technique inuse was the determination of mercury in cosmetics by ¯owinjection cold vapour generation atomic spectrometry with on-line pre-concentration.108 The method involves the acidtreatment of the sample in a focused-microwave digestor, on-line pre-concentration on a C18 column and cold vapourgeneration AFS determination. The method was applied to thetarget analyte at the pg level in different eye cosmetics (i.e., eye-liner, eye shadow, eye pencil), which have a maximumallowable level of 0.007% (m/m) Hg.

The latter method gives a clear illustration of the progressmade in the coupling of various sample preparation andinstrumental techniques together, which enable the trace metalsto be determined in dif®cult matrices.

2.2.2 Solvents. In the previous review there was muchinterest shown in the effects of adding solvents to aqueoussystems to improve the signal intensity, and although thereviewer expected further investigative work to be carried outin this area, no papers were received in this review period.

Solvent extraction for pre-concentration, however, has beendominant. The use of solvent extraction coupled to ETAASappears to be the favoured combination. A detection limit of3.3 ng l21 was achieved for CrVI via the use of this approach.109

The sample was aspirated (5.5.ml) into a FIA manifold(schematic diagram shown in the paper) and merged with areagent stream of MIBK (0.22 ml min21) and 0.065% ammo-nium pyrrolidine dithiocarbamate (0.5 ml min21). The mixturewas passed through a knotted PTFE extraction coil, afterwhich the organic extract was separated by a gravity phaseseparator (diagram given) and delivered (0.1 ml min21) into acollection tube. The collected organic extract (55 ml) wasintroduced via an air¯ow (0.25 ml min21) into a graphite tube.The operation details are given. The calibration graph waslinear from 5 to 600 ng l21, and the methodology enabled asample throughput of 24 samples h21. The method was appliedto waste water and synthetic sea-water.

Two other papers report the use of ®ltration in differentguises after solvent pre-concentration. Taguchi et al.110

describe the determination of copper reactive pesticides inwater after pre-concentration with a solvent soluble membrane.After acidi®cation the samples (200 ml) were treated with 24%diammonium hydrogen citrate (4 ml), 10% ascorbic acid (4 ml)and 2 ml of 40 mM CuSO4 and left to stand for a few minutes.The pH was readjusted to 6 and the solution applied to a mixedcellulose ester membrane. The membrane was washed with20 ml of water containing 1 drop of 0.1 mM methyl violet. Thedyed area was cut out and dissolved in methoxyethanol.

Detection limits in the order of 0.2±0.5 mg l21 in the originalsample were achieved: a novel way to pre-concentrate.

The second paper111 reports the use of solvent extractioncoupled with cobalt(III) oxide collection for the determinationof As in environmental and geological samples. The basics ofthe system were to acidify the sample solutions, mix with KIand extract with benzene, then stir the organic layer with 3 mlof IBMK and 30 ng of cobalt(II) oxide powder. The mixturewas next vacuum ®ltered on a PTFE membrane ®lter. Thecontents of the ®lter were then slurried with water prior toanalysis by ETAAS. A detection limit of 12 mg l21 was achievedwith a calibration linear to 500 mg l21.

The other thrust in the solvent area is the continued use ofmembrane desolvation systems that reduce the solvent loadingon plasma systems. Generally, the more volatile the solvent thebetter the removal capabilities of such systems. Gasoline canthus be aspirated directly into the plasma; under normalconditions this would extinguish the plasma immediately. Theuse of a microporous PTFE membrane desolvator has beenevaluated for the on-line removal of organic solvents tofacilitate the determination of trace contaminants in solventsby ICP-AES.112 Three organic solvents, isopropyl alcohol(IPA), methanol and DMSO, were studied. They report viamonitoring the C I emission a reduction of the solvent by 82±89%. The net intensity of Fe, Al and Cu was increasing.

Akinbo et al.113 experimented with a ¯at sheet desolvator(FSMD). The system enabled the introduction of methanolwithout extinguishing the plasma. The bluish green colour ofthe plasma due to methanol was returned to its original colourby increasing the desolvator counter current gas to 8 ml min21.The maximum emission intensities of analyte signals dependedupon the counter current gas ¯ow rate. For Cl the maximumintensity was observed at 5 ml min21. The FSMD was alsoused as an interface between HPLC and the MIP-AES system.This was demonstrated using 2,6-dichlorobenzene and 5,7-dichlorohydroxyquinoline as analytes.

The next move forward was the use of a double membranedesolvator, (DMD).114 A system coupled to a MCN was builtand tested, using isopropyl alcohol, on both an ICP-AES andan ICP-MS. The DMD enabled a reduction (50%) in the lengthof membrane normally used, with an increase in surface area.The in¯uence of sweep gas was studied and reported.

2.3 Inorganic chemicals and acids

There have been some interesting developments this year whichimpact on inorganic chemicals analysis in industrial applica-tions, particularly in ICP-MS. Elimination and reduction ofspectral interferences using collision cell technology in ICP-MSis becoming a commercial reality as indicated by an increasingnumber of papers which discuss the technique. Direct solidsample analysis remains popular, with innovations in laserdesign and improvements in instrument performance increas-ing the viability of the technique. Several papers this year havefocused on isotope ratio measurements using various massspectrometric techniques. New developments in instrumenta-tion in this area are expanding the range of elements to whichhigh precision isotopic measurements can be applied.

Some interesting applications using electrothermal vapor-ization AAS have been reported this year. A wavelengthmodulation technique has been employed for the measurementof Li isotope ratios, using diode laser ETAAS.115 In this work,the relative absorption sensitivity for 6Li was reduced by tuningthe laser to apply 2f-wavelength modulation (2f-WM) in thecentre of the 6Li D1 ®ne structure component. Conversely, theabsorption sensitivity of 6Li could be increased by tuning themodulation to the maximum in the red wing of the 2f-WM linepro®le. By calculating the 2f-WM line strengths, overlappingabsorption lines could be deconvoluted, thereby facilitating themeasurement of 7Li : 6Li isotope ratios as large as 2000. This


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


work identi®ed a potentially viable alternative for measuring Liisotope ratios, compared to ICP-MS or TIMS, both of whichare adversely affected by large mass discrimination effects inthe mass region of Li.

The use of hydro¯uoric acid to decrease the backgroundabsorption signal caused by sodium chloride in ETAAS hasbeen reported.116 Addition of a small volume of 40 to 80% HFsolution to the samples lead to the formation of NaF duringatomization, which has a much lower absorption signal thanNaCl. The authors reported that addition of HF caused nodamage to the pyrolytic material or the quartz windows of theatomizer.

A number of articles in which ¯ame AAS was used as thedetection system have appeared this year. A study of the releaseof Ni and Cr from stainless steel cooking utensils into foodduring cooking was performed.117 Ingestion of Ni and, to alesser extent, CrVI can exacerbate dermatitis in people who arealready Ni-sensitive. The authors measured Ni and Cr in 11different meals cooked in different grades of stainless steelutensils as well as in glass saucepans. A signi®cant difference inNi and Cr content could be identi®ed between glass andstainless steel utensils, but this difference was found to be lowcompared with the levels of Ni and Cr already contained in thefood. Hence, there was reported to be no bene®t in Ni sensitivepatients switching to glass in place of stainless steel utensils.

A procedure for indirectly measuring Si in cobaltosic oxideby ¯ame AAS has been described.118 A fairly complex samplepreparation procedure was performed involving two recon-stitution and evaporation stages, mixing with ammoniummolybdate and ®nally an organic solvent extraction step.During the procedure, the trace Si was converted to aheteropolymolybdate Si species, which was collected in theorganic extract. The Si was quanti®ed indirectly by measuringMo, facilitating a detection limit for Si of 0.2 mg ml21.

On a more fundamental note, a review on the subject of acidinterference effects on analyte signals in atomic spectrometrywas published this year.119 Acid interference effects arecomplex and their magnitude is dependent on several variables,including nebulizer ¯ow rate, spray chamber geometry andplasma parameters. In the review, the methods which have beendeveloped to overcome such interferences are discussed and astrategy for minimizing these interferences is presented.

Applications of emission detectors feature strongly in theliterature again this year. The use of a microwave plasmadevice, operated with either Ar or an Ar±air mixture, for thedetermination of tetraethyllead, via Pb emission at 283.31 and405.78 nm, has been reported.120 This instrument can beoperated with either air or argon as the carrier gas. Optimumdetection limits (using the more sensitive 405.78 nm emissionline) in the region of 0.02 ppb Pb were reported and theinstrument response was linear over three orders of magnitude.This performance is not as good as can be achieved by ICP-MS,but the instrumentation has the advantage of being simpler andcheaper to purchase and operate. It is likely that the range ofapplications to which this type of instrumentation can beapplied is large, but the small linearity range may be alimitation.

An on-line monitoring system for the determination of boron indichlorosilane, using ICP-AES detection, has been described.121

On-line monitoring of the gas was achieved using a modi®edsampling and gas introduction system. Calibration of thesystem was performed with a mixture of diborane and argon,together with dichlorosilane, using a standard additionsapproach. This procedure offered a detection limit of around0.6 mg B per gram of dichlorosilane, which was suf®cient for theapplication. From a process analysis perspective, it will beinteresting to see if future developments make this type ofinstrumentation viable for on-line analyses.

An elaborate system for the measurement of Ge in zincelectrolytic solutions, using ICP-AES, has been reported this

year.122 Germanium is present in zinc ores and is a problem asit adversely affects the electrodeposition of zinc during there®nement of this metal. The system which was developed wascomprised of an on-line separation stage, followed by hydridegeneration. Germanium in the samples was complexed withHCl (8.5 M), thereby forming GeCl4, which was extracted on-line into xylene. The two liquid phases were separated on-lineand the xylene phase then mixed with NaBH4, dissolved in adimethylformamide±acetic acid mixture, to generate GeH4.For the liquid±liquid separation stage, a gravitational separa-tor and a membrane separator were evaluated. The generatedGeH4 was separated via a gas±liquid separator and transportedto the plasma by an argon stream. Detection limits for Ge of 1and 3 ng ml21 were achieved using the membrane andgravitational separators, respectively. Despite its apparentcomplexity, the procedure was suf®ciently robust for thesuccessful measurement of three real samples, the results ofwhich compared well with those of a routine method.

The use of a parameter related internal standard (PRISM)method for measuring Ni in high salt and high acidity samples,using ICP-OES detection, has been evaluated as an alternativeto conventional internal standardization.123 The PRISMapproach is based on the assumption that the emissionintensity of an analyte signal is affected only by changes inthe excitation temperature of the plasma and changes in thesample introduction ef®ciency from sample to sample. Theauthors used La and Y to monitor the effect of changes in theexcitation temperature and sample introduction ef®ciency,respectively, on Ni emission signals in aqueous samples.Changes in these parameters were simulated by varying theforward power and sample uptake rates, using a factorialanalysis approach. The results of these experiments were usedto derive correction factors for the Ni emission intensity for arange of high acid and high salt matrix samples. This approachwas more ef®cient than conventional internal standardizationfor correcting emission intensities for higher matrix samples,but for lower salt content samples and lower analyteconcentrations there was no discernible difference. Themethod seems to be bene®cial for speci®c applications but, ifthe samples can be diluted, using the conventional internalstandard approach will probably be faster and just as effective.

As has been the case in recent years, ICP-MS has featuredheavily in the literature this year. Of particular interest is thediscussion of applications of collision cell technology to reduce oreliminate certain interferences in ICP-MS. Collision cellsoperate by allowing ions produced in the plasma to collidewith a gas such as He, N2 or ammonia in a pressurized celllocated behind the sampling interface and before the massanalyser. These collisions result in molecular ion dissociationand exchange reactions as well as thermalization of the sampledions. A particular bene®t of collision cell technology is the nearelimination of the 40Ar16Oz interference on 56Fe under normalplasma operating conditions, leading to the possibility ofmeasuring Fe at ppt levels on quadrupole instruments.Interferences on other problematic elements such as K, Caand Se are also signi®cantly reduced. VoÈ llkopf et al. haveapplied a collision cell ICP-MS system to the determination ofK, Ca, Cr, Fe, As and Se at ppt levels in high purity hydrogenperoxide for the semi-conductor industry.124 The authorsfound that ammonia was the most effective collision gas for thisapplication. All the elements of interest could be measuredunder one set of plasma conditions in a single run. Long termstability of the instrument (20 h) was not degraded comparedwith conventional operation. In a related work, the collisioncell ICP-MS instrument was used for the determination of 41elements in high purity HCl, HNO3 (diluted by a factor of 10with water) and de-ionized water.125 Ammonia was used as thecollision gas and was effective in eliminating 40Ar16Oz,40Ar1Hz and 40Ar2z, but not the 40Ar35Clz and 35Cl16Oz

interferences, on 75As and 51V, respectively. In addition, the


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


authors indicated that use of a low K quartz torch and Pt coneswould probably improve the detection limits for K and Ni,respectively. Nonetheless, currently available collision cellinstrumentation is already capable of meeting nearly all thesemiconductor industry's speci®cations. Future developmentsin the technology will very likely be directed towards the use ofother gases or mixtures of gases to eliminate a wider range ofinterferences. It is less likely at present that collision cells willprove to be useful in environmental analyses because ofrecombination reactions such as the formation of CaO in placeof ArO in the cell, when matrix containing samples areanalysed.

Coupling chromatography systems with ICP-MS continuesto be of interest. GoÈessler et al. have used ion chromatographycoupled to ICP-MS to separate and quantify inorganic sulfurspecies, via the 32S16Oz ion signal with the instrument tuned togive high oxide ratios (under cool and hot plasma condi-tions).126 A mobile phase based on NaOH was found to benecessary to generate the required SOz signal. A membranesuppressor system was used to remove Na prior to the ICP-MSmeasurement. Detection limits were in the range from 35 to270 ppb depending on the sulfur species. Signals derived fromsul®de were found to be suppressed for saline samples, undercool plasma conditions, and such samples also reduced theretention time for sul®de. The cause of both effects wasidenti®ed as chloride ions. This method illustrates an interest-ing way of indirectly measuring an element which cannot bemeasured directly with the instrument con®guration used.However, when an oxide signal is used in place of the parention, care must be taken that the oxide formation rate is keptconstant for both standards and matrix containing samplesthroughout the analysis.

New applications of laser ablation ICP-MS continue toappear. An Nd:YAG laser coupled to a quadrupole ICP-MSwas used to measure the major matrix and trace elements inCd±Zn±Te crystals.127 The spatial distribution of a range ofelements across the surface of the material was studied anddepth pro®le experiments were also performed. Using therelative ion signals for the trace and matrix elements, theauthors estimated the relative mass fraction of each element inthe area of the sample analysed. An excimer laser coupled to aquadrupole ICP-MS was used for the determination of minorand trace elements in eight USGS geological referencematerials.128 The samples were fused into pellets withLi2B4O7 as an alternative to a time consuming digestionprocedure. Elements of interest were quanti®ed by externalcalibration with the NIST 612 glass reference material and SiO2

was used as the internal standard. A total of 40 isotopes werequanti®ed down to concentrations as low as 240 ppb in thesolid. The results compared favourably with both XRF andsolution nebulization ICP-MS and illustrated how LA-ICP-MScould be used as a complementary technique in the analysis ofgeological materials. Improvements in laser systems andinstrument design are now making it possible to quantifyelements at ppb levels in the solid. This, coupled with anincreasing range of available solid calibration materials, isstarting to make LA-ICP-MS a viable alternative to eithersolution ICP-MS or the less sensitive XRF technique for arange of analyses.

The development of multi-collector ICP-MS (MC-ICP-MS)over the past few years is leading to an increasing number ofarticles discussing applications of high precision isotope ratiomeasurements for geochronological, nuclear and high accuracyisotopic composition analysis and atomic weight determinationpurposes. A particular MC-ICP-MS article of interest this yearwas a study of the variations in Ca isotopic composition incarbonate materials.129 Under conventional plasma conditions,the very large 40Arz signal prevents measurement of 40Ca and,in addition, interference from Ti on masses 46 and 48 preventssatisfactory data being obtained for these low abundance Ca

isotopes. So, for conventional ICP-MS operation, Ca isotoperatio measurements are practically limited to masses 42, 43 and44. The authors measured the 44Ca : 42Ca ratio in an aqueouscalcium solution and in digested marine and terrestrialcarbonate samples and compared the results with measure-ments of the NIST 915a Calcium Carbonate reference material.Variations in the 44Ca : 42Ca ratio were expressed as d44Ca units(deviations in parts per 1000 from the same ratio in NIST915a). Deviations of up to 0.7½ were observed, which agreedwell with the results of previous studies using TIMS. Thesource of isotopic deviations of Ca between terrestrial andmarine carbonates is believed to be due to fractionation of thelatter during carbonate precipitation from the surrounding sea-water environment. Using cool plasma methodology incombination with multi-collector ICP-MS offers the potentialfor making high precision Ca isotope ratio measurements using40Ca as well, although ionization suppression from the matrixof digested samples could limit the range of application tosimple matrix samples.

Other mass spectrometric methods of detection have beenapplied in a range of applications this year. Boyle et al. usedsecondary ion mass spectrometry (SIMS), together with X-rayphotoelectron spectroscopy, to study impurities in CdS/CdTephotovoltaic cells.130 SIMS was used to quantitativelydetermine 12C, 16O, 34S and 35Cl in the thin ®lm voltaic cells.The distribution pro®les of these isotopes throughout the cellmaterials was also studied. The authors found that the cellswere tolerant to high concentrations of these impurities,indicating that the low-cost, wet chemical method of manu-facture of the devices is potentially viable. Fast atombombardment mass spectrometry (FAB-MS) was used forthe identi®cation and characterization of silicate complexes incalcium chloride solutions.131 Dissolution of silica in aqueousCaCl2 resulted in the formation of several silicate complexes,ranging from the simple monomeric Si(OH)3O2 to large cyclicand linear species such as Si4(OH)3O10Ca3

2. This latter linearcomplex type was not found in solutions of NaCl in which silicahad been dissolved. This was suggested to be due to the factthat Ca2z could assist in forming intra-molecular bondsbetween neighbouring Si-O2 groups, whereas Naz could not.An electrospray ionization mass spectrometry method wasdeveloped for the quantitation of perchlorate in drinking watersamples.132 Determination of perchlorate has become an issuesince this species was discovered in drinking water supplies inthe US. Usually, an ion-chromatography method is used forthe measurement, but chromatographic retention times aloneare not considered to be unique identi®ers in a court of law, andso an additional con®rmatory method such as mass spectro-metry must be applied. However, mass spectrometric methodslack the required sensitivity, and, without prior chromato-graphic separation, quadrupole mass spectrometers lack theresolution required to conclusively identify the perchlorate ionin the presence of other species. The aim of the work was to usetetraalkylammonium cations and sterically hindered, nucleo-philic organic bases to improve selectivity using the electro-spray ionization mass spectrometer without losing sensitivity.Selectivity was achieved by the formation of a stableassociation complex between the base molecule and theperchlorate anion. Using chlorhexidine in methanolic solutionas the base molecule, the authors were able to selectivelydetermine perchlorate (via the complex species at mass 605)down to a lower limit of detection of 10 ppb, which comparedfavourably with the 5 ppb limit achievable with ion chromato-graphic methods.

A study was performed into the isotopic composition andatomic weight of zirconium, using surface ionization massspectrometry.133 In this work, enriched 90Zr and 94Zr mixtureswere used to calibrate the instrument. The calculated atomicweight of Zr was found to agree closely with the currentlyaccepted IUPAC value and may in future be useful in re®ning


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


the current value. Thermal ionization mass spectrometry(TIMS) was used for measurement of the absolute isotopiccomposition and atomic weight of germanium.134 The TIMSinstrument was calibrated using gravimetrically preparedsynthetic mixtures of enriched germanium isotopes (as highpurity oxides). The isotopic composition of Ge in severalterrestrial materials was subsequently measured and noisotopic fractionation was found. An alternative procedurefor measuring the isotopic composition and atomic weight ofGe was reported by Kippardt et al.135 The approach adoptedhere was to convert Ge to GeF4, using both direct ¯uorinationand a wet chemical procedure, before measuring the gaseousproduct by isotope ratio mass spectrometry. A full assessmentof the sources of uncertainty in the measurements, rangingfrom weighing uncertainties to uncertainty in the massdiscrimination measurement, was performed following therecommendations of the ISO/BIPM Guide to the Expression ofUncertainty in Measurement. The results of the measurementswere compared to previously published values in the frame-work of improving the quality of the existing data.

2.4 Nuclear materials

The proportion of the literature devoted to inductively coupledplasma mass spectrometry continues to grow along similar linesto those reviewed in previous years. The determination oflanthanides, actinides and iodine, in terms of both total andisotopic composition, in radioactive wastes and a Ta targetfrom a spallation source, is typical of the variety of tasks thatcan be undertaken using SF-ICP-MS.136 Under optimalconditions, anthropogenic actinides exhibited limits of detec-tion of ca. 0.4±1 fg cm23 and good agreement with a-spectro-metry for isotope ratios as low as 1026. To reduce dose uptaketo the operator and contamination of the instrument, ¯owinjection was employed to allow the analysis of ml volumes ofsolution at the pg cm23 level. Precise isotope ratio measure-ments of ca 0.06% RSD were also demonstrated for favorablecases, e.g., 235U : 238U in NBL 500 (50% enrichment). Thedetermination of 129I was enhanced by vapor generation ofelemental iodine and introduction of that vapor to the SF-ICP-MS via a gas-liquid separator. The determination of isotopicabundances and concentrations of lanthanides in a Taspallation target was enabled by the coupling of HPLC (ionchromatography) and SF-ICP-MS. This was considered to beparticularly advantageous since the large differences in theisotopic abundances of the analytes of interest from naturalabundance lanthanides would generate a large number ofisobaric interferences. Sample introduction studies using highef®ciency nebulizers such as a MicroMist microconcentricnebulizer, a direct injection high ef®ciency nebulizer and anultrasonic nebulizer were reported for applications based onboth quadrupole137 and sector ®eld instruments.138 In the lattercase,138 a shielded torch, ¯ow injection and chemical separa-tions were also applied for ultratrace and isotopic determina-tion of actinides.

Materials control and accountancy (MC&A) is of utmostimportance in the nuclear industry. Analysis, undertaken forthe purposes of MC&A, provides a `Gold Standard' for anylaboratory in terms of accuracy, precision and reliability. Thiscrucial area has seen some development in the period coveredby this review and includes: the certi®cation of a newgeneration of uranium isotopic CRMs,139 multi-collectorICP-MS,140 X-ray ¯uorescence spectrometry,141 improvedTIMS methodology142 and rapid sample preparation forTIMS.143 A number of instrumental and procedural develop-ments were reported in the quest to achieve lower uncertaintiesin the next generation of uranium isotopic CRMs.139 Theseimprovements included: the combined use of very highprecision gas mass spectrometry (UF6) and TIMS, upgradeof TIMS detectors, a multi-stage TIMS instrument capable of

very high abundance sensitivity measurements, production ofnew primary isotopic calibration mixtures, more preciseinstrumental calibration procedures and a new Class 100clean room for sample preparation. The introduction of multi-collector ICP-MS (MC-ICP-MS) instruments is certain to havea dramatic effect upon MC&A measurements. High accuracyand precision measurements of uranium isotope compositionwere obtained using MC-ICP-MS.140 To correct for drift in themass bias correction, Pb or Th was added to the samplesolutions as internal references. This approach allowed thedetermination of major and minor isotopes with a precisioncomparable to benchmark standards. Importantly, this preci-sion could be achieved with a sample throughput that exceededTIMS by a factor of 4±5. Radioisotope excited, transmissioncorrected, K-line XRF was used for U and Pu assay.141 Amixed 57Coz153Gd transmission source was used to correct forvariations in absorption. This correction allows a single pointcalibration to cover the entire desired concentration range upto 300 g dm23. The chemical equilibration of the spike andsample, and an internal evaluation of the mass bias of theinstrumentation, were integral parts of an assessment of TIMSfor Pu accountancy.142 It was concluded that the accuracy andprecision achievable with TIMS was comparable to that of areference method (coulometry) and could be used as one of theanalytical tools for future certi®cation exercises and inter-laboratory studies. The application of extraction chromato-graphy for the determination of U and Pu in spent fuelsolutions by TIMS for MC&A was reported.143 After chemicalequilibration of the tracer and sample, the sample was loadedonto a single UTEVA cartridge, washed to remove ®ssionproducts and a sequential elution program used to producepure Pu and U fractions suitable for TIMS. This rapidseparation reduced overall sample preparation times by afactor of three.

Isotopic analysis to the highest standard of precision andaccuracy, as offered by TIMS or MC-ICP-MS, may not alwaysbe required and more moderate performance may be `®t forpurpose'. Quadrupole ICP-MS provided a rapid and cost-effective means of determining uranium enrichment in aprocessing monitoring role.144 Optimal precision and accuracywas achieved by the use of a single standard. This standard wasmatched closely to the sample in terms of enrichment andconcentration. Similarly, the isotopic homogeneity of auranium metal billet, produced from two feedstocks ofdiffering enrichment, was assessed by Q-ICP-MS.145 Theanalysis was suf®ciently precise to allow an assessment of thehomogeneity of the billet where the aggregate variation in theisotopic composition was about 1%.

Laser induced breakdown spectroscopy was applied to thedetermination of impurities in uranium and plutoniumoxides146 using an optical ®ber system for transmission ofthe laser pulse and collection of the resultant emission. Theinstrumentation was based around a frequency doubled, Q-switched, Nd-YAG laser and a 1 m spectrograph ®tted with aCCD. The plasma was generated in air. Eighteen impurities inUO2 were detected at the 500 mg g21 level and 12 impurities inPuO2 at the 100 mg g21 level. Isotopic analysis of U in UO2 wasperformed by the combination of a laser induced plasma anddiode laser induced atomic ¯uorescence spectrometry.147

Resonant atomic ¯uorescence spectra were obtained by rapidscanning of the diode immediately after each laser samplingevent. Alternatively, time integrated measurements, with theexcitation laser ®xed at a speci®c isotope wavelength, were alsoobtained. Precision and accuracy, for natural abundance U, of5 and 7%, respectively, were achieved. In both cases of theapplication of laser induced plasmas, further re®nement of thetechniques are probably required in terms of limits ofdetection146 and accuracy/precision.147

Micro-analytical techniques, such as secondary ion massspectrometry and electron probe microanalysis, were applied to


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


Table 2 Summary of analyses of chemicals

Element Matrix


PETROLEUM AND PETROLEUM PRODUCTSÐC and H Petroleum liquids AE;GC;L The samples are injected directly onto the column; instrument

optimization is discussed155

Fe, Moand Sn

Petroleum crude AA;F;L After treatment with acids Fe, Mo and Sn are separated from the matrixelements by simultaneous solvent extraction of 5,5'-methylenedisalicylhydroxamic acid complexes from HCl±NaClO4

solution into a Bu Me ketone±tributyl phosphate solution

156

Mn Gasoline AE;GC;L The DB-5-MS column was operated with a 7 psi column head pressurewith He carrier gas. O2 and H2 reagent gases were at 25 psi and 70 psi,respectively. The samples were injected directly

67

Pb Gasoline MS;ICP-ETV;L Isotope ratio was used to determine the source of Pb in blood. It wasfound to be ceramic cookware rather than leaded fuel

64

Pb Gasoline AA;GF;L 5 ml of gasoline and 5 ml HNO3 were added together and irradiated withmicrowave

69

Pb Atmosphericparticles, leadedpetrol, pineneedles

MS;ICP;L The 206Pb : 207Pb ratio was determined by direct analysis in rainwatercollected in Scotland to study the effects of leaded fuel

66

S Coal/petroleum MS;Ð;L Isotope information gathered by MS is investigated, sample preparation isdiscussed

157

Various(6)

Naphtha MS;ICP;L Samples were emulsi®ed with Triton X-100 prior to analysis by ICP-MS. Detection limits of 0.09 and 0.12 mg l21 for Pb and Hg wereachieved

158

Various Petroleumfractions

MS;ICP;L Samples were analysed after four different sample routes including: theform of a burnt gas; micro-emulsions; use of surface active agent; andwith the aid of oxidizing agents. Advantages and disadvantages of themethods are described

71

OILS, FUELS AND CRUDE OIL FRACTIONSÐAs Natural gasoline,

gas condensateAA;GF;L An in situ absorption technique was developed to directly determine

arsenic. Pd alloy was used as the solid absorbent159

Cd, Cu,Pb

Coal AA;GF;L The sample is introduced into the ICP as a slurry, which consisted of5±30 mg of coal (ground) in 1.5 ml of a diluent mixture of 5% (v/v)HNO3, 0.05% Triton-100 and 10% ethanol

77

Cr, Cu,Fe, Pb

Lubricating oils AA;F;L Sample preparation was via a closed vessel microwave digestion system,using HNO3 and H2O2

85

Cr Lubricating oils AA;ETV;L A 1 ml plug of sample was injected into a carrier stream of hexane, mixedwith streams of 3.8% (m/v) NaCl, 5% Na dodecylsulfate and 5% of sec-butanol. An emulsi®ed sub-sample was collected and introduced to thespectrometer

82

Ge Coal XRF;Ð;S The Compton peak was used for matrix matching when developing theXRF method. The samples were presented as fused glass beads

72

Hg Natural gas liquidand condensate

AA;ET;L Activated carbon is used to extract and pre-concentrate the Hg present inthe samples. The sample was presented to the instrument as a slurry

81

Mn Fuel additive AA;DL-HPLC;L Speciation of methylcyclopentadienylmanganese tricarbonyl (MMT) wasachieved by a combination of HPLC with diode laser atomicabsorption spectrometry (DLAA)

68

Pb Crude oil AA;ET;L Organic palladium and palladium±magnesium chemical modi®ers are usedto unify the behavior of lead present in different forms in distillationfractions.

89

Pb Fuel MS;ICP;L A low pressure ICP-MS system was used to determine tetraethyllead infuel. A review of systems coupled together is discussed, e.g., GC-MIP-AE

65

S Diesel oil XRF;Ð;L The evaluation of EDXRF for the determination of S in diesel fuels andthe in¯uence of C/H is reported

160

S Coal AE;ICP;L The samples were digested with microwaves prior to analysis; informationre the different forms of sulfur present was investigated

79

Sn Lubricating oils AA;HG;L 1 g of sample was microwave digested via 4 stages 83V Oil AA;F;L Three sample pre-treatment routes were evaluated: ashing; microwave

digestion; and burning in a bomb calorimeter161

Various(5)

Waste oils AE;ICP;L The analysis of non-metals, e.g., Cl, I, P, using the 130±190 nm region, isreported

91

Various(9)

Aviation engineoils

AE;ICP;L The sample is treated with activated carbon, to reduce the risk of traceelement loss, and then digested with a dry digestion method. Thedigested ash is dissolved in HCl±HNO3 (2 : 1) prior to analysis

162

Various Aviation engineand hydraulicoils

MS;ICP;L Samples were heated overnight in a Parr bomb reaction vessel with 1 mlHNO3; the resulting solutions were analysed directly. Other sampleswere dissolved in a 60% propanol±0.1% Triton mixture and analysedusing a USN membrane desolvator attached to ICP-MS

86

Various Waste oils AA;ET;L Particulate materials were collected via cartridges which separated them into size. Each fraction was digested using HCl±HNO3

163

Various Lubricating oils MS;ICP-ETV;L The sample was injected into the graphite furnace without sample dilutionor it was introduced after freezing and placing into a modi®ed graphitefurnace

164

Various(6)

Coals, lignites and¯y ash

AE,ICP;L The samples were burnt, muf¯ed at 775 ³C and then dissolved in HF 165


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


Table 2 Summary of analyses of chemicals (continued)

Element Matrix


Various Coal AE;GD;L The sample preparation was limited to ashing and pressing the resultantsample into discs. Using glass beads was also evaluated

76

Various(9)

Coal MS;ICP;L Microwave digestion using concentrated nitric acid was a suitablepreparation route for the analysis

78

Various Oil XRF;Ð;L The use of EDXRF for the analysis of used oils is demonstrated andcompared and contrasted to other techniques. No sample pre-treatmentwas necessary

88

Various Oil XRF;Ð;L The use of a compact X-ray ¯uorescence spectrometer to monitor real-time wear metal analysis is described. Sample is introduced form the¯owing stream with no pre-treatment

166

Various Waste engine oil XRF;Ð;S The sample is presented to the XRF as a homogeneous pellet on a mylarbacked aluminium ring

167

Various(17)

Fuel oils MS;ICP;L Microwave digester was used to extract trace elements from a relativelysmall samples mass, 20 mg prior to analysis

168

Various(16)

Wood, coal MS;ICP;L 1-Methyl-2-pyrrolidinone (NMP) was used to extract samples of woodand coal. These underwent further sample preparation before analysis.

169

Various(24)

Fuel oil MS;ICP;L The sample was digested using pressurized closed vessel microwavedigestion. The in¯uence of sample size, reagent composition andduration of heating was studied

170

SOLVENTSÐAs Organic solvents,

winesMS;FI-ICP;L The samples was introduced directly into the FIA system using a MCN

nebulizer into the plasma102

As Geologicalsamples

AE;ICP;L The samples (solids) were digested with a mixture of HNO3, HClO4 andHF (5 : 5 : 3) solution on a hotplate at 230 ³C. The digest wasevaporated to dryness. The solid was dissolved in 10 ml HCl (1z10)and ®ltered. The ®ltrate was mixed with acid and back extracted withbenzene

111

As, Se Drinking water XRF;-;L The samples were extracted with solvent, which were then analysed fortrace metal contamination

171

Cr Waste water,synthetic sea-water

AA;ET;L The use of solvent extraction as a preconcentration technique isdemonstrated to achieve detection limits down to 3.3 mg l21

109

Ca, Cr,Mn

Isopropyl alcohol(IPA)

AE;ICP;L The use of a double membrane desolvator for the analysis of IPA isdescribed

114

Ru Bittern AA;GF;L The sample was extracted with 10 mM bromothymol blue and 50 mM 18-crown-6. The organic phase was analysed via GFAA

172

Various Organic solutions AE;MIP;L A ¯at sheet membrane desolvator was coupled to a MIP-AE for theanalysis. No sample preparation was required

113

Various DMSO, IPA,methanol

AE;ICP;L A microporous PTFE membrane desolvator was built and evaluated forthe on-line removal of organic solvents, the samples were introduceddirectly

112

ORGANIC CHEMICALSÐAl, Ca,

Fe, MgSteel solid solution AE;ICP;L The method includes low temperature electrolysis using an electrolyte

solution containing tetramethylammonium chloride, triethanolamine,glycerol, methanol or the latter substituted by ethylglycerol, absoluteethanol. The elements are separated by liquid chromatography

173

AsV, AsIII, organoarsenicspecies

Aqueous solutions XRF;Ð;SAsV, AsIII, dimethylarsinic acid (DMAA) and phenylarsonic acid

(PAS)were separated via the use of various activated carbon species.PAS was separated using V-loaded activated C, AsV was collected onLa-loaded C. AsIII was separated via co-precipitation with ammoniumpyrrolidine dithiocarbamate, the precipitate being adsorbed onactivated C, and ®nally DMAA was collected on Zr-loaded C. Thevarious solid fractions were then analysed by ED-XRF

174

Arsenic(sp)andvarious

Chinese medicine MS;ICP;L The samples were digested via conventional wet oxidation and microwavedigestion using combination of HNO3±HClO4, HNO3±H2O2

96

Au Rock AE;ICP;L The rock extract was mixed with HCl to a ®nal concentration of 0.1 M,

1 mM malachite green and 1±3 ml of 20% naphthalene solution inacetone and the mixture ®ltered

175

13C Organic andinorganicmaterials

RM-MS;GC;G Carbonaceous compounds volatized by a laser are quantitativelyconverted to CO2 gas by a combustion furnace. The gases are swept byHe carrier gas into a GC prior to their determination by isotopemonitoring mass spectrometer (IM-MS)

176

Cd, Pb Chinese crudedrugs

AA;GF;L The samples were digested with 3 ml of concentrated HNO3 177

Co Cobaltmesoporphyrindrug

AA;F;L The drug (100 ml) was mixed with 1% Triton-100 (10 ml) prior to analysis 178

Cr Gelatine AA;ETV;L No sample pre-treatment was necessary 179Cr, K,

Na, NiChinese medicine AA;F;L 11 Chinese medicines were analysed following digestion with HNO3 and

HClO4 Their possible effects in the therapy of coronary heart diseasesare discussed

101


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online



Element Matrix


Cr, Mo,Yb

Biological,environmental,high puritysamples

AE;ETV-ICP;LAA;ET;L

The in¯uence of PTFE slurry on the refractory elements in ETV-ICP-AEand ETAA is reported

93

Cu, Mn Single cell protein,cod muscle,freeze driedanimal blood

AA;ETV;L A PTFE knotted reactor was pre-coated with 1-phenyl-3-methyl-4-benzoylpyrazol-5-one and a portion of test solution was injected intothe carrier stream and passed through the reactor for 15 s. Theabsorbed chelates were eluted with methanol which was injecteddirectly into a pyrolytically coated graphite tube for analysis. Thedetection limits for Cu and Mn were 5.7 and 5 ng l21, respectively

180

Hg Cosmetics AFS;CV;L The method involves the acid treatment of the sample in a focused-microwave digester and on-line pre-concentration on a C18 column

108

I Glacial acetic acid MS;ICP;L In was added to the diluted samples as an internal standard and thereduction in memory effect of I in glacial acetic was studied

181

I, Pt Diiodoplatinumanti-cancercomplexes

MS;ICP;L Samples were diluted in KOH containing Te as the internal standard 102

Ir, Rh Photographicemulsions

MS;ICP;LMS;NTI-ID;L

The silver matrix was removed by dissolving the emulsions inconcentrated ammonia solution; for the NTI-IDMS the gelatine matrixof the emulsion was also removed

104

Mn Chinese medicinalherbs

AA;F;L The samples were dried and pulverized to 160 mesh, and 1.5 g wassuspended in aqueous 1.5 g l21 agar. The suspension was stable for10 min

98

Ni, Pb, V Xylem sap TXRF;Ð;L The effect on organic acid transport in xylem sap of Pb, Ni and V wasstudied. After the introduction of various nutrients into the soil, threeorganic acids of the Krebs cycle were measured by RP-HPLC.Simultaneously, the heavy metal content was determined by TXRF

182

Organ-otin,organo-arseniccom-pounds

Aqueoussolutions

MS;HPLC-ICP;L Solid phase extraction (SPME) was used to extract ionic organotin andorganoarsenic without derivatization

183

Pt, Ru Drugs MS;GPC-ICP;L The Pt based or Ru based drugs were incubated at 37 ³C and regularsamples were taken for analysis. The sub-samples were diluted 6100with 30 mM Tris hydrochloride buffer and analysed. GPC columns wereused to obtain a more detailed characterization of the protein±drugspecies

103

Se Shampoo AFS,GF;L The samples are digested using microwave digestion and reduced viacontinual derivatization (hydride formation)

107

Si Organic matrices GEXRF;Ð;S The sample was deposited on an optically ¯at carrier on an air cooledrotating table ready for irradiation

184

Tl Waste water, freshwater

AA;ET;L The sample was passed through a tribuyl phosphate extraction resin aftertreatment with FeCl3 (30 mg l21) and H2O2 and heating. The Tl waseluted off the column with 0.25% ammonium sul®te and 0.5% ascorbicacid solution. Limit of detection obtained was 3 mg l21

185

TrimethylSe

Urine MS;MIP;L The urine was passed through various columns prior to analysis by MIP-MS. They included ODS GH-C18, pre-concentration column, anionexchange resin IC-C75 and, ®nally, an Asahipac GS-220HQ column

186

Various(32)

High purity metal-organiccompounds

AE;ICP;L Trimethylgallium was decomposed slowly at low temperature without theaddition of oxide prior to analysis. 32 elements were determined withdetection limits of y1 mg g21 being reported

187

Various(73)

Heroin MS;ICP;L ICP-MS data (73) elements was used to ®ngerprint heroin from varioussources

188

Various(6)

Drugs AA;GF;LTRXRF;Ð;L

An iminodiacetic acid cellulose (IDAEC) column was used for pre-concentration of the elements. CrIII and CrVI were separated usingIDEAC and anion exchanger diethylaminoethyl (DE) cellulose

189

Various Chinese medicines AA;F;L The samples were carbonized and ashed at 550 ³C and the residue wasdissolved in HNO3 and HCl

100

Various Tobacco AA;F;L Tobacco was soaked overnight with HNO3 in a sealed phial. The extractwas evaporated with HClO4 to near dryness and the residue wasdiluted to 25 ml

190

Various Fluorcarbon resin AA;GF;L The sample was placed on a Si wafer and decomposed at 550 ³C in air.The surface layer of the wafer was etched with HF±HNO3 and theetching solution analysed

191

Various Amberlite XAD-7functionalizedwithchromotropicacid

AA;F;L The paper details the study to assess the performance of the new polymermatrix

192

W Drugs AE;ICP;LMS,ICP;L

A portion of sample was mixed with concentrated nitric acid±H2O (4 : 1) 193


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online



Element Matrix


INORGANIC CHEMICALS AND ACIDSÐAg Road salt AA;ETA;L Samples dissolved in water. Ag preconcentrated and separated from the

salt matrix by co-precipitation with Co pyrrolidinedithiocarbamate,followed by re-solubilization

194

Al Moltengermanium

MS;Ð;S Germanium samples ablated with Nd : YAG laser to melt the surface. Aldiffusion through the molten Ge studied using SIMS

195

Al Aluminiumchlorohydrate(ACH)

AMS;Ð;L ACH labelled with 26Al prepared to study Al absorption from the use ofanti-perspirants. Sample fractionated using gel ®ltration and fractionsproduced were studied for 26Al using accelerator mass spectrometry

196

Al Ferrosilicon AE;ICP;L Sample digested with a HNO3±HF±HClO4 mixture, evaporated to neardryness, then reconstituted with HCl and H2O

197

As Hydrogenperoxide,ammonia andwater solutions

MS;ICP;L Samples acidi®ed with HNO3 198

As Antimony trioxide HG-AFS;Ð;G Sample converted on-line to SbH3. Arsenic simultaneously converted toAsH3. Hydrides passed through KMnO4 solution where SbH3

decomposes much faster than AsH3. Remaining AsH3 passed intodetector

199

As andSb

Aqueous solutions AA;ETA;L Samples were mixed with Pd and Ir chemical modi®ers and a study madeof the effect of these modi®ers on the measurement of As and Sb

200

As and V Airborne matterreferencematerials

MS;ICP;L Samples digested using a HNO3±H2O2±HF mixture in a high pressuredigestion system

201

Au and Si Gold silicide MS;Ð;S Gold coated onto Si substrate and annealed under vacuum at 363 ³C toform gold silicide. Unreacted gold removed with aqua regia; goldsilicide layer studied using SIMS

202

C, Ge, Sand Si

Toxic hydridegases

AE;Ð;G No sample pre-treatment required. Gas chromatographic procedure usedto separate gaseous impurities of interest prior to detection

203

Ce K3Li2Nb5O15

crystalsMS;ICP;L Samples digested on a hotplate with a H2SO4±H2O2 mixture, then diluted

with water204

Cl Aqueous solutions MS;Ð;G Cl2 and inorganic chloramines separated from aqueous solution using a¯ow-through membrane introduction system coupled to the massspectrometer

205

Cl, Brand I

Aqueous solutions AE;ICP;L No sample pre-treatment required 206

Co XF-210phosphono-aciddirt preventingagent

AA;F;L Sample digested with HNO3±HClO4 mixture. Digest evaporated to 0.5 ml,then diluted to 10 ml with water

207

Co, Feand Ni

Lithium carbonateand potassiumcarbonate melts

AA;F;L Sample (1 g) dissolved in concentrated HNO3 (3 ml), next diluted to 50 mland then aspirated directly into the instrument

208

Cr Tannery wastewater

AE;ICP;L Samples were ®rst digested with a HNO3±H2SO4 mixture, then KMnO4

was added to convert CrIII to CrVI in the form of Cr2O722

209

Cu, Feand Ni

Caustic soda AA;F;L Sample dissolved in concentrated HCl (to pH 2). Ethanolicphenolphthalein (1 drop) added, solution diluted and puri®ed NaOHadded (slight excess). Samples introduced to instrument via a ¯owinjection manifold

210

Er andNd

Bismuth telluriteoptical crystals

AA;ETA;L Samples were dissolved with concentrated HCl and mixed with a chemicalmodi®er (triammonium citrate)

211

Fe and Ni Carbon monoxide FT-IR;Ð;G None performed. Fe and Ni carbonyls were measured and quanti®edagainst in-house prepared standards

212

I Glacial acetic acid MS;ICP;L Samples were diluted 1 : 3 with water, spiked with In as internal standardand introduced to the instrument using ¯ow injection, with anammonium hydroxide carrier stream. Standard additions used forquanti®cation

181

I Calcium iodidetablets

AE;ICP;L Sample dissolved in water. HClO4 and H2O2 were added (precipitateformed) and the supernatant solution aspirated directly into theinstrument

213

N Propionibacteria MS;Ð;G Propionibacteria was cultivated in a yeast extract lactate medium for 3 d.A portion of the culture was mixed with 14N and 15N-enriched KNO3.The 15NO and 14NO formed were passed directly into the massspectrometer

214

Ni Alkali metal salts AE;ICP;L Aqueous solutions of the salts were mixed with hexamine buffer andpassed through an Amberlite XAD-2 column loaded with 1-(2-pyridazol)-2-naphthol. The Ni chelate so formed was eluted with HCland analysed off-line

215

Pb Table salt AA;F;L Samples dissolved in dilute HNO3. Solution buffered to pH 4, thenAPDC added. The chelates formed were extracted into IBMK, thenback extracted into dilute HCl

216

S Gaseous samples XRF;Ð;G Samples passed through a ¯ow cell containing a Be ®lm. The ®lm wasirradiated with the X-ray source and S emission from the sample¯owing through it detected

217


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online



Element Matrix


Se Table salt AA;F;G Samples dissolved in water, then mixed with HCl and NaBH4 to produceH2Se, which was then passed into the detector

218

Si Silicon dioxide onsilicon substrate

XPS;Ð;S No sample pre-treatment required 219

Si Airborne matter MS;LA-ICP;S Airborne particulates collected on PTFE membrane ®lters before directlaser ablation of the ®lters. Data compared with XRF results

220

Tl Caesium iodidecrystals

AA;ETA;L Powdered samples were dissolved in water. Aqueous NH3 was added,then the sample was mixed with Pd and Mg(NO3)2 chemical modi®ers

221

Zn Zinc phosphatecoated steel

XRF;Ð;S No sample pre-treatment performed 222

Zn Nickel electrolyte AA;F;L Sample introduced via a ¯ow injection manifold onto a strongly basicanion exchange column. Column eluted with water and eluate directedinto the instrument

223

Various Chemical gradepotassium salts

AA;F;L Sample dissolved in dilute HNO3, then buffered and mixed with achelating agent. Metal chelates collected on Amberlite XAD4 resin,then eluted, evaporated to dryness and ®nally reconstituted with 1 M

HNO3

224

Various Sodium chloride AA;F;L Samples dissolved and diluted in water. Main focus of work was onoptimizing the FAA to minimize interference effects

225

Various Hydrogenperoxide

MS;ICP;L Samples analysed directly using a standard additions approach 226

Various Barium titanatepowders

MS;ICP;L Samples digested with HCl and a few drops of H2O2, then diluted withwater

227

Various Sediments MS;ICP;L Dried samples digested ®rst with XeF2 at high temperature and pressure,then using aqua regia. Digests then diluted with water

228

Various Inorganic salts MS;ICP;L Samples were injected into a carrier stream of ammonium acetate bufferand passed through Dionex Metpac CC-1 chelating resin columns.Trace elements were retained, then eluted with dilute acid and analysedoff-line

229

Various Wood samplesimpregnatedwith inorganicpreservatives

AE;Laser inducedemission;S

No sample pre-treatment required. Nd:YAG laser focused onto thesample and pulsed for 7 ms. Plasma spark formed from which analyteswere measured by their emission spectra

230

Various Osmium powder AE;ICP;L Sample heated with HNO3 in a distillation ¯ask. Os matrix removed asoxide vapour (trapped in 10% NaOH solution). Sample diluted andmeasured directly

231

Various Trimethylgallium AE;ICP;L No sample pre-treatment required 232NUCLEAR MATERIALSÐ137Cs Micro-particles MS;LI;S Laser desorption and ionization followed by mass analysis in ion trap 233Cs

isotopesWaste U and

MOX fuelMS;IC-ICP;L Cs isotopes determined using on-line ion chromatography coupled to

ICP-MS. Sample injection~200 ml, column~CS5 cation exchange(Dionex), eluent~1 M nitric acid, LOD~16 pg g21. Quanti®cation byisotope dilution using natural abundance Cs spike

234

Er z Erisotopes

Er doped, highenrichment Mo±UO2 fuel

MS;TI, GD-MS;- Double spike ID using 167Er and 233U with chemical separation prior toTIMS. Direct solids analysis using GD-MS with calibration against in-house standards

235

Pu z Puisotopes

Algae, sediments,soils and lichens

MS;HR-ICP;L Spiked with 242Pu tracer, dry ashed at 500 ³C, ash taken up in multi-stagedigestion with aqua regia, HCl and nitric acids. Pu separated on AG1-X4 anion exchange resin

236

Pu z Puisotopes

Environmentalmaterials

MS;ICP;L Sample spiked with 242Pu tracer, ash extracted 3 times with boiling 8 M

nitric acid. Combined extracts taken to incipient dryness, re-dissolvedin nitric acid and diluted with water to give ®nal nitric acidconcentration of either 2 or 8 M, NaNO2 added to oxidize Pu to PuIV.Analyte separated on either AG1-X4 or TEVA and eluted with eitherNH4I or quinol. Eluate taken to dryness, residue taken back up in 4%v/v nitric acid, Bi added as internal standard and whole made up to5 cm3. LOD~0.05 mBq cm23 (239Pu) and 0.17 mB cm23 (240Pu) or0.02 pg cm23. Derived 239Puz240Pu value agreed with CRMs

237

Puisotopes

Environmental MS;ICP, SF;L After digestion, on-line, sequential separation of Pu using Sr-SPEC andTEVA-SPEC extraction chromatography resins automated using`PrepLab'. Sample introduction to ICP-MS via a CETAC 6000desolvating MCN. LOD~9 fg g21

238

Pudau-ghters

Pu MS;TI;Ð Age determination of Pu material 239

Pu, Sr, Y Precipitates frombrine storagesolutions

XRF;ED;SmXRF;ED;S

Elemental mapping and bulk analysis 240

226Ra Mineral waters MS;ICP,SF;L Pre-concentrated on cation exchange resin. Eluate taken to dryness,digested with HNO3 (1 cm3, 1.1 M), diluted with water. MS in low-resolution mode, conventional pneumatic nebulization, recoveries~98±102%, LOD~0.01 pg dm23 (500 cm3 aliquot). LOD with CETACMCN 6000~0.004 01 pg dm23 (500 cm3 aliquot)

241

Tc Environmental MS;ICP;L Bulk of matrix removed by evaporation/precipitation. Rudecontamination via TEVA

242


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


the examination of radioactive particles148 and melted fuelassemblies.149 Particles in soils, swipes and forensic sampleswere examined by SIMS and identi®ed qualitatively in terms ofU and Pu content and the isotopic composition. The lattercould be determined with a typical accuracy and precision of0.5%. Statistically meaningful results could be obtained from aspecimen containing 104 atoms m23 of U contained in particlesweighing a few picograms. Fuel assemblies were irradiated to aburn-up of 23 GWd/tU, heated by ®ssion power to about2500 ³C and the resultant melted bundles sectioned for opticalmicroscopy and EPMA.149 At mid-height, the bundle hadcollapsed forming a void and the molten material had pooled.This solidi®ed melt was a solid solution resulting from thefusion of the UO2 fuel and Zircalloy cladding. Oxide andmetallic inclusions were observed. The former were rich in Feand Cr, the latter in Ni and contained small amounts of Mo,Tc, Ru and Pd.

Resonance ionization and accelerator mass spectrometrycontinue to attract interest. The determination of 129I in airby means of accelerator mass spectrometry offers detectionlimits of 104 atoms m23.150 Air (350 m3) was sampled by meansof charcoal ®lters. A tracer was added to the charcoal, beforeextraction of the analyte of interest, by slurrying the charcoalwith water, adding a stable tracer (NaI), treatment with nitricacid and sodium nitrite to convert the tracer to iodine andequilibration of the tracer with the solid. The charcoal was

separated, washed and dried, and the uptake of the tracerestimated by determination of iodine, as iodide, in thesupernatant (ion chromatography). The iodine was extractedfrom the charcoal by extraction with aqueous NaOH±NaHSO3

and puri®ed by multiple extractions and back extractions ofelemental iodine into chloroform. Finally, the source wasprepared by precipitation as AgI and introduced to theAMS. The status of AMS was reviewed brie¯y with anemphasis on recent technology developments.151 Similarly, thestatus of the TANDAR AMS facility (Argentina) wasreviewed, recent improvements and the focus of the currentwork on chlorine-36 and Ni beams described.152 Themeasurement of Pu and U using resonance ionization time-of-¯ight mass spectrometry, and some of the limitations of thetechnique, was discussed.151 Samples were vaporized from a Rh®lament and ionized by a single color, 3-photon process. Twomajor limitations were identi®ed. Firstly, the chemistry of theion source yielded both atomic and molecular species that ledto a variety of interferences. Secondly, the low detectionef®ciency of the instrumentation due to a combination of acontinuous atom beam and a pulsed ionization laser was noted.The relative merits of different ®lament preparation schemeswere discussed and a technique proposed that addressed thelow duty cycle of the instrumentation. Ionization schemes forthe measurement of strontium-90 by diode based RIMS weredescribed.153 Double and triple resonance schemes, used in


Element Matrix


99Tc Biological MS;ICP;L Chemical separation of Tc followed by mass spectrometry 243230Th,

234U,235U

Marine sediments ICP; MS, SF, ID;L

HF±HClO4 or Na peroxide fusion. Analytes separated on an anionexchange column. MS resolution~4430, yielded 230/232 abundancesensitivity~561027. 229Th and 233U spikes used for quanti®cation

245

233U THOREX processsolutions

AE;HR-ICP;L Th separated by precipitation as oxalate from 1 M nitric acid. 233Udetermined in supernatant by high-resolution spectrometry at the UII

385.96 nm line

246

Uisotopes

CRM MS;HR-ICP;L Accuracy better than 0.2% 247

234U/238U Natural watersand carbonates

MS;ICP;L U co-precipitated from sea-waters on Fe carrier, separated onTEVA. Carbonates decomposed with nitric acid. Internal massdiscrimination correction based upon 191Ir40Arz/193Ir40Arz

248

U, Am,Cm

Spent fuel MS;ICP;LMS;TIMS;L

U separated from fuel solution (8 M HNO3) by anion exchange and with3 M HNO3. U fraction taken to dryness, re-constituted with 0.2 M

HNO3 and subjected to ICP-MS and TIMS. Unretained fraction,containing Am and Cm taken to dryness, reconstituted and separatedon a 5 mm Nucleosil SA column with an eluent of 2-hydroxy-2-methylbutyric acid at pH 4.1 with on-line a-spectrometry. Isotopiccomposition of Am and Cm fractions determined using double spike,isotope dilution methodology

249

U, Pu Calcites andbioassay

MS;ICP;L LOD for 244Pu~0.1 fg cm23 using an ultrasonic nebulizer 250

U, Th Waters MS;ETV-ICP;L Chelation pre-concentration followed by ETV-ICP-MS. LOD~24 pg (U),60 pg (TH). LODs determined by blanks

251

U, Th Waters and pineneedles

MS;ETV-ICP;L On-line matrix removal. Various sample preparation techniques applied topine needles, wet ashing, dry ashing and Li metaborate fusion

252

U, Th, Puisotopes

Environmentaland wastes

MS;ICP;L Cross ¯ow and microconcentric nebulizers compared. External precisionfor NBL 050 at 1 ng cm23 U~0.05% RSD

253

Various Reactor grade U AE;ICP;L Uranium oxide (Ä2.4 g) dissolved in minimum volume of 50% v/v nitricacid, taken to dryness and reconstituted in 50% v/v HCl. Analytescomplexed with 1,2 diaminocyclohexane-NNN'N'-tetraacetic acid and1,10-phenanthroline and U precipitated as hydroxide by addition ofexcess NH4OH. Sample ®ltered, washed with dilute NH4OH,supernatant acidi®ed and made up to volume (50 cm3). Recoveriesw90%

254

Various(Na±Pb)

U3O8 XRF;Ð;S Single element LOD 10±20 ppm. Measured at peak (50 s) and 2background positions (2650 s)

255

93Zr,107Pd,135Cs

Wastes MS;ETV-ICP;L Solvent extraction and chromatographic separation methods described 256

aHy indicates hydride and S, L, G and Sl signify solid, liquid, gaseous or slurry sample introduction, respectively. Other abbreviations arelisted elsewhere.


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


combination with single mode diode lasers, provided a highdegree of optical selectivity. It was suggested that a tripleresonance scheme, in conjunction with mass spectrometry,should produce a system with suf®cient abundance sensitivityto allow measurement of 90Sr at background environmentallevels. The application of multi-step, cw-RIMS to odd isotopesis usually hampered by hyper®ne structure.154 The splitting ofthe transition strength leads to lower ionization ef®ciencies andlarge uncertainties in isotopic ratio measurements. The use ofappropriate optical pumping schemes overcomes these pro-blems and allows the determination of 41Ca abundances using adouble-resonance, three photon ionization in a collimatedatomic beam combined with quadrupole mass spectrometry.

3 Advanced materials

3.1 Polymeric materials and composites

The results for two comparisons (`round-robins') of anti-fouling257 and lead-based paints258 were reported. The formerwas concerned with a draft procedure for Cu leach rates (ISO/DIS 15181-1,2) and the latter with a ®eld study of portabletechnologies. Differences in the Cu leach rates were notattributed to either analytical methodology or to the physicalapplication of the paints.257 The ®eld study concluded thatchemical test kits were not effective in distinguishing lead-basedpaints but portable XRF instruments, under certain circum-stances, were effective for this task. Secondary ion massspectrometry was used to map the relative resistance ofautomotive paints to photo-oxidation.259 Paint systems wereexposed to UV light and heat in an 18O2 atmosphere and theresultant 18O-labelled products imaged using SIMS. These18O2 maps matched the expected effects of various additives onthe photo-oxidation resistance of the various paint systems.

The use of X-ray spectrometry in the study of ®ne art andarchaeological artefacts is a fascinating area of analyticalatomic spectroscopy. Conventional XRF can be used toidentify pigments,260±263 e.g., identi®cation of blue pigmentsderived from either mineral or synthetic routes on Bronze-Agewall paintings from Greece and Cyprus.262 Simple identi®ca-tion of pigments may not provide suf®cient evidence for a fullcharacterization of a painting but the arrangement andsequence of paint layers is considered to be a distinguishingquality of an artistic studio or even an individual painter. Thisinformation can be derived from proton induced X-rayemission260,262 or grazing emission X-ray ¯uorescence spectro-metry.

Forensic analysis can be considered as the direct ancestor ofthe study of ®ne art and archaeological artefacts by analyticalatomic spectroscopy. The determination of trace elementpro®les was used to distinguish between plastic garbagesacks of nominally the same colour.264 After dissolution inHNO3±H2O2, the trace element pro®le of the polymers wasdetermined by ICP-MS. Lead isotope ratios were alsodetermined and found to be indicative of products thatcontained signi®cant levels of Pb based additives, e.g.,pigments. These approaches were considered to providesuf®cient discrimination of the various products to be usefulfor evidentiary purposes. However, an attempt to extend thisapproach to polyethylene cling ®lms was not successful due tothe low intrinsic trace element content of these products.

3.2 Semiconductor and conducting materials

There have been many reports this year on the analysis of siliconand GaAs wafers for trace element contaminants and dopants.The determination of ultra-trace germanium on silicon wafersby HF acid vapour decomposition-microconcentric nebuliza-tion-ICP-MS has been reported.265 This analysis is importantas there is some evidence that there can be cross contamination

from Ge in Si devices as both SiGe and Si devices can be madeon the same Si wafer, using the same process. Using nitric acidas an oxidizer recovery solution the authors adopted aconventional HF vapour decomposition method. Themethod revolved around the use of the MCN nebulizer,which in turn enhanced the sensitivity and precision of the ICP-MS detection but also allowed the minimization of the samplevolume required for analysis. Detection limits were 13 pg ml21

Ge for 0.5 ml recovery solution and 36108 atoms cm22 for a 6inch wafer. RSDs were in the range of v3% for a 5 ng ml21 Gestandard solution.

The oxidation and carbon contamination of GaAs wettreatments has been studied by XPS, Auger electron spectro-scopy and SIMS.266 Treatments studied include a variety ofcleaning and etching pretreatment procedures prior to immer-sion in either (NH4)2S, Na2S aqueous solutions or S2Cl2solution in CH2Cl2. It was found that S passivation removessurface oxide and minimizes C contamination in the surfacestreated in (NH4)2S and S2Cl2. Pretreatment in basic solutionsshowed signi®cantly lower O and C levels than GaAs treatedwith anionic solutions. The authors also state that surfacepretreatment performed ex-situ showed a higher risk of surfacecontamination prior to S passivation.

The comparison of shallow depth pro®les of cobalt implantedsilicon wafers as determined by total re¯ection XRF analysis andRutherford backscattering spectrometry (RBS) after repeatedstrati®ed etching has been described over two papers.267,268 Anovel method which combines a stepwise wet-chemical etchingof an implanted wafer with total re¯ection XRF was comparedto a traditional RBS method on prepared samples with 50±150 nm Co layers. A rectangular section of Si wafer wasoxidized by treatment with 30% H2O2 for 40 min at650 ³C. Then, 50 ml of HF was pipetted onto the wafer and,after the surface layer had been dissolved, the acid solution wastransferred to a Plexiglas carrier and Se added as an internalstandard. The mixture was then evaporated under an IR lampand analysed by XRF. Depth resolution was 0.6 nm at best andthe limit of detection 0.01% or 461018 Co atoms cm23 for awafer sample 3.4 cm2 area. The characteristic parameters of thepro®les, e.g., concentration and depth at the maximum, meandepth, FWHM and total dose, showed a relative deviation ofonly 4±6% between both methods.

The peak concentration of nitrogen implanted into a Si waferhas been determined by the in-situ internal standard implanta-tion of 14Nz followed by the SIMS depth pro®le analysis of30Si14N2.269 As an internal standard, the N ions with a known¯uence were directly implanted into the sample using a SIMSinstrument. The depth pro®le of 30Si14N2 was then measured.The actual concentration of the N was then evaluated from themeasured DRp, and the ion intensity for each peak. Theestimated concentration was in good agreement with the actualconcentration and the depth pro®les were also compared to thetheoretical ones.

The spark source mass spectrometric (SSMS) assessment ofboron and nitrogen270 concentrations in crystalline GaAs has beendescribed. The MS instrumentation incorporated GaAs sampleelectrodes (15 mm, cross-section up to 464 mm) and aMattauch±Herzog ion focusing system for simultaneous multi-element detection by Q plate. A detection limit of4.461013 cm23 was achieved for both elements. The SSMSmethod was also used as a reference method for the calibrationof FTIR analysis of B and N in GaAs after comparison withTIMS for the reference determination of B. The method wasfurther modi®ed for the analysis of C,271 again comparing toFTIR data. For C, a detection limit of 1.461013 cm23 wasachieved by SSMS. The method is being further evaluated forseveral other elements to assess the suitability of SSMS as areliable reference method for the analysis of GaAs. The sameauthors using this technique for C found a strictly linear relationto the total chemical C concentration as measured by


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


SSMS.272 By using charged particle activation analysis as areference method for C, a new calibration factorf77~(7.2¡0.2)61015 cm21 for the absorption integral at 77 Kwas derived. Based on the temperature dependence of theabsorption, the authors arrived at a calibration factorf300~(7.5¡0.5)61015 cm21 for room temperature measure-ment.

The quantitative SIMS analysis of impurities in GeN andAlxGa12xN ®lms using molecular ions MCsz and MCs2

z

(M~element to be determined) has been reported.273 It wasfound that under Cs bombardment the MCs2

z ions had alarger ion yield than the MCsz ions when M was electro-negative. Application of these molecular ions has made itpossible for the analysis of both electropositive and electro-negative elements in a single run. It was also found that thesemolecular ions minimized matrix effects in the AlxGa12xN ®lmmatrix. The authors postulate that these molecular ions areformed by recombination processes in which sputtered neutralspecies (M and/or MCs) combine with Csz ions.

3.3 Glasses

There are two clear themes among the reports covered by thisreview. Firstly, the application of surface analysis techniquesfor elemental mapping and depth pro®ling, and secondly, theapplication of elemental analysis for archeological and forensicinvestigation of glasses.

A variety of techniques were reported for elemental mappingand depth pro®ling. These included: radiofrequency glowdischarge atomic emission spectrometry;274 secondary ion massspectrometry;275±279 secondary neutral mass spectrometry;275,280

Auger electron spectroscopy;275 and electron probe microana-lysis.275,281±283

Solar control coatings on architectural glasses were inves-tigated comprehensively using Auger electron spectroscopy,SIMS, SNMS and EPMA.275 All methods found a system oftwo metallic Ag layers embedded between dielectric SnOx

layers. Additionally, thin (1±2 nm) layers of Ni and Cr weredetected on top of each of the Ag layers. The capabilities ofeach of the techniques were assessed critically for routineinvestigation of these coatings. This assessment concluded thatthe complementary nature of these surface analysis techniquesallowed individual measurement artifacts to be deconvolutedand a rigorous characterization of the material to be obtained.The capabilities of rf-GD-AES were demonstrated for this classof coated glasses274 and the presence of an extraneous overlayof a Si containing material (20 nm) con®rmed earlier SEMobservations.

Defects in glasses were categorized and investigated byappropriate micro-analytical techniques.283 A combination ofEPMA and LA-ICP-MS allowed the determination ofelemental concentrations to the low mg g21 level. Thiscapability allowed identi®cation of a speci®c source for thedefect from otherwise non-distinguishable refractories. In aseparate study, the migration of alkali metal in glasses underinvestigation by EPMA was investigated.281 Experimentalconditions were derived to minimize this phenomenon andallow reliable quantitative analysis using EPMA.

Glasses of various types remain popular targets for laserablation based sample introduction. However, in many cases,there is little technological interest in the glass itself. A detailedstudy and assessment of LA-ICP-MS for the depth pro®ling ofsilica based samples reported on elemental fractionationeffects, as functions of spot size and laser ¯uence, for ablationat 1064, 266 and 248 nm.284 It was observed that the geometryof the crater controlled the extent of elemental fractionationand this could become signi®cant when the depth : diameterratio of the crater is w6. The use of He, rather than Ar, as acarrier gas was bene®cial and, as is generally recognized forglasses, ablation in the UV was favorable. The conclusion was,

not surprisingly, that a number of experimental parametersaffected the utility of laser ablation in obtaining usefulconcentration : depth pro®les. The following conditions allmaximized the performance of the system: ablation in the UV,a large crater size at laser ¯uences well above the ablationthreshold and a He carrier gas. The structure of the crater wasdescribed in terms of a three section model, i.e., an ablationfront, intermediate section and crater opening.

Forensic and archaeological applications continue to growand are closely related. The sources of variance in the use ofICP-MS for the forensic identi®cation of glass fragments wereconsidered.285,286 ANOVA was applied to the ICP-MS analysisof both NIST CRMs and to an inter-laboratory study ofsamples taken across a sheet of ¯oat glass. The output of thisstatistical analysis was used to provide a more accurateinterpretation of the analytical data for forensic purposesand an increased understanding of the discrimination offeredby an ICP-MS analytical methodology. Non-destructiveanalysis (NDA) of medieval glasses was used to identifymanufacturing processes and technologies. This was accom-plished by external beam PIXE and a statistical analysis usingprinciple components methodology.287 Initial measurementswere also undertaken using XRF, EPMA and LA-ICP-MS. Anumber of variations on X-ray spectrometry were tested forsuitability in determining the major, minor and trace elementalcontent of medieval glasses.288 Scanning electron microscopy,with a wavelength dispersive spectrometer, was compared withPIXE for trace elemental analysis. Wavelength and energydispersive spectrometers were compared for major and minorelemental analysis. The reported PIXE method was clearlysuperior in terms of detection limits but could not detect lightelements of importance in glass research, e.g., Na, Al, Mg andSi.

3.4 Ceramics and refractories

Articles continue to be received concerning the problems ofdetermining rare earth elements in their oxide matrices. Asummary of such methods is provided in Table 3.

This year, the use of ETV for the analysis of refractorysamples, coupled to a variety of detectors, has proved to bepopular. Peng et al. have analysed silicon nitride by a variety ofmethodologies. Using a PTFE emulsion, the vaporizationbehaviour of silicon and three refractory elements (Al, Ti, andY) have been studied289 using ICP-AES detection. It was foundthat when using slurry samples and a 60 s ashing step at 700 ³C,approximately 90% of 100 mg of Si3N4 could be decomposedand evaporated without trace element loss. Detection limitsvaried from 0.11 mg g21 for Al to 0.09 mg g21 for Ti with RSDsranging from 1.9±4.2%. This method was modi®ed to includethe determination of Cu, Cr, Al, Y and Ti.290 A 1% m/v slurryof Si3N4 was dispersed with an ultrasonic wave vibrator for20 min before injection of 10 ml into the furnace. The resultswere in good agreement with those obtained by a dissolutionbased pneumatic nebulization ICP-AES method. Solid sam-pling ETAAS has been used for the direct determination of 11trace elements in high-purity tungsten trioxide and high-puritytungsten blue oxide.291 The extremely high background fromthe matrix was eliminated by reducing the tungsten to themetallic form with the addition of hydrogen as a purge gasduring the pyrolysis stage. Calibration was achieved usingaqueous standards. Detection limits ranged from 0.07 ng g21

for Mg, Na, and Zn to 1.7 ng g21 for Fe. The multi-elementanalysis of graphite and silicon carbide by solid sampling ETV-ICP-AES has been reported.292 Vaporization of the tracemetals was facilitated by the addition of Freon 1,2 gas(3 ml min21) to the Ar carrier gas. Sample sizes of 2±16 mg ofSiC (v5 mm particle size) produced detection limits of 5±250 ng g21 for 15 target elements. The analysis of high-puritytantalum powders by ETV-ICP-AES has been published.244


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


Table 3 Summary of analyses of advanced materials

Element Matrix


POLYMERIC MATERIALS AND COMPOSITESÐAl Polymers with

gradient andcompositestructures

AA;Ð;Ð Sample sectioned and sampled locally along gradient or compositestructure

309

Br, Pb,Hg

Polyethylene m-XRF;Ð;S Foils (93±453 mm) prepared. Elemental mapping and bulk concentrationsdetermined. Local concentrations estimated using the backscatterfundamental parameter method

310

C, O Polycarbonate andaluminizedpolycarbonates

XPS;Ð;S Surface modi®cation during plasma etching and metallization examined 311

Co, Mn,P, Ti

PET MS;ETV, ICP;S Direct solids analysis. Pd±ascorbic acid modi®er required for Pdetermination. Results compared with XRF and ICP-AE after sampledissolution.

312

Cu; S Polyimide on Cusubstrate

SIMS;Ð;S Cu migration into polymer ®lm studied. Polymer ®lm prepared by eithercoating and curing polyamic acids onto the substrate or by vapordeposition of Cu onto a PI ®lm

313

Cu TiOxNy ®lms SIMS;Ð;S Cs adduct approach applied 314Cu, Fe,

Co, NiGrafted

polypropylenesheets

XRF;Ð;S Ð 315

Cu, Fe,Mg,Mn, Zn

Wood pulp AE;ICP;S Pyrolytic carbon direct sample insertion probe with in-situ treatment withHCl and NaF. Samples were dried and ashed prior to plasma ignition.LOD~20±400 ng g21

316

Cu, Fe Ancientmanuscripts

AA;ETV;SMS;LA-ICP;S

Manuscript micro-sampled and analysed by slurry sampling ETV-AAwith calibration against aqueous samples. LA-ICP-MS used to de®nedistribution of Fe and Cu on the manuscript surface

317

Cr Polyethylene AA;Ð;Ð Attempted Cr speciation by co-precipitation on an alumina carrier 318F Ca silicate±¯uoride

compositesXRF;Ð;S Sample fused to yield a glass bead using Li borate ¯ux 319

Fe Cloth XRF;Ð;S Direct determination 320Pd Polymers MS;ETV, ICP;S Calibration obtained either externally or by single standard addition. Ir or

Ar dimer used as an internal standard. Absolute LOD ca. 1 pg or1 ng g21 relative

321

Pd, Ag,Ni

Pd alloy ®lms onstabilizedalumina orzirconiasupports

m-PIXE;SEM-EDAX;S

Elemental maps and depth pro®les obtained 322

Sb PET AA;ETV;L Treated with 4% v/v acetic acid. Characteristic mass 31 pg, recovery~92±98%

323

Sb PVC AA;ETV;S Rapid screening methodology 324Sn PVC AA;ETV;S Direct solids analysis with Pd as modi®er. Two-stage pyrolysis. PVC (0.1±

0.25 mg) suspended in 20 ml Pd modi®er, whole pipetted into furnace,aliquot of ascorbic acid added, sample dried at 120 ³C for 30 min,pyrolysed at 600 ³C for 45 s and at 1400 ³C for 30 s, atomized at2400 ³C. Absorbance measured at 326.2 nm with D2 backgroundcorrection. Values in good agreement with those obtained by FAA orETV-AA after dissolution

325

Ti, Si TiSix thin ®lms Auger ES;Ð;S Corrections for preferential sputtering and matrix composition applied 326Various Cloth AA;SE;L Cloth extracted with a biological simulant (saliva and perspiration) at

40 ³C for 1 h. Analytes of interest extracted into MIBK (10 cm3) asAPDC (2% w/v, 2 cm3) complexes

327

Various Polyethylene±polypropylenepolymer blend

AE;ICP;L 0.15 g sample wet-ashed with 2.5 cm3 of concentrated nitric acid at hightemperature and pressure in a sealed quartz vessel

328

Various Finger paints AE, AA;CV, HG,ICP;L

Microwave digestion followed by CVAA (Hg), HGAA (As, Se, Sb) andICP-AE (Ba, Cd, Cr, Pb)

329

Various Pigments and®llers inpolymers

AA;Ð;L Bulk material micro-sampled using ®ne capillaries. Sub-samplescombusted and these residues taken up in dilute acids

330

Various Pigments onmedievalmanuscripts

TXRF Surface micro-sampled by rubbing gently with a cotton wool swab (`Q-Tip'). Abraded material transferred to a glass carrier

331

Various Pigments onmedievalmanuscripts andoil paintings

TXRF;Ð;Ð Surface micro-sampled by rubbing gently with a cotton wool swab (`Q-Tip'). Abraded material transferred to a glass carrier

332

Zr Polyole®ns MS;ID-ICP;L 0.25±0.3 g microwave digested in sealed vessel with HNO3±HF. Spike ofenriched Zr added prior to digestion. Sample cooled, diluted with waterand isotope ratio determined by QICP-MS. LOD~18 ng g21

333

SEMICONDUCTOR MATERIALSÐAl Si XRF;Ð;Ð A combination of vapour-phase decomposition and total re¯ection XRF

gave DLs of 26109 atoms cm22334


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


Table 3 Summary of analyses of advanced materials (continued)

Element Matrix


B Si MS;ID-ICP;L Boron doped thin ®lms were dissolved in 0.3 M LiOH spiked with10B. Uncertainties were v4% with DLs of 2.161017 atoms cm23

335

Na Si XRF;Ð;Ð As for Al. DLs 361010 atoms cm22 334O Si wafer SIMS;Ð;S Quanti®cation is based on 16O/30Si secondary ion signal. Problems with

signal instability (RSD v2%) were overcome with vacuumizing for 2 h336

Various Microelectronicmaterials

MS;ICP;L On-line ion chromatography ICP-MS is compared with NAA, GD-MSand ETV-ICP-MS for the analysis of Mo, MoO3, MoSi2.5, W, WO3,W5Si3, As, P and Re

337

Various(4)

Si wafers MS;ICP;L HNO3±HF was used to decompose the Si. Si was removed by evaporationas SiF. Recoveries for Fe, Ni and Cr were 95±106%. Microwavedigestion gave better results for Zn but worse for Cu

338

Various(9)

Semiconductormaterials

XRF;Ð;S A rapid thin layer method with the direct digesting of the materials onthe substrate. Determination of Cr, Co, Ni, Cu, Zn, Ga, Se, Sb and Ywith DLs of 0.034%±0.113% for a 0.5 mg sample

339

Various(11)

YBa2Cu3O7-x AE;ICP;L ICP was optimized using the Mn 259.373 nm line for Ca, Mg, Fe, Mn,Al, Ni, Si and Sr. DLs ranged from 2.061025±1.261024% m/m

340

GLASSESÐCr Metal coated

glassesAE;rf-GD;S Depth pro®ling 341

Fe Metal coatedglasses

AE;rf-GD;S As for Cr 341

N Glasses and glassceramics

EPMA;Ð;S Energy and wavelength dispersive EPMA applied to determination of N 282

Ni Metal coatedglasses

AE;rf-GD;S As for Cr 341

O Nuclear wasteglass

SIMS;Ð;L Glass leached in solution containing enriched 29Si and 18O 277

Si Nuclear wasteglass

SIMS;Ð;L As for O 277

Sn Float glass SIMS;Ð;S Depth pro®les obtained by low energy SIMS (4 keV O2z) with electron

beam charge compensation. Quanti®cation from RSF derived from¯oat glass CRM

279

Various TV screen glass,glass ceramic,quartz

MS;ICP,LA;S Excimer laser ablation. Results compared to those obtained from wetchemical analysis

342

Various Low-levelradioactivewaste, glassprecursors

XRF;Ð;SMS;ICP;L

Mixtures of low active waste and glass precursors heat treated andresultant material analysed

343

Various Optical ®bres AE;ICP;L Three sample preparation methods:100 mg of glass fused with 1 g ofmetaborate ¯ux and resultant melt taken up in 150 cm3 concentratednitric acid; slurry nebulization with 10 mg glass dispersed in 100 cm3

surfactant solution and Mn added as internal standard; 25 mg of glasstaken up, with gentle heating, in 100 cm3 of 4 M boric acid and 3% v/vHCl

344

Various Glass ®bres SNMS;Ð;S Depth pro®ling on as-prepared ®bres; ®bres exposed to humidity, waterleach

280

Various(5)

Glass-polyalkenoatecement

SIMS;Ð;S Elemental mapping and depth pro®les 276

CERAMICS AND REFRACTORIESÐBa BaTiO3 ceramics EPMA;Ð;S BaTiO3 and Y2O3 were used as standards. A Joel JXA 840A electron

probe microanalyser under a 20 kV, 50 nA beam current was used.Results suggest Y incorporated preferentially at the Ba-sites

345

Cr Silicon nitride AE;ETV;Sl Sample (50 mg) was treated with 0.5 ml of 60% PTFE emulsion, 0.5%agar, and 0.1% Triton X-100. RSDs between 1.9±4%. DL for Cr1.58 ng ml21

346

Cu Rare earth oxide AA;F;L Spectral interferences are overcome by the use of PLS. Linear range 0±20 mg ml21, RSD 2.84±5.10%, with recovery of 100.1%

347

Cu Silicon nitride AE;ETV;Sl As or Cr. DL for Cu 1.05 ng ml21 346Eu Rare earth oxide AA;F;L Spectral interferences are overcome by the use of PLS. Linear range 2±

18 mg ml21, RSD 1.07±1.24%, with recovery of 98.6%347

Eu Standards XRF;Ð;S Samples were separated and preconcentrated on thorin modi®ed XAD-7.Preconcentration factors of 6500 were obtained. DLs of 13.8, 17 and15.7 mg l21 for Sm, Eu and Gd, respectively

348

Gd Standards XRF;Ð;S As for Eu 348Sm Standards XRF;Ð;S As for Eu 348Ti BaTiO3 ceramics EPMA;Ð;S As for Ba 345Various

(15)Eu, Gd AE;ICP;L Spectral interferences are overcome by the use of high resolution

sequential spectrometer349

Various(15)

Dy,Sm AE;ICP;L Spectral interferences are overcome by the use of high resolutionsequential spectrometer

350

Various(15)

Geochemicalsamples

MS;ICP;L Non-spectroscopic matrix effects were minimized using matrix matchedstandards and using Rh and In as internal standards

351


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


Up to 14 trace elements were determined using an automatedAWD 10 workstation to load the samples (8±40 mg) onto thepyrolytically coated graphite platform. Matrix removal wasachieved during the ashing stage (1000 ³C, 5 s). Calibration wasperformed using aqueous standards pipetted onto the platform.Detection limits ranged from 5 ng g21 for Ag to 250 ng g21 for K.

Several papers have been received this year on the analysis ofcement and concrete products and materials. The determinationof Th and U in activated concrete by ICP-MS after anion-exchange removal of the matrix293 has been reported. Althougha few mg ml21 of some matrix elements such as Al and Ca werenot separated from the target analytes, no interference could beobserved with the ®nal determination. Instrument detectionlimits were 2.3 pg ml21 for Th and 1.8 pg ml21 for U withprecisions of generally v7% in the solid. The accuracy of themethod was tested using the GSJ rock standard with recoveriesranging from 218% to 0.4% for Th and 214% to 25.7% for U.

An unusual variation on the concrete theme has beenpublished by Groenewold et al. with a description of theanalysis of the nerve agent VX (O-Et,S-2-diisopropyl-aminoethyl Me phosphonothiolate) on the surface of concretesamples.294 The authors used an ion-trap SIMS instrument todetermine VX down to an absolute quantity of 5 ng on aconcrete chip. To get down to these levels of detection the m/z268 and 128 ion fragmentation was measured using MS-MSwhere 268 corresponds to [VXzH]z and 128 corresponds to adiisopropylvinylammonium isomer that is formed by theelimination of the phosphonothiolate moiety. The authorswere able to show that VX degraded on the concrete surfaceover time. However, the degradation products of VX wereshown to stay detectable on the surface of the concrete for somelength of time. The authors did not mention whether thesedegradation products were toxic as well!

A ceramic and refractory section would not be completewithout some mention of what has been going on in the world oflaser ablation. The laser ablation ICP-MS analysis of sinteredsilicon nitride has been reported.295 The surface of the SiN was

subjected to ablation for 3 min using a Q-switched Nd:YAG laser(150 mJ) operating at 1064 nm. The laser sampled particles werecarried in a Ar stream and passed through 10 ml of 0.1 M nitricacid, which was subsequently analysed by ICP-MS. The methodwas successfully used for the determination of Mg, Ti, Mn, Coand W in sintered silicon nitride. A method for the quantitativedetermination of trace elements in single SiC crystals using LA-ICP-MS has been developed.296 As above, a 1064 nm Nd:YAGlaser was used in `free running' mode as this provides bettersignal-to-noise ratios than when using the laser in Q-switchedmode. No sample preparation was necessary other than purifyingthe crystal surface with HF. Calibration was achieved by addingmulti-element standard solution to SiC powder. The powder wasdried and pressed into pellets with carbon powder as a bindingmaterial. Recovery rates from the analysis of SiC referencematerials ranged from 95 to 101%. Detection limits were between361029 g g21 for V to 461028 g g21 for Cu. RSDs at the161026 g g21 level were v10% when the intensities of 10 craters,each with 500 laser shots, were averaged.

One last word for this section is that a larger than normalselection of papers has been noticed for the analysis ofarchaeological ceramic-type samples. Methods used rangefrom NAA,297 DCP,298 PIXE,299±301 XRF,302±305 ICP-AES,306

and LA-MS.307

3.5 Catalysts

There are a limited number of reports incorporated in thisreview and these are, almost exclusively, concerned with surfacecharacterization. The usual suspects of surface characterizationtechniques feature strongly, e.g., XPS and SIMS. A differentapproach to the derivation of elemental maps of platinumgroup metals on automotive catalysts was reported, i.e., laserinduced breakdown spectroscopy.308 With some considerableeffort, radial and axial distributions were obtained on sectionedcatalysts. Success was dependent upon careful experimentaloptimization, coupled to a detailed examination of the

Table 3 Summary of analyses of advanced materials (continued)

Element Matrix


Various Gadolinium oxide MS;ICP;L Groups of REE were determined after various extractions using 2-ethylhexylhydrogen-ethylhexylphosphonate chromatographic separation

352

Various Praseodymiumoxide

MS;ICP;L Internal standards worked for REE except Tb which required aseparation step using chromatography. Recoveries were 89.1±105% withDLs of 0.02±0.09 mg g21

353

Various(14)

Eu2O3 MS;ICP;L Internal standardization successfully compensated for matrix effects for 13REE. Tm had to be separated using chromatographic separation. DLswere in the range 0.005±0.021 mg l21, RSDs 1.4±8.1% and recoveries84±112%

354

Various(7)

Praseodymiumoxide

MS;ICP;L Sample (10 mg) was decomposed with 2 ml of 4 M HCl, evaporated, re-dissolved in 2 M HCL plus Re internal standard. REE DLs were 5±21 mg l21 with recoveries of 89.1±102%

348

Various(14)

Lanthanum oxide AE;ETV-ICP;L Sample was treated with PTFE emulsion to produce volatile ¯uorides.DLs range from 2 ng ml21 for Yb to 130 ng ml21 for Ce with RSDsv5%

355

Various Yttrium oxide MS;ICP;L Sample (10 mg) was dissolved in a quartz vessel with HNO3±H2O (1 : 3)on a hot plate. The effect of the Y matrix could be eliminated with Gaand an internal standard

356

Various(21)

BaTiO3 powders MS;ICP;L To correct for polyatomic interferences a `blank' matrix was prepared andsubtracted from results. Main impurities found were Sr and Ca

227

Y BaTiO3 ceramics EPMA;Ð;S As for Ba 345CATALYSTSÐC Spent MnO2±CeO2 XPS, S-SIMS;Ð

;ÐCarbonaceous deposits characterized 357

C Pt±Al2O3, Pd±SiO2

catalystsSIMS, XPS;Ð;Ð Carbonaceous deposits characterized 358

O Spent MnO2±CeO2 XPS, S-SIMS;Ð;Ð

As for C 357

aHy indicates hydride and S, L, G and Sl signify solid, liquid, gaseous or slurry sample introduction, respectively. Other abbreviations arelisted elsewhere.


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


resultant spectra and the application of appropriate internalstandards.

4 References

1 J. Prohaszka, J. Dobranszky and P. J. Szabo, X-Ray Spectrom.,1999, 28, 233.

2 E. Denes, P. J. Szabo and D. Zsambok, X-Ray Spectrom., 1999,28, 267.

3 P. J. Szabo and E. Denes, Mikrochim. Acta, 2000, 132(2±4), 345.4 H. Dillen, C. Xhoffer, H. Storms and L. Kestens, Mikrochim.

Acta, 2000, 132(2±4), 323.5 J. Nickel and A. N. Shuaib, Nucl. Instrum. Methods Phys. Res.,

Sect. B, 1999, 158(1±4), 729.6 R. Maibusch, H.-M. Kuss, A. G. Coedo, T. Dorado and

I. Padilla, J. Anal. At. Spectrom., 1999, 14(8), 1155.7 R. Noll, V. Sturm and L. Peter, Proc. Chem. Conf., 1997, 49th, 22.8 S. Palanco, L. M. Cabalin, D. Romero and J. J. Laserna, J. Anal.

At. Spectrom., 1999, 14(12), 1883.9 C. Aragon, J. A. Aguilera and F. Penalba, Appl. Spectrosc., 1999,

53(10), 1259.10 L. M. Cabalin, D. Romero, J. M. Baena and J. J. Laserna,

Fresenius' J. Anal. Chem., 1999, 365(5), 404.11 U. Engel, A. Kehden, E. Voges and J. A. C. Broekaert, Spectro-

chim. Acta, Part B, 1999, 54, 1279.12 J.-C. Hubinois, A. Morin, P. Marty, J.-P. Larpin and

M. Perdereau, J. Anal. At. Spectrom., 1999, 14(9), 1405.13 T. Akiyoshi, A. Sakage, Y. Ishibashi, A. Chino and T. Maegawa,

Jpn. Kokai Tokkyo Koho JP 11 108,829 [99 108,829] (Cl.G01N21/31), 23 Apr 1999, Appl. 97/281,143, 30 Sep 1997; 5 pp.

14 J. Geyer, J. Flock and J. A. C. Broekaert, Mikrochim. Acta, 1999,131(3±4), 191.

15 H. Dillen, Proc. Chem. Conf., 1997, 49th, 99.16 T. Mochizuki, Bunseki, 1999, 12(12), 1019.17 H. Kondo, M. Aimoto, A. Ono and K. Chiba, Anal. Chim. Acta,

1999, 394(2±3), 293.18 W. Stankiewicz, B. Bolibrzuch and M. Marczak, Gold Bull.

(London), 1998, 31(4), 119.19 P. L. Guo, J. Q. Wang, J. Q. Zhu and A. Q. Le, Guangpuxue Yu

Guangpu Fenxi, 1999, 19(6), 871.20 K. Janssens, G. Vittiglio, I. Deraedt, A. Aerts, B. Vekemans,

L. Vincze, F. Wei, I. Deryck, O. Schalm, F. Adams, A. Rindby,A. Knoechel, A. Simionovici and A. Snigirev, X-Ray Spectrom.,2000, 29, 73.

21 G. Vittiglio, K. Janssens, B. Vekemans, F. Adams and A. Oost,Spectrochim. Acta, Part B, 1999, 54B(12), 1697.

22 C. E. Lyman, R. E. Lakis, H. G. Stenger Jr., B. Totdal andR. Prestvik, Mikrochim. Acta, 2000, 132(2±4), 301.

23 M. Hajivaliei, M. L. Garg, D. K. Handa, K. L. Govil,T. Kakavand, V. Vijayan, K. P. Singh and I. M. Govil, Nucl.Instrum. Methods Phys. Res., Sect. B, 1999, B150(1±4), 645.

24 M. H. Abraham, G. W. Grime, J. P. Northover and C. W. Smith,Nucl. Instrum. Methods Phys. Res., Sect. B, 1999, B150(1±4), 651.

25 G. Demortier, Y. Morciaux and D. Dozot, Nucl. Instrum.Methods Phys. Res., Sect. B, 1999, B150(1±4), 640.

26 G. Demortier, F. Fernandez-Gomez, M. A. Ontalba Salamancaand P. Coquay, Nucl. Instrum. Methods Phys. Res., Sect. B, 1999,158(1±4), 275.

27 J. Noelte and M. Paul, At. Spectrosc., 1999, 20(6), 212.28 O. V. Borisov, X. L. Mao, A. Fernandez, M. Caetano and

R. E. Russo, Spectrochim. Acta, Part B, 1999, 54, 1351.29 S. Pattberg and R. Matschat, Fresenius' J. Anal. Chem., 1999,

364(5), 410.30 Y. Hayakawa, Y. Hirao, Z. Y. Jin and G. Zheng, Hozon Kagaku,

1999, 38, 98.31 S. Richter, M. Berglund and C. Hennessy, Fresenius' J. Anal.

Chem., 1999, 364(5), 478.32 H. Emteborg, X. Tian and F. C. Adams, J. Anal. At. Spectrom.,

1999, 14(10), 1567.33 G. De Wannemacker, F. Vanhaecke, L. Moens, A. Van Mele and

H. Thoen, J. Anal. At. Spectrom., 2000, 15(4), 323.34 G. A. Giacomozzi, R. R. U. Querioz, I. G. Souza and

J. A. G. Neto, J. Autom. Methods Manage. Chem., 1999, 21(1),17.

35 J. Zhang and C. H. Cai, Lihua Jianyan, Huaxue Fence, 1999,35(3), 136.

36 M. Bertilia Oss Giacomelli, J. Bento Borba da Silva andA. J. Curtius, Mikrochim. Acta, 1999, 132(1), 25.

37 A. G. Coedo, T. Dorado and I. Padilla, Appl. Spectrosc., 1999,53(8), 974.

38 K. Fujimoto, M. Shimura and K. Yoshioka, Tetsu to Hagane,1999, 85(2), 114.

39 J. B. Borva da Silva, M. B. Oss Giacomelli and A. J. Curtius,Analyst (Cambridge, U. K.), 1999, 124(8), 1249.

40 F. Guo, X. J. Li and Z. Y. Chen, Guangpuxue Yu Guangpu Fenxi,1999, 19(3), 437.

41 K. Matsusaki, M. Nomi, M. Higa and T. Sata, Anal. Sci., 1999,15(2), 145.

42 Y. Ning, Z. Wang, S. Liu, F. Ge and H. Li, Zhenkong Kexue YuJishu, 1998, 18(Suppl.), 165.

43 D. Ma, Y. Okamoto, T. Kumamaru and E. Iwamoto, Anal. Sci.,1999, 15(2), 193.

44 M. A. Taher, J. Anal. At. Spectrom., 2000, 15(5), 573.45 K. Cai, C. H. Li, Z. D. Liu and G. Y. Li, Guangpuxue Yu

Guangpu Fenxi, 1999, 19(3), 441.46 K. Ohta, K. Kawaguti, H. Uegomori and T. Mizuno, Chem.

Anal. (Warsaw), 1999, 44(2), 187.47 F. X. Jin, Y. Zou, Z. J. Chen and D. R. Qiu, Guangpuxue Yu

Guangpu Fenxi, 1999, 19(4), 593.48 Z.-X. Jin, C.-H. Tan, G.-Z. Liu, Z.-Y. Tang, H.-O. Qiu and S.-

H. Hu, Gaodeng Xuexiao Huaxue Xuebao, 1999, 20(5), 61.49 J. F. Zhang and G. M. Zhen, Lihua Jianyan, Huaxue Fence, 1999,

35(5), 235.50 A. Bengtson, S. Hanstrom, E. L. Piccolo, N. Zacchetti,

R. Meilland and H. Hocquaux, Surf. Interface Anal., 1999,27(8), 743.

51 R. Shekhar, M. V. Balarama Krishna, J. Arunachalam andS. Gangadharan, At. Spectrosc., 1999, 20(1), 25.

52 R. O. Keto, J. Forensic Sci., 1999, 44(5), 1020.53 M. V. Balarama Krishna, R. Shekhar, D. Karunasagar and

J. Arunachalam, Anal. Chim. Acta, 2000, 408(1±2), 199.54 S. Q. Cao, H. T. Chen and X. J. Zeng, Guangpuxue Yu Guangpu

Fenxi, 1999, 19(6), 854.55 D. Joseph and I. G. Sharma, J. Radioanal. Nucl. Chem., 1999,

240(1), 353.56 A. Marucco, C. Marcolli and R. Magarini, At. Spectrosc., 1999,

20(4), 134.57 X. R. Wang, Lihua Jianyan, Huaxue Fence, 1999, 35(12), 563.58 S.-I. Hasegawa, T. Kobayashi, K. Sato, S. Igarashi and K. Naito,

Nippon Kinzoku Gakkaishi, 1999, 63(8), 1069.59 S. Sakao, Kenkyu Hokoku - Kanagawa-ken Sangyo Gijutsu Sogo

Kenkyusho, 1998, 4, 64.60 T. Imakita, M. Inui, K. Hamada, M. Taniguchi and T. Nakahara,

Tetsu to Hagane, 1999, 85(10), 724.61 S. T. Liu and P. Luo, Lihua Jianyan, Huaxue Fence, 1999, 35(5),

231.62 A. G. Coedo, I. Padilla, T. Dorado and F. J. Alguacil, Anal.

Chim. Acta, 1999, 389(1±3), 247.63 S. Kozono, R. Takashi and H. Haraguchi, Anal. Sci., 2000, 16(1),

69.64 M. Chaudhary, D. C. Paschal, W. C. Elliott, H. P. Hopkins,

A. M. Ghazi, B. C. Ting and I. Romieu, At. Spectrosc., 1998,19(5), 156.

65 G. O'Connor, L. Ebdon and E. H. Evans, J. Anal. At. Spectrom.,1999, 14(9), 1303.

66 J. G. Farmer, L. J. Eades, M. C. Graham and J. R. Bacon,J. Environ. Monit., 2000, 2(1), 49.

67 H. B. Swan, Bull. Environ. Contam. Toxicol., 1999, 63(4), 491.68 D. J. Butcher, A. Zybin, M. A. Bolshov and K. Niemax, Anal.

Chem., 1999, 71(23), 5379.69 X.-J. Sun and Z.-H. Zhang, Gaodeng Xuexiao Huaxue Xuebao,

1999, 20(5), 84.70 H.-G. Lohmannsroben and Th. Roch, J. Environ. Monit., 2000,

2(1), 17.71 Y. Nakamoto, Idemitsu Giho, 1998, 41(5), 457.72 Y. Zhang, J. L. Talbott, L. Wiedenmann, J. DeBarr and I. Demir,

Adv. X-Ray Anal., 1999, 41, 879.73 J. Kierzek, B. Malozewska-Bucko, P. Bukowski, J. L. Parus,

A. Ciurapinski, S. Zaras, B. Kunach and K. Wiland, J. Radioanal.Nucl. Chem., 1999, 240(1), 39.

74 C. Bachmann and T. Sauer, Schuettgut, 1999, 5(3), 362.75 C. A. Booth, D. A. Spears, P. Krause and A. G. Cox, Fuel, 1999,

78(14), 1665.76 W. Luesaiwong and R. K. Marcus, (Dept. Chem., Howard

L. Hunter Lab., Clemson Univ., Clemson, SC 29631-1905, USA).Presented at Pittcon.'99, Orlando, FL, USA, March 7±12, 1999.

77 M. M. Silva, M. Goreti, R. Vale and E. B. Caramao, Talanta,1999, 50, 1035.

78 R. Richaud, H. Lachas, M.-J. Lazaro, L. J. Clarke, K. E. Jarvis,A. A. Herod, T. C. Gibb and R. Kandiyoti, Fuel, 1999, 79(1), 57.

79 K. L. Laban and B. P. Atkin, Fuel, 2000, 79(2), 173.


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


80 M. Bettinelli, S. Spezia and S. Roberti, At. Spectrosc., 1999,20(1), 13.

81 J. Shiowatana, A. Siripinyanond, W. Waiyawat and S. Nilmanee,At. Spectrosc., 1999, 20(6), 224.

82 J. L. Burguera, R. A. de Salager, M. Burguera, J. L. Salager,C. Rondon, P. Carrero, M. Gallignani, M. R. Brunetto andM. Briceno, J. Anal. At. Spectrom., 2000, 15(5), 549.

83 M. B. Martin-Garcia, D. Bellido-Milla, A. Jimenez-Jimeniz andM. P. Hernandez-Artiga, Fresenius' J. Anal. Chem., 1999, 364(6),527.

84 D. Langer and J. A. Holcombe, Prepr. Am. Chem. Soc., Div. Pet.Chem., 1999, 44(3), 274.

85 C. Sanz-Segundo, M. P. Hernandez-Artiga, J. L. Hidalgo-Hidalgo de Cisneros, D. Bellido-Milla and I. Naranjo-Rodriguez,Mikrochim. Acta, 1999, 132(1), 89.

86 C. van Netten, Sci. Total Environ., 1999, 229(1±2), 125.87 Y. Kamata, T. Takeshima, T. Okada and K. Terada, Adv. Space

Res., 1999, 23(11), 1829.88 G. R. Humphrey, Lubr. Eng., 1999, 55(10), 19.89 Z. Kowalewska, E. Bulska and A. Hulanicki, Spectrochim. Acta,

Part B, 1999, 54, 835.90 C. Nerin, C. Domeno, J. I. Garcia and A. del Alamo,

Chemosphere, 1999, 38(7), 1533.91 K. Krengel-Rothensee, U. Richter and P. Heitland, J. Anal. At.

Spectrom., 1999, 14(4), 699.92 E. Larras-Regard, Zhenkong Kexue Yu Jishu, 1998, 18(Suppl.),

23.93 W. Fuyi, J. Zucheng, H. Bin and P. Tianyou, J. Anal. At.

Spectrom., 1999, 14(10), 1619.94 M. Howard, H. A. Jurbergs and J. A. Holcombe, J. Anal. At.

Spectrom., 1999, 14(8), 1209.95 E.-S. Ong and Y.-L. Yong, Gaodeng Xuexiao Huaxue Xuebao,

1999, 20(5), 7.96 X. R. Wang, Z. X. Zhuang, D. H. Sun, J. X. Hong, X. H. Wu,

F. S. C. Lee, M. S. Yang and H. W. Leung, At. Spectrosc., 1999,20(3), 86.

97 E. S. Ong, Y. L. Yong and S. O. Woo, J. AOAC Int., 1999, 82(4),963.

98 L. H. Liu, Q. K. Zhang, M. Y. Wang and J. L. Lei, Yaowu FenxiZazhi, 1999, 19(3), 181.

99 L. H. Liu, M. Y. Wang and J. H. Lei, Fenxi Ceshi Xuebao, 1999,18(6), 59.

100 Q. F. Zhang, S. S. Peng, M. Ni, X. Y. Hu and W. Y. Yang,Guangpuxue Yu Guangpu Fenxi, 1999, 19(2), 203.

101 S. F. Dong, Z. G. Zhu, J. Liu, Y. Zhang and Z. A. Xu,Guangpuxue Yu Guangpu Fenxi, 1999, 19(3), 406.

102 M. Patriarca, N. A. Kratochwil and P. J. Sadler, J. Anal. At.Spectrom., 1999, 14(4), 633.

103 J. Szpunar, A. Makarov, T. Pieper, B. K. Keppler andR. Lobinski, Anal. Chim. Acta, 1999, 387(2), 135.

104 P. Krystek and K. G. Heumann, J. Anal. At. Spectrom., 1999,14(9), 1443.

105 A. LeBlanc, P. Dumas and L. Lefebvre, Sci. Total Environ., 1999,229(1±2), 121.

106 D. Q. Mo, Y. Y. Ni and Z. Huang, Guangpuxue Yu GuangpuFenxi, 1999, 19(4), 598.

107 L. Gamiz-Gracia and M. D. Luque de Castro, Talanta, 1999, 50,875.

108 L. Gamiz-Gracia and M. D. Luque de Castro, J. Anal. At.Spectrom., 1999, 14(10), 1615.

109 S. C. Nielsen, S. Sturup, H. Spliid and E. H. Hansen, Talanta,1999, 49(5), 1027.

110 S. Taguchi, A. Kakinuma and I. Kasahara, Anal. Sci., 1999,15(11), 1149.

111 T. Narukawa, W. Yoshimura and A. Uzawa, Bull. Chem. Soc.Jpn., 1999, 72(4), 701.

112 J. S. Lee and H. B. Lim, Bull. Korean Chem. Soc., 1999, 20(9),1040.

113 O. T. Akinbo and J. W. Carnahan, Anal. Chim. Acta, 1999,390(1±3), 217.

114 Y. Sung and H. B. Lim, Microchem. J., 2000, 64(1), 51.115 H. D. Wizemann, Spectrochim. Acta, Part B, 1999, 54, 1267.116 I. Lopez-Garcia, M. Sanchez-Merlos and M. Hernandez-Cor-

doba, Anal. Chim. Acta, 1999, 396(2±3), 279.117 M. Accominotti, M. Bost, P. Haudrechy, B. Mantout, P. J. Cunat,

F. Comet, C. Mouterde, F. Plantard, P. Chambon andJ. J. Vallon, Contact Dermatitis, 1998, 38(6), 305.

118 J. P. Huang and G. P. Hang, Guangpuxue Yu Guangpu Fenxi,1999, 19(3), 421.

119 J.-L. Todoli and J.-M. Mermet, Spectrochim. Acta, Part B, 1999,54, 895.

120 B. W. Pack, G. M. Hieftje and Q. Jin, Anal. Chim. Acta, 1999,383(3), 231.

121 M. Eschwey, E. Pulvermacher, C. Benninghoff and U. Telgheder,J. Anal. At. Spectrom., 2000, 15(3), 277.

122 J. C. Florez Menendez, A. Menendez Garcia, J. E. Sanchez Uriaand A. Sanz-Medel, Anal. Chim. Acta, 1999, 402(1±2), 319.

123 H. Kola and P. Peramaki, At. Spectrosc., 1999, 20(4), 142.124 U. Vollkopf, K. Klemm and M. P¯uger, At. Spectrosc., 1999,

20(2), 53.125 D. S. Bollinger and A. J. Schleisman, At. Spectrosc., 1999, 20(2),

60.126 B. Divjak and W. Goessler, J. Chromatogr., A, 1999, 844(1±2),

161.127 C. Hackett, H. Hermon, E. Cross, P. Doty, E. Tarver and

R. James, J. Electron. Mater., 1999, 28(6), 774.128 D. Gunther, A. Quadt, R. Frishknecht and V. J. Dietrich (Lab.

Inorg. Chem., Swiss Fed. Inst. Technol., Zurich, Switzerland).Presented at Instrumental Methods of Analysis. Modern Trendsand Applications (IMA '99), 19±22 September, 1999, Chalkidiki,Greece.

129 L. Halicz, A. Galy, N. S. Belshaw and R. K. O'Nions, J. Anal. At.Spectrom., 1999, 14(12), 1835.

130 D. S. Boyle, S. Hearne, D. R. Johnson and P. O'Brien, J. Mater.Chem., 1999, 9(11), 2879.

131 M. Tanaka and K. Takahashi, Anal. Chim. Acta, 2000, 411(1±2),109.

132 E. T. Urbansky, M. L. Magnuson, D. Freeman and C. Jelks,J. Anal. At. Spectrom., 1999, 14(12), 1861.

133 M. Nomura, K. Kogure and M. Okamoto, Bull. Res. Lab. Nucl.React. (Tokyo Inst. Technol.), 1998, 22, 4.

134 T.-L. Chang, W.-J. Li, G.-S. Qiao, Q.-Y. Qian and Z.-Y. Chu,Int. J. Mass Spectrom., 1999, 189(2±3), 205.

135 H. Kipphardt, S. Valkiers, F. Henriksen, P. De Bievre,P. D. P. Taylor and G. Tolg, Int. J. Mass Spectrom., 1999,189(1), 27.

136 W. Kerl, Ultratrace and isotopic analysis of long-livedradionuclides by double-focusing sector ®eld ICP mass spectro-metry, Ber. Forschungszent. Juelich, Juel-, 3605, 1998, 122.

137 J. S. Becker, H.-J. Dietze, J. A. McLean and A. Montaser, Anal.Chem., 1999, 71(15), 3077.

138 J. S. Becker and H.-J. Dietze, J. Anal. At. Spectrom., 1999, 14(9),1493.

139 S. A. Goldberg, Nucl. Mater. Manage., 1998, 27(2), 1272.140 I. Bowen, A. J. Walder, T. Hodgson and R. R. Parrish, ASTM

Spec. Tech. Publ., 1998, 1344(Applications of InductivelyCoupled Plasma-Mass Spectrometry to Radionuclide Determi-nations: Second Volume), 22.

141 R. W. Ryon and W. D. Ruhter, X-Ray Spectrom., 1999, 28, 230.142 U. Narayan, S. Goldberg, F. Jones, C. Leahy, M. Legel, P. Mason

and B. Srinivasan, (New Brunswick Lab., US Dept. Energy,Argonne, IL 60439, USA). Presented at Pittcon.'99, Orlando, FL,USA, March 7±12, 1999.

143 P. Goodall and C. Lythgoe, Analyst (Cambridge, U. K.), 1999,124(3), 263.

144 T. A. Policke, R. N. Bolin and T. L. Harris, ASTM Spec. Tech.Publ., 1998, 1344(Applications of Inductively Coupled Plasma-Mass Spectrometry to Radionuclide Determinations: SecondVolume), 3.

145 J. S. Crain, ASTM Spec. Tech. Publ., 1998, 1344(Applications ofInductively Coupled Plasma-Mass Spectrometry to RadionuclideDeterminations: Second Volume), 16.

146 P. Fichet, P. Mauchien and C. Moulin, Appl. Spectrosc., 1999,53(9), 1111.

147 B. W. Smith, A. Quentmeier, M. Bolshov and K. Niemax,Spectrochim. Acta, Part B, 1999, 54, 943.

148 G. Tamborini and M. Betti, Mikrochim. Acta, 2000, 132(2±4),411.

149 P. D. W. Bottomley, S. Bremier, J.-P. Glatz and C. T. Walker,Mikrochim. Acta, 2000, 132(2±4), 391.

150 J. M. Lopez-Gutierrez, M. Garcia-Leon, C. Schnabel,A. Schmidt, R. Michel, H.-A. Synal and M. Suter, Appl.Radiat. Isot., 1999, 51(3), 315.

151 A. W. McMahon, J. D. Gilmour, M. B. Hernandez andM. Rateitzak, AIP Conf. Proc., 1998, 454(Resonance IonizationSpectroscopy), 269.

152 J. F. Niello, D. E. Alvarez, R. G. Liberman, A. Arazi, D. Abriola,E. Achterberg, O. A. Capurro, A. M. J. Ferrero, M. Ditada,G. V. Marti, A. J. Pacheco, M. Ramirez, J. E. Testoni andS. R. Souza S. R. Souza (Ed.), Current status of the AMSprogram at the TANDAR laboratory. Nucl. Phys., Proc. Braz.


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


Workshop, 20th 1997, World Scienti®c: Singapore, Singapore,Singapore, 1998, 391±391.

153 B. A. Bushaw and B. D. Cannon, AIP Conf. Proc., 1998,454(Resonance Ionization Spectroscopy), 177.

154 P. Muller, B. A. Bushaw, K. Blaum, W. Nortershauser,N. Trautmann and K. Wendt, AIP Conf. Proc., 1998,454(Resonance Ionization Spectroscopy), 73.

155 B. D. Quimby and D. A. Grudoski, (Hewlett-Packard,Wilmington, DE 19352, USA). Presented at Pittcon.'99, Orlando,FL, USA, March 7±12, 1999.

156 M. Sanchez-Vinas, G. M. Bagur, D. Gazquez, M. Camino andR. Romero, J. Anal. Toxicol., 1999, 23(2), 108.

157 M. Derda, Sulfur isotopes in nature. Methods for determinationof sulfur isotope ratios in coal and petroleum by mass spectro-metry. Rap. IChTJ. Ser. B, 1999, 1±20.

158 S. J. Kumar and S. Gangadharan, J. Anal. At. Spectrom., 1999,14(6), 967.

159 Z.-X. Zhuang, Z. Yan, B. Chen and J.-X. Hong, GaodengXuexiao Huaxue Xuebao, 1999, 20(5), 74.

160 S. Pessayre, R. Bacaud, C. Geantet and M. Vrina, Fuel, 1999,78(7), 857.

161 Z. Czovek, A. Gaspar, M. Braun and J. Posta, ACH - ModelsChem., 1999, 136(1±2), 95.

162 G.-C. Wang, G.-H. Zhu, L. Peng and Q.-H. Xu, GaodengXuexiao Huaxue Xuebao, 1999, 20(5), 31.

163 B. Michalke and P. Schramel, Electrophoresis, 1999, 20(12), 2547.164 D. Langer and J. A. Holcombe, Prepr. - Am. Chem. Soc., Div.

Pet. Chem., 1999, 44(3), 274.165 D. Kaminaris, M. Koulaxidis and E. Ntafou, (Chem. Div., Inst.

Geol. and Mineral Exploration, Peania, Greece). Presented atInstrumental Methods of Analysis.Modern Trends and Applica-tions (IMA '99), 19±22 September, 1999, Chalkidiki, Greece.

166 I. Nelson, U.S. US 5,982,847 (Cl. 378±47; G01N23/223), 9 Nov1999, US Appl. 29,490, 28 Oct 1996; 21 pp.

167 W. Njue, A. M. Kinyua and M. T. Thinguri, Bull. Chem. Soc.Ethiop., 1999, 13(2), 99.

168 H. Lachas, R. Richaud, A. A. Herod, D. R. Dugwell andR. Kandiyoti, Rapid Commun. Mass Spectrom., 2000, 14(5), 335.

169 R. Richaud, M.-J. Lazaro, H. Lachas, B. B. Miller, A. A. Herod,D. R. Dugwell and R. Kandiyoti, Rapid Commun. MassSpectrom., 2000, 14(5), 317.

170 T. Wondimu, W. Goessler and K. J. Irgolic, Fresenius' J. Anal.Chem., 2000, 367(1), 35.

171 Y. N. Makarovskaya, L. P. Eksperiandova and A. B. Blank,J. Anal. Chem. (Transl. of Zh. Anal. Khim.), 1999, 54(11), 1031.

172 B. Zhang and L. R. Xiang, Fenxi Huaxue, 1999, 27(6), 661.173 W. Ye and Q. Lin, Faming Zhuanli Shenqing Gongkai

Shuomingshu CN 1,120,167 (Cl. G01N30/00), 10 Apr 1996,Appl. 94,115,528, 12 Sep 1994; 8 pp.

174 S. Latva, S. Peraniemi and M. Ahlgren, Analyst (Cambridge,U. K.), 1999, 124(7), 1105.

175 B. Cai, L. X. Wei, H. C. Xiong, Z. H. Liao, B. Hu and Z. C. Jiang,Fenxi Kexue Xuebao, 1999, 15(2), 103.

176 M. E. Wieser and W. A. Brand, Rapid Commun. Mass Spectrom.,1999, 13(13), 1218.

177 I. C. Chuang, Y. L. Huang and T. H. Lin, Anal. Sci., 1999,15(11), 1133.

178 K. L. Hoffman, M. R. Feng and D. T. Rossi, J. Pharm. Biomed.Anal., 1999, 19(3±4), 319.

179 S. P. Quinaia and J. A. Nobrega, Food Chem., 1999, 64(3), 429.180 K. Benkhedda, E. Ivanova and F. Adams, J. Anal. At. Spectrom.,

1999, 14(6), 957.181 K. L. Ackley, J. A. Day, K. L. Sutton and J. A. Caruso, Anal.

Commun., 1999, 36(8), 295.182 E. Tatar, V. G. Mihucz, A. Varga, G. Zaray and E. Cseh, J. Inorg.

Biochem., 1999, 75(3), 219.183 T. P. Gbatu, K. L. Sutton, O. Ceylan, H. B. Mark and

J. A. Caruso, (Dept. Chem., Univ. Cincinnati, Cincinnati, OH45221±0172, USA). Presented at Pittcon.'99, Orlando, FL, USA,March 7±12, 1999.

184 M. Claes, K. van Dyck, H. Deelstra and R. van Grieken,Spectrochim. Acta, Part B, 1999, 54(10), 1517.

185 J.-X. Luo, Gaodeng Xuexiao Huaxue Xuebao, 1999, 20(5), 20.186 K. Kohda, T. Yokokura, K. Yamamoto and T. Shirasaki,

Chromatography, 1999, 20(4), 378.187 L. Yu, X.-Z. Sun, H.-Q. Fang, B.-Y. Lu and L.-W. Qiu, Gaodeng

Xuexiao Huaxue Xuebao, 1999, 20(5), 24.188 R. Myors, R. J. Wells, S. V. Skopec, P. Crisp, R. Iavetz,

Z. Skopec, A. Ekangaki and J. Robertson, Anal. Commun., 1998,35(12), 403.

189 A. Kelko-Levai, I. Varga, K. Zih-Perenyi and A. Lasztity,Spectrochim. Acta, Part B, 1999, 54, 827.

190 Z. G. Zhu, G. X. Wang and J. H. Cheng, Guangpuxue YuGuangpu Fenxi, 1999, 19(2), 210.

191 K. Fujiwara, K. Murata, M. Inada and T. Nakahara, BunsekiKagaku, 1999, 48(8), 783.

192 P. K. Tewari and A. K. Singh, Analyst (Cambridge, U. K.), 1999,124(12), 1847.

193 T. Wang, Z. Ge, J. Wu, B. Li and A.-S. Liang, J. Pharm. Biomed.Anal., 1999, 19(6), 937.

194 M. G. Baron, R. T. Herrin and D. E. Armstrong, Analyst(Cambridge, U. K.), 2000, 125(1), 123.

195 R. A. Ismail and A. M. Moussa, Qatar Univ. Sci. J., 1996, 16(2),245.

196 R. Flarend, C. Keim, T. Bin, D. Elmore, S. Hem and M. Ladisch,J. Inorg. Biochem., 1999, 76(2), 149.

197 Y. X. Li, Y. Q. Li and Y. P. Xu, Lihua Jianyan, Huaxue Fence,1999, 35(4), 189.

198 N. Takeda, S. Sasaki and K. Taketa, Jpn. Kokai Tokkyo KohoJP 11 101,780 [99 101,780] (Cl. G01N27/62), 13 Apr 1999, Appl.97/259,779, 25 Sep 1997; 4 pp.

199 X.-F. Wang, Y.-C. Hao, L.-L. Zhou, H.-X. Bao and J.-Y. Wang,Gaodeng Xuexiao Huaxue Xuebao, 1999, 20(5), 72.

200 H. T. Uggerud and W. Lund, Spectrochim. Acta, Part B, 1999,54(11), 1625.

201 C. F. Wang, C. Y. Chang, C. J. Chin and C. J. Men, GaodengXuexiao Huaxue Xuebao, 1999, 20(5), 71.

202 B. Sundaravel, K. Sekar, G. Kuri, P. V. Satyam, B. N. Dev,S. Bera, S. V. Narasimhan, P. Chakraborty and F. Caccavale,Appl. Surf. Sci., 1999, 137(1±4), 103.

203 T. L. Ramus, S. J. Hein, M. W. Raynor and V. H. Houlding,(Diablo Analytical Inc., Concord, CA 94524, USA). Presented atPittcon.'99, Orlando, FL, USA, March-12, 1999.

204 H.-J. Shi, X.-H. Wang and H.-S. Liu, Gaodeng Xuexiao HuaxueXuebao, 1999, 20(5), 34.

205 C. Shang and E. R. Blatchley III, Environ. Sci. Technol., 1999,33(13), 2218.

206 G. N. Coleman, G. R. Dulude, R. W. Starek and R. L. Stux,(Thermo Jarrell Ash, Franklin, MA 02038, USA). Presented atPittcon.'99, Orlando, FL, USA, March 7±12, 1999.

207 Y. G. Dong and J. J. Shen, Guangpuxue Yu Guangpu Fenxi, 1999,19(2), 206.

208 S. Scaccia, Talanta, 1999, 49, 467.209 S. Balasubramanian and V. Pugalenthi, Talanta, 1999, 50(3), 457.210 Y. L. Zhang, Lihua Jianyan, Huaxue Fence, 1999, 35(4), 174.211 L. Bencs, O. Szakacs and T. Kantor, Spectrochim. Acta, Part B,

1999, 54, 1193.212 R. Tepe, T. Jacksier and D. Vassallo, (Air Liquide, Countryside,

IL 60525, USA). Presented at Pittcon.'99, Orlando, FL, USA,March 7±12, 1999.

213 C. M. Wang, S. Z. Zhang, Q. Wu and J. G. Wang, GuangpuxueYu Guangpu Fenxi, 1999, 19(3), 375.

214 J. C. Avice, A. Ourry, P. Laine, N. Roland, S. Louahlia,E. Roussel, S. Brookes and J. Boucaud, Rapid Commun. MassSpectrom., 1999, 13(12), 1197.

215 S. L. C. Ferreira, C. F. de Brito, A. F. Dantas, N. M. Lopo deAraujo and A. C. S. Costa, Talanta, 1999, 48(5), 1173.

216 Z. L. Yang and J. G. Jia, Lihua Jianyan, Huaxue Fence, 1999,35(4), 188.

217 K. Tsuruya, T. Ueda and T. Misawa, Jpn. Kokai Tokkyo KohoJP 11 211,680 [99 211,680] (Cl. G01N23/223), 6 Aug 1999, Appl.1998/11,279, 23 Jan 1998; 4 pp.

218 D. Lu and W. J. Zhang, Lihua Jianyan, Huaxue Fence, 1999,35(3), 135.

219 T. Jach, J. Gormley and S. Thurgate, Spectrochim. Acta, Part B,1999, 54(10), 1539.

220 C.-F. Wang, F.-H. Tu, S.-L. Jeng and C.-J. Chin, GaodengXuexiao Huaxue Xuebao, 1999, 20(5), 70.

221 T. Y. Chen, Fenxi Shiyanshi, 1999, 18(3), 27.222 P. Neumaier, JOT, J. Ober¯aechentech., 1999(Spec., JOT

Automotive Surface Technology), 84.223 Z. T. Zhou, Y. H. Wang, Z. Q. Dong, K. Y. Tong, X. M. Guo

and X. W. Guo, Guangpuxue Yu Guangpu Fenxi, 1999, 19(5), 721.224 M. Soylak, L. Elci and M. Dogan, J. Trace Microprobe Tech.,

1999, 17(2), 149.225 C. Zhou, Y. Fan and L. H. Gao, Guangpuxue Yu Guangpu Fenxi,

1999, 19(5), 728.226 A. G. Gutierrez, R. A. Mortensen and J. Thomas, (Hewlett-

Packard Co., Wilmington, DE 19808, USA). Presented atPittcon.'99, Orlando, FL, USA, March 7–12, 1999.


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


227 W. Eiser and H. P. Beck, Fresenius' J. Anal. Chem., 1999, 364(5),417.

228 E. Hoffmann, C. Ludke, J. Kurner, H. Scholze, E. Ullrich andH. Stephanowitz, Fresenius' J. Anal. Chem., 1999, 365(7), 592.

229 O. Keil and D. A. Volmer, CLB Chem. Labor Biotech., 1999,50(12), 452.

230 A. Morak, A. Unkroth, R. Sauerbrey and K. Schneider, FieldAnal. Chem. Technol., 1999, 3(3), 185.

231 B. L. He, T. T. Peng and Z. G. Zhong, Guangpuxue Yu GuangpuFenxi, 1999, 19(5), 713.

232 Y. Lei, B.-Y. Lu and L.-W. Qui, (Dept. Chem., Nanjing Univ.,Nanjing 210093, China). Presented at Pittcon.'99, Orlando, FL,USA, March 7±12, 1999.

233 K. H. Hong, K. S. Song, H. K. Cha, M. Yang, J. M. Lee,C. W. Lee and G. H. Lee, J. Radioanal. Nucl. Chem., 1999,241(3), 533.

234 J. M. Barrero Moreno, M. Betti and G. Nicolaou, J. Anal. At.Spectrom., 1999, 14(5), 875.

235 F. Chartier, M. Aubert, M. Salmon, M. Tabarant and Bich HangTran, J. Anal. At. Spectrom., 1999, 14(9), 1461.

236 I. Rodushkin, P. Lindahl, E. Holm and P. Roos, Nucl. Instrum.Methods Phys. Res., Sect. A, 1999, 423(2±3), 472.

237 Y. Muramatsu, S. Uchida, K. Tagami, S. Yoshida andT. Fujikawa, J. Anal. At. Spectrom., 1999, 14(5), 859.

238 C.-S. Kim, C.-K. Kim, J.-I. Lee and K.-J. Lee, J. Anal. At.Spectrom., 2000, 15(3), 247.

239 M. Wallenius and K. Mayer, Fresenius' J. Anal. Chem., 2000,366(3), 234.

240 J. R. Schoonover and G. J. Havrilla, Appl. Spectrosc., 1999,53(3), 257.

241 C. J. Park, P. J. Oh, H. Y. Kim and D. S. Lee, J. Anal. At.Spectrom., 1999, 14(2), 223.

242 M. McCartney, K. Rajendran, V. Olive, R. G. Busby andP. McDonald, J. Anal. At. Spectrom., 1999, 14(12), 1849.

243 L. A. Lewis and G. K. Schweitzer, ASTM Spec. Tech. Publ.,1998, 1344(Applications of Inductively Coupled Plasma-MassSpectrometry to Radionuclide Determinations: Second Volume),99.

244 K.-C. Friese and V. Krivan, Fresenius' J. Anal. Chem., 1999, 364,(1±2), 72.

245 J. Hinrichs and B. Schnetger, Analyst (Cambridge, U. K.), 1999,124(6), 927.

246 K. Radhakrishnan, V. T. Kulkarni, A. B. Patwardhan,A. Ramanujam and A. G. Page, J. Anal. At. Spectrom., 1999,14(12), 1889.

247 H. A. Furusawa, J. E. S. Sarkis, M. H. Kakazu and C. Rodrigues,J. Radioanal. Nucl. Chem., 1999, 242(3), 647.

248 M. E. Ketterer and C. J. Khourey, ASTM Spec. Tech. Publ.,1998, 1344(Applications of Inductively Coupled Plasma-MassSpectrometry to Radionuclide Determinations: Second Volume),120.

249 F. Chartier, M. Aubert and M. Pilier, Fresenius' J. Anal. Chem.,1999, 364(4), 320.

250 R. Hearn, (AEA, Harwell, UK). Presented at Atomic Spectro-metry Updates Joint Meeting with Atomic Spectroscopy Group,Teddington, UK, March 18, 1999.

251 E. H. Evans, J. B. Truscott, L. Bromley, P. Jones, J. Turner andB. E. Fairman, ASTM Spec. Tech. Publ., 1998, 1344(Applicationsof Inductively Coupled Plasma-Mass Spectrometry to Radio-nuclide Determinations: Second Volume), 79.

252 J. B. Truscott, L. Bromley, P. Jones, E. H. Evans, J. Turner andB. Fairman, J. Anal. At. Spectrom., 1999, 14(4), 627.

253 J. S. Becker and H.-J. Dietze, Fresenius' J. Anal. Chem., 1999,364(5), 482.

254 R. K. Malhotra and K. Satyanarayana, Talanta, 1999, 50(3), 601.255 J. L. Parus, W. Raab and R. Mikolajczak, Adv. X-Ray Anal.,

1998, 40, 339.256 P. G. Bienvenu, E. A. Brochard and E. A. Excof®er, ASTM Spec.

Tech. Publ., 1998, 1344(Applications of Inductively CoupledPlasma-Mass Spectrometry to Radionuclide Determinations:Second Volume), 51.

257 S. Arias, Eur. Coat. J., 1999(3), 122.258 R. L. Schmehl, D. C. Cox, F. G. Dewalt, M. M. Haugen,

R. A. Koyak, J. G. Schwemberger Jr. and J. V. Scalera, Am. Ind.Hyg. Assoc. J., 1999, 60(4), 444.

259 J. L. Gerlock, T. J. Prater, S. L. Kaberline, J. L. Dupuie, E. J. Blaisand D. E. Rardon, Polym. Degrad. Stab., 1999, 65(1), 37.

260 C. Neelmeijer, I. Brissaud, T. Calligaro, G. Demortier,A. Hautojarvi, M. Mader, L. Martinot, M. Schreiner,T. Tuurnala and G. Weber, X-Ray Spectrom., 2000, 29, 101.

261 J. L. Ferrero, C. Roldan, M. Ardid and E. Navarro, Nucl.Instrum. Methods Phys. Res., Sect. A, 1999, 422(1±3), 868.

262 E. Aloupi, A. G. Karydas and T. Paradellis, X-Ray Spectrom.,2000, 29, 18.

263 P. Moioli and C. Seccaroni, X-Ray Spectrom., 2000, 29, 48.264 K. E. Nissen, J. T. Keegan and J. P. Byrne, Can. J. Anal. Sci.

Spectrosc., 1998, 43(4), 122.265 K. Fujiwara, Y. Toumori, H. Mitsumata, M. Inada and

T. Nakahara, Bunseki Kagaku, 1999, 48(7), 681.266 R. F. Elbahnasawy, J. G. McInerney and G. Hughes, Mater. Res.

Soc. Symp. Proc., 1999, 573(Compound Semiconductor SurfacePassivation and Novel Device Processing), 145.

267 R. Klockenkaemper and A. von Bohlen, Spectrochim. Acta, PartB, 1999, 54(10), 1385.

268 R. Klockenkaemper, A. von Bohlen, H. W. Becker andL. Palmetshofer, Surf. Interface Anal., 1999, 27(11), 1003.

269 S. Seki, H. Tamura and H. Sumiya, Appl. Surf. Sci., 1999, 147(1±4), 14.

270 B. Wiedermann, G. Raedlinger, H. C. Alt, K. G. Heumann andK. Bethge, Fresenius' J. Anal. Chem., 1999, 364(8), 772.

271 B. Wiedermann, H. C. Alt, J. D. Meyer, R. W. Michelmann andK. Bethge, Fresenius' J. Anal. Chem., 1999, 364(8), 768.

272 H. Ch. Alt, B. Wiedemann, J. D. Meyer, R. W. Michelmann,K. Bethge, Z. Liliental-Weber(Ed.) and C. Miner (Ed.), Carbonin semi-insulating gallium arsenide: a comparative study betweenFTIR, SSMS and CPAA. Semicond. Insul. Mater. 1998, Proc.Conf., 10th 1998, Inst. Electrical and Electronics Eng., NewYork, NY, USA, 1999, 53±56.

273 C. Hongo, M. Tomita and M. Suzuki, Appl. Surf. Sci., 1999, 144,306.

274 B. J. Kartheuser, K. Crener, P. Grange, R. Payling andP. Chapon, (UCL-CERTECH-CTAS, Seneffe 7180, Belgium).Presented at Pittcon.'99, Orlando, FL, USA, March 7±12, 1999.

275 M. Pidun, N. Lesch, S. Richter, P. Karduck, W. Bock,M. Kopnarski and P. Willich, Mikrochim. Acta, 2000, 132(2±4), 429.

276 T. Maeda, K. Mukaeda, T. Shimohira and S. Katsuyama,J. Dent. Res., 1999, 78(1), 86.

277 N. Valle and G. Libourel, Mineral. Mag., 1998, 62A(Pt. 3), 1561.278 T. G. Alley, S. R. J. Brueck and M. Wiedenbeck, J. Appl. Phys.,

1999, 86(12), 6634.279 A. Sears, D. Holland and M. G. Dowsett, Top. Issues Glass, 1998,

2(Reactions at Glass Surfaces), 69.280 C. Muller-Fildebrandt, S. Priller and G. H. Frischat, Glass Sci.

Technol. (Frankfurt/Main), 1999, 72(7), 227.281 O. Gedeon, V. Hulinsky and K. Jurek, Mikrochim. Acta, 2000,

132(2±4), 505.282 G. Volksch and J. M. Aroni, Mikrochim. Acta, 2000, 132(2±4),

511.283 K. Bange, H. Muller and C. Strubel, Mikrochim. Acta, 2000,

132(2±4), 493.284 A. J. G. Mank and P. R. D. Mason, J. Anal. At. Spectrom., 1999,

14(8), 1143.285 J. R. Almirall, K. G. Furton, D. C. Duckworth, C. K. Bayne,

S. J. Morton and R. D. Koons, (Intl. Forensic Res. Inst., Dept.Chem., Florida Intl. Univ., Miami, FL, USA). Presented atPittcon.'99, Orlando, FL, USA, March 7±12, 1999.

286 J. R. Almirall, D. C. Duckworth, C. K. Bayne, S. J. Morton,D. H. Smith, R. D. Koons and K. G. Furton, Proc. SPIE-Int.Soc. Opt. Eng., 1999, 3576(Investigation and Forensic ScienceTechnologies), 87.

287 Z. Smit, P. Pelicon, G. Vidmar, B. Zorko, M. Budnar,G. Demortier, B. Gratuze, S. Sturm, M. Necemer, P. Kumpand M. Kos, Nucl. Instrum. Methods Phys. Res., Sect. B, 2000,161, 718.

288 P. Kuisma-Kursula, X-Ray Spectrom., 2000, 29, 111.289 P. Tianyou, J. Zucheng and Q. Yongchao, J. Anal. At. Spectrom.,

1999, 14(7), 1049.290 T.-Y. Peng, Z.-C. Jiang, B. Hu and Z.-H. Liao, Gaodeng Xuexiao

Huaxue Xuebao, 1999, 20(5), 57.291 M. Hornung and V. Krivan, Spectrochim. Acta, Part B, 1999, 54,

1177.292 U. Schaeffer and V. Krivan, Anal. Chem., 1999, 71(4), 849.293 K. Kato, M. Ito and K. Watanabe, Fresenius' J. Anal. Chem.,

2000, 366(1), 54.294 G. S. Groenewold, A. D. Appelhans, G. L. Gresham, J. E. Olson,

M. Jeffery and M. Weibel, J. Am. Soc. Mass Spectrom., 1999,11(1), 69.

295 T. Tanaka, J. Kuramata, M. Seki and M. Hiraide, BunsekiKagaku, 2000, 49(1), 11.


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


296 E. Hoffmann, C. Ludke, J. Skole, H. Stephanowitz andG. Wagner, J. Anal. At. Spectrom., 1999, 14(11), 1679.

297 M. Mihay and R. D. Foust Jr, (Dept. Chem., Northern ArizonaUniv., Flagstaff, AZ 86011±5698, USA). Presented at 217th ACSNational Meeting, Anaheim, CA, USA, March 21±25, 1999.

298 L. Paama, T. Ilomets, I. Pitkanen, P. Peramaki andH. Ronkkomaki, (Inst. Chem. Phys., Univ. Tartu, 51014Tartu, Finland). Presented at Instrumental Methods of Analysis.Modern Trends and Applications (IMA '99), 19±22 September,1999, Chalkidiki, Greece.

299 J. L. Ruvalcaba-Sil, M. A. Ontalba-Salamanca, L. Manzanilla,J. Miranda, J. Canetas Ortega and C. Lopez, Nucl. Instrum.Methods Phys. Res., Sect. B, 1999, B150(1±4), 591.

300 I. Gyodi, I. Demeter, K. Hollos-Nagy, I. Kovacs andZ. Szokefalvi-Nagy, Nucl. Instrum. Methods Phys. Res., Sect.B, 1999, B150(1±4), 605.

301 J. Miranda, M. L. Gallardo, D. M. Grimaldi, J. A. Roman-Berrelleza, J. L. Ruvalcaba-Sil, M. A. Ontalba-Salamanca andJ. G. Morales, Nucl. Instrum. Methods Phys. Res., Sect. B, 1999,B150(1±4), 611.

302 J. Shi, Y. Hu, Z. Liu, H. Huang, Z. Yao, J. Hao, C. Zhou andC. Shan, Zhenkong Kexue Yu Jishu, 1998, 18((Suppl.)), 140.

303 M. Hall, C. Amraatuvshin and E. Erdenbat, J. Radioanal. Nucl.Chem., 1999, 240(3), 763.

304 A. E. Pillay, C. Punyadeera, L. Jacobson and J. Eriksen, X-RaySpectrom., 2000, 29, 53.

305 P. Mirti, X-Ray Spectrom., 2000, 29, 63.306 P. Mirti, M. Aceto and M. C. P. Ancona, Archaeometry, 1998,

40(2), 311.307 D. L. Hogan, V. V. Golovlev, M. J. Gresal®, J. A. Chaney,

C. S. Feigerle, J. C. Miller, G. Romer and P. Messier, Appl.Spectrosc., 1999, 53(10), 1161.

308 P. Lucena, J. M. Vadillo and J. J. Laserna, Anal. Chem., 1999,71(19), 4385.

309 K. Sumitani and H. Sugitani, Jpn. Kokai Tokkyo Koho JP 10300,649 [98 300,649] (Cl. G01N21/28), 13 Nov 1998, Appl. 97/110,578, 28 Apr 1997; 4 pp.

310 D. Wegrzynek, B. Holynska and J. Ostachowicz, X-RaySpectrom., 1999, 28, 209.

311 C. Seidel, H. Kopf, B. Gotsmann, T. Vieth, H. Fuchs andK. Reihs, Appl. Surf. Sci., 1999, 150(1±4), 19.

312 M. Resano, M. Verstraete, F. Vanhaecke, L. Moens, A. vanAlphen and E. R. Denoyer, J. Anal. At. Spectrom., 2000, 15(4),389.

313 N. Miki, K. Tanaka, A. Takahara and T. Kajiyama, J. Vac. Sci.Technol., B, 2000, 18(1), 313.

314 J. B. Metson and K. E. Prince, Surf. Interface Anal., 1999, 28(1),159.

315 A. H. Ashour, M. B. S. Osman and S. M. Mokhtar, J. Polym.Mater., 1999, 16(1), 23.

316 M. E. Rybak, P. Hatsis, K. Thurbide and E. D. Salin, J. Anal. At.Spectrom., 1999, 14(11), 1715.

317 B. Wagner, S. Garbos, E. Bulska and A. Hulanicki, Spectrochim.Acta, Part B, 1999, 54(5), 797.

318 D. Kolasa, K. Samsonowska and K. Zorawska, Chemik, 1998,51(4), 100.

319 H. Asakura, K. Ikegami and H. Wakita, Bunseki Kagaku, 1999,48(11), 973.

320 G. van Dalen, X-Ray Spectrom., 1999, 28(3), 149.321 F. Vanhaecke, M. Verstraete, L. Moens, R. Dams and

M. Nekkers, Anal. Commun., 1999, 36(3), 89.322 J. N. Keuler, L. Lorenzen, R. D. Sanderson, V. Prozesky and

W. J. Przybylowicz, Nucl. Instrum. Methods Phys. Res., Sect. B,1999, 158(1±4), 678.

323 L. L. Wang and Y. L. Bai, Guangpuxue Yu Guangpu Fenxi, 1998,18(5), 606.

324 M. A. Belarra, I. Belategui, I. Lavilla, J. M. Anzano andJ. R. Castillo, Talanta, 1998, 46(6), 1265.

325 M. A. Belarra, M. Resano, S. Rodriguez, J. Urchaga andJ. R. Castillo, Spectrochim. Acta, Part B, 1999, 54, 787.

326 C. Palacio, Surf. Interface Anal., 1999, 27(12), 1092.327 J. Chen and X.-W. Huang, Gaodeng Xuexiao Huaxue Xuebao,

1999, 20(5), 21.328 K. D. Besecker, C. B. Rhoades Jr. and B. T. Jones, At. Spectrosc.,

1998, 19(6), 193.329 H. Minamisawa, H. Kuroki, N. Arai and T. Okutani, Anal.

Chim. Acta, 1999, 398(2±3), 289.330 S. A. Baker and N. J. Miller-Ihli, (Dept. Agric., ARS, Beltsville

Human Nutrition Res. Center, Beltsville, MD 20705, USA).Presented at Pittcon.'99, Orlando, FL, USA, March 7±12, 1999.

331 B. Wehling, P. Vandenabeele, L. Moens, R. Klockenkamper,A. von Bohlen, G. Van Hooydonk and M. de Reu, Mikrochim.Acta, 1999, 130(4), 253.

332 R. Klockenkaemper, A. von Bohlen and L. Moens, X-RaySpectrom., 2000, 29, 119.

333 J. Diemer and K. G. Heumann, Fresenius' J. Anal. Chem., 1999,364(5), 421.

334 M. Yamagami, M. Nonoguchi, T. Yamada, T. Shoji, T. Utaka,Y. Mori, S. Nomura, K. Taniguchi, H. Wakita and S. Ikeda,Bunseki Kagaku, 1999, 48(11), 1005.

335 C. J. Park, K. J. Kim, M. J. Cha and D. S. Lee, Analyst(Cambridge, U. K.), 2000, 125(3), 493.

336 C. C. Wang, M. S. Hsu, W. J. Wei and Y. C. Ling, ZhenkongKexue Yu Jishu, 1998, 18(Suppl.), 97.

337 A. Seubert, Fresenius' J. Anal. Chem., 1999, 364(5), 404.338 H. Y. Chung, Y. H. Kim, H. D. Yoo and S. H. Lee, J. Korean

Chem. Soc., 1999, 43(4), 412.339 J. Jurczyk, R. Sitko, B. Zawisza, F. Buhl and E. Malicka,

Mikrochim. Acta, 1999, 132(1), 41.340 L. Paama, E. Parnoja and P. Peramaki, J. Anal. At. Spectrom.,

2000, 15(5), 571.341 A. B. Anfone and R. K. Marcus, (Dept. Chem., Clemson Univ.,

Clemson, SC 29634±1905, USA). Presented at Pittcon.'99,Orlando, FL, USA, March 7±12, 1999.

342 C. Strubel, L. Meckel and R. Effenberger, Glass Sci. Technol.(Frankfurt/Main), 1999, 72(1), 15.

343 J. G. Darab, E. M. Meiers and P. A. Smith, Mater. Res. Soc.Symp. Proc., 1999, 556(Scienti®c Basis for Nuclear WasteManagement XXII), 215.

344 O. Abollino, M. Braglia, C. Contardi, G. Dai, E. Mentasti,S. Mosso and C. Sarzanini, Anal. Chim. Acta, 1999, 383(3), 243.

345 Z. Samardzija, D. Makovec and M. Ceh, Mikrochim. Acta, 2000,132(2±4), 383.

346 T. Y. Peng, Z. C. Jiang, B. Hu and Z. H. Liao, Fresenius' J. Anal.Chem., 1999, 364(6), 551.

347 M.-H. Zhong, Gaodeng Xuexiao Huaxue Xuebao, 1999, 20(5), 5.348 I. E. De Vito, A. N. Masi and R. A. Olsina, Talanta, 1999, 49,

929.349 Z.-H. Sun, D.-H. Sun, S. Gu, H. Ying, X.-R. Wang and B.-

L. Huang, Gaodeng Xuexiao Huaxue Xuebao, 1999, 20(5), 15.350 S. Gu, H. Ying, Z.-X. Zhuang, P.-Y. Yang, X.-R. Wang, Z.-

H. Sun and B.-L. Huang, Gaodeng Xuexiao Huaxue Xuebao,1999, 20(5), 69.

351 S.-H. Hu, S.-L. Lin and S. Gao, Gaodeng Xuexiao HuaxueXuebao, 1999, 20(5), 79.

352 X. D. Cao, M. Yin and B. Li, Talanta, 1999, 48(3), 517.353 M. Yin, B. Li, X. D. Cao and Y. Zhang, Fenxi Huaxue, 1999,

27(3), 304.354 M. Yin, B. Li, Y. Zhang and X. D. Cao, Fenxi Shiyanshi, 1999,

18(3), 1.355 C. Shizhong, P. Tianyou, J. Zucheng, L. Zhenhuan and H. Bin,

J. Anal. At. Spectrom., 1999, 14(11), 1723.356 X. Liu, S. Cai, P. An, X. Wu, J. Chen and A. Zhang, Fenxi

Huaxue, 1999, 27(7), 782.357 S. Hamoudi, F. Larachi, A. Adnot and A. Sayari, J. Catal., 1999,

185(2), 333.358 P. Albers, K. Siebold, G. Prescher and H. Muller, Appl. Catal. A,

1999, 176(1), 135.


Publ

ishe

d on

28

Nov

embe

r 20

00. D

ownl

oade

d on

10/

12/2

013

18:4

3:44

.

View Article Online


Documents

Industrial analysis: metals, chemicals and advanced materials