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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1 29R

ATOMIC SPECTROMETRY UPDATE-CLINICAL MATERIALS, FOODS

AND BEVERAGES
Alistair A. Brown
Pye Unicam Ltd., York Street, Cambridge CB7 2PX, UK
David J. Halls
Trace Metals Unit, Department of Biochemistry, Royal Infirmary, Castle Street, Glasgow G4 OSF, UK
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Andrew Taylor
Supra-Regional Assay Service Metals Reference Laboratory, Robens Institute of Industrial and
Environmental Health and Safety, University of Surrey, Guildford, Surrey GU2 5XH, UK

Summary of Contents

1 Clinical Analysis
1.1, Application of Inductively Coupled Plasmas in Clinical and Biological Analysis
1.2. New Ideas and Developments
1.3. Progress for Individual Elements
1.3.1. Aluminium
1.3.2. Arsenic
1.3.3. Cadmium
1.3.4. Calcium and Magnesium
1.3.5. Chromium
1.3.6. Cobalt
1.3.7. Copper
. . and zinc
1.3.8. Iron
1.3.9. Lead
1.3.10. Manganese
1.3.1 1. Mercury
1.3.1 2. Nickel
1.3.13. Platinum
1.3.14. Rubidium
1.3.15. Selenium
1.3.16. Thallium
1.3.17. Vanadium
1.4. Conclusions
Table 1. Summary of An lyses of Bod! Fluids and Tissues

2 Analysis of Foods and Beverages

2.1. Sample Preparation
2.2. Analytical Techniques
2.3. Reference Materials and Quality Control Programmes
2.4. Topical Applications
2.5. Conclusions
Table 2. Summary of Analyses of Foods and Beverages

This review is the second Atomic Spectrometry Update and describes developments in the analysis of clinical materials,
foods and beverages. It is based upon publications and conference reports, received during the period September 1st
1984 to August 31st 1985. The references cited, prefixed by S/ or, for conference reports, S/C, may be found in the
supplement distributed to subscribersjo JAAS. References prefixed 86/ will appear in Volume 1 of JAAS. The format of
tables is similar to that used in A a d a I Reports on Analytical Atomic Spectroscopy. In the tables, in addition t o the
abbreviations listed elsewhere, Hy is used to show where hydride generation was employed and S, L and G in the
"Analyte form" column signify solid, liquid or gaseous sample introduction, respectively.
At a first glance (see tables) it is apparent that the analysis of clinical materials attracted the majority of research
interest. This may be related to the severe difficulties encountered in the analysis of these samples especially for the
determination of those elements which are present at microgram per litre levels in body fluids and tissues. In contrast,
the analysis of foods and beverages received little attention and this is reflected in the contributions t o this subject. The
authors have tried to present a critical appraisal of the reviewed literature. Readers who wish to comment on the text are
welcome to express their views through the letters section of JAAS. The authors would welcome any comments or
suggestions for improvements to future reviews.

30R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1
1. CLINICAL ANALYSIS
For the period of this review, two particular areas are
prominent. One is the large number of papers on ICP-OES
produced as new and experienced users try to justify a role for
it in the clinical laboratory. This is reviewed separately. The
second is the large number of papers on Al, which surely
qualifies it for the title “Element of the Year.” Interesting new
developments have occurred in FAAS, ETA-AAS and
ETA-AES for clinical applications. After these developments
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are reviewed, progress for individual elements is summarised.
1.1. Application of Inductively Coupled Plasmas in Clinical
and Biological Analysis
The large number of recent papers shows an increasing
interest in the use of inductively coupled plasma optical
emission spectrometry in this field (TableJ). Some of the work
is exploratory [e.g., Ca in serum (WOO) and Cd and Pb in
whole blood (S/176)] and appears to offer little advantage over
existing AAS techniques. The true multi-element capability of
ICP-OES is realised in studies such as that of Smith et al.
(S/592) on the determination of 12 metallic elements and B in
teeth enamel and dentine and that of Wanot et al. (S/981) who
determined Ca, Mg and P in stones. One advantage of the
ICP-OES technique is the ability to determine non-metals
such as B, P and S. This, together with the ability to determine
Ba, Bi, Ca, Mg and Sr with better sensitivity than existing
techniques, is cited by Allain and Mauras (S/C417) as reasons
for the spread of the technique. For the last five years, they
have routinely used a simultaneous Jobin-Yvon 48 spec-
trometer with 35 lines for the determination of Al, B, Ba, Ca,
Cu, Fe, K, Mn, P, S, Si and Sr in whole blood, plasma, urine,
dialysis fluids and tissue samples.
The advantages of ICP-OES in serum analysis seem
somewhat limited in that only a few of the important elements
have high enough concentrations to be determined. Kohl-
meier and Diehn (S/C530) introduced the technique into their
laboratory for the simultaneous determination of Cu, Fe and
Zn giving a between-batch RSD of less than 5 % for all
elements. Deijk et al. (MOO) compared different pre-
treatment methods for the determination of Ca in a serum
reference material (Precinorm U). Direct dilution gave results
which agreed with high-pressure digestion and low-
temperature ashing. Pre-concentration can be used to extend
the range of elements. Trace elements in digested samples can
be chelated on a poly(dithi0carbamate) resin which is then
digested with H202and HN03. This procedure was applied by
Mianshi and Barnes (S/984) to the determination of Cd, Co,
Cu, Fe, Mo, V and Zn in serum; As and Se were determined
by hydride generation ICP-OES. With all these steps, the
possibilities of contamination increase and this was reflected
in unrealistically high values for Mo (20.7 yg 1-1) and V (98.5
pg 1-1) in a normal serum. As others have shown [e.g.,
Kollmeier and Diehn (S/C530)], it is not necessary to
pre-concentrate for Cu, Fe or Zn. An alternative approach is
to use electrothermal atomisation. Matusiewicz and Barnes
(S/974) determined A1 and Si by injecting 5 yl of serum, urine
or dialysate fluid on to a Varian-Techtron CRA90
electrothermal atomiser for atomisation into a Plasma-Therm
ICP. Detection limits of 1.5 and 500 yg 1-1 were achieved for
A1 and Si, respectively.
To determine Cd and Pb in 5 ml of whole blood, Deijck et al.
(S/176) tried three different approaches: the
matrix-modification procedure of Stoeppler et al. (Analyst,
1978, 103, 714), low-temperature ashing and dry ashing. The
last two techniques were applied with pre-concentration using
8-hydroxyquinoline immobilised on controlled-pore glass.
Final determination was by microsampling of the analyte
essentially free from the matrix. While dry ashing followed
by pre-concentration gave reasonable results, it was recom-
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mended that to determine just these elements alone, AAS or
electrochemistry was simpler.
The technique of ICP-OES seems more at home with the
analysis of materials such as soft tissue (S/172, S/C455, S/613,
S/928), hair (S/506), nails (S/C455, S/C679), teeth (S/592),
stones (S/981) and bone (S/193, S/C455, S/613). Procedures
generally involve wet digestion with acid mixtures (S/193,
S/928, S/981); some workers prefer pressure digestion (S/172,
S/506, S/592). Chen et al. (S/506) compared dry ashing at
500-600 “C with H N 0 3 digestion under pressure followed by a
further HF - HC104 digestion. Dry ashing at 500 “C gave
comparable results to acid digestion but losses of A1 and Mg
were found on ashing at 600 “C. Good analytical performance
for the analysis of digested material is generally achieved for a
wide range of elements. For example, Marquardt et al. (S/193)
achieved RSDs of 0.5-1.6% for P; 1-3% for Ba, Ca, Cu, Fe,
Mg, Mn, Sr and Zn; and 4 9 % for K and Na.
Sulphur determination by ICP-OES using a VUV spec-
trometer at 180.7 nm has been investigated by Morita et al.
(S/921). Standard reference materials (serum, hair, liver,
mussel, Chlorella and orchard leaves) were analysed with
satisfactory accuracy following a high-pressure digestion with
HN03. The detection limit was about 10 yg 1-1.
Inductively coupled plasma mass spectrometry has yet to
make its impact on clinical or biological analysis; only one
p a s x (S/C294) discussed a biological analysis, oyster tissue.
1.2. New Ideas and Developments
The greater speed and convenience of flame atomic absorption
spectrometry compared with ETA-AAS make it the preferred
technique whenever sensitivity and sample size allows. An
interesting development in this area was the use of a slotted
quartz tube in the flame by Brown et al. (S/198,86/193) to give
greater sensitivity allowing the determination of Cd, Cu and
Pb in urine and Cd and Pb in blood after deproteinisation with
TCA. Devitrification of the quartz tube by urine samples was
reduced by coating the tube with La203. The technique has
also been applied to the determination of Cu and Zn in serum
(S/996) where the greater sensitivity allows greater dilution of
the sample (1 + 20) and a reduction of the sample volume, if
necessary, down to 20 yl. For the determination of Cu and Zn
in fractionated blood plasma, Bahreyni-Toosi et al. (S/999)
looked at various ways to increase sensitivity and decrease
sample requirement: pulse nebulisation, the slotted quartz
tube with pulse nebulisation and atomisation from a Delves
cup and from a Mo wire loop. They found only modest
improvements with the slotted quartz tube, preferring direct
pulse nebulisation for their particular determination.
The range of analyses possible by FAAS can also be
extended by pre-concentration. Platzer et al. (S/C514)
enriched trace metals from 100 ml of sample by using
dithiocarbamate groups bound to a solid carrier. The dithio-
carbamate chelates were then volatilised directly into the
burner of an FAAS instrument. Detection limits for Cd, Co,
Cu, Ni and Pb were between 0.02 and 0.2 yg 1-1. Realistic
applications of this technique are awaited.
Rocks and co-workers have coupled flow injection with
FAAS for the determination of Ca and Mg in serum (S/964)
and have taken the technique one step further with a new
development called “controlled-dispersion analysis’’ (CDA)
(Analyst, 1985, 110, 493). In this, a computer-controlled
peristaltic pump takes up a fixed volume of sample. The
sample probe then moves to the carrier solution and the pump
propels the sample slug within the carrier stream to the
spectrometer. This eliminates sample wastage as in conven-
tional FI sampling systems. Controlled-dispersion analysis has
been applied to the determination of Ca, Cu, Li, Mg and Zn in
serum.
If electrothermal atomic absorption spectrometry is to cope
with increasing workloads in clinical laboratories, it must run
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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1 31R

Table 1. SUMMARY OF ANALYSES OF BODY FLUIDS AND TISSUES

Technique;
atomisation ;
Element h/nm Matrix Concentration analyte form Sample treatment Reference
A1 - Dialysis fluids 4-67 pg I-' AA; ETA; L ETA-AAS with L'vov platform Sl118
A1 - Serum 6-220 pg I-' AA; ETA; L ETA-AAS with Zeeman background 9192
correction
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A1 - Biological samples, - AA; ETA; L ETA-AAS with metal atomiser and Zeeman SIC268
acid rain background correction
A1 - Serum 5-50 pg 1-1 AA; ETA; L Samples analysed directly or with dilution, s1479
graphitelzr-coated graphite furnace
A1 - Bone - AE; ICP; Lor Comparison of ICP-OES versus FAAS; Sl480
AA; F, both rechniques gave reliable results,
NzO - CzH2; L ICP-OES gave better detection limit
A1 - Serum, blood, 2-77 pg 1-1 AA; ETA; L Liquid samples diluted with Triton X-100, s1642
urine and tissues tissues wet ashed
A1 - Serum 1-150 pg I-' AA; ETA; L Samplesdiluted 1 + 1with H20,platform Sl858
atomisation, integrated absorbance, matrix
modificationsplus O2ashing
A1 309.3 Haemodialysis - AA; ETA; L Concentrated NO3added as matrix modifier Sl965
concentrates
A1 - Serum, hair 9-300 pg 1-1 AA; ETA; L Matrix destroyed by O2ashing in a Sl967
Zr-coated graphite tube at 500 "C
A1 - Body fluids 0-80 pg 1-1 AA; ETA; L Samples incubated with 2,4-pentanedione, s/973
extracted with 4-methyl-2-pentanedione
A1 308.2 Biological 0-100 pg I-' AE; ICP with None s1974
materials ETA; L
A1 - Serum 0-100 pg I-' AA; ETA; L Comparison of a direct analysis using L'vov Sl985
platform and matrix modification with a
protein precipitation method
A1 - Biological 0.3-300 pg 1-1 AE; ICP; L Matrix modificationwith Cs, Ga used as 86147
samples internal standard
A1 309.3 Dialysis fluids 1-120 pg 1-1 AA; ETA; L Matrix effects overcome by addition of 2% 86165
HN0, as matrix modifier
A1 - Biological - AA; ETA; Lor Comparison of ETA-AAS versus NAA 86lC160
materials NAA
A1 309.3 Serum - AA; ETA; L Optimisation of gases, tube materials, 861195
wavelengths and matrix modifiers
A1 309.3 Biological - AE; ETA; L Samples digested in HNO, 861197
materials
As - Body fluids, - AA; Hy; L Total As determined after wet ashing with Sl166
foods / HNO, - HC104- H2S04
As - Marine biological - AA; Hy; L Also includes determination of Hg and Se; S/590
tissues samples digested in pressure bomb with
HNO, for Hg; digested further with
HC104 - H2S04for As and Se
determination
As - Dietary - AA; ETA; L Metals separated from the matrix by solvent Sl863
supplements extraction with APDC - IBMK system
As - Biological - AA; Hy; L Wet digestion with HNO, - H2S04- Sl976
samples K2Cr207;both organic and inorganic
As compounds determined
Ca 393.37 Serum - AE; ICP; L High-pressure ashing, low-temperature ashing s1100
and direct dilution of sample investigated;
simple dilution preferred
Ca - Tissue - AA;-;L Content and intracellular distribution of S1647
Ca and Mg studied
Ca - Serum - AA; F, Flow injection coupled with FAAS, Sl964
air - C2H2;L 4 pl of sample injected into a flowing,
non-segmented reagent stream
Ca 315.9 Human stones - AE; ICP; L Samples digested in H N 0 3- HC104 Sl981
Cd 228.8 Urine 0-2 pgl-1 AA; ETA; L Standard-additions procedure; samples s1159
acidified with HN03
Cd 220.35 Blood - AE; ICP; L Comparison of digestion procedures Sl176
Cd 228.8 Biological - AA; ETA; S Solid samplingon to a graphite boat; Sl182
materials Zeeman background correction
Cd - Biological - AA; ETA; L Applications of O2ashing in ETA-AAS SIC553
materials
Cd 228.8 Liver tissue - AA; ETA; L or S Comparison of solid sampling and Zeeman SIC555
ETA-AAS versus a wet-digestion procedure
Cd - Hair - AA; -; L Samples soaked in neutral detergents, Sl589
washed with de-ionised H 2 0 , treated
with 95% ethanol; hair finally digested
with 7 ml H N 0 3 + 3 ml HC104,
evaporated, re-dissolvedin 0.1% Na2S04
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32R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1

Table 1. SUMMARY OF ANALYSES OF BODY FLUIDS AND TISSUES-continued

Technique;
atomisation;
Element hJnm Matrix Concentration analyte form Sample treatment Reference
Cd - Dietary - AA; ETA; L See As, ref. Sl863 Sl863
supplements
Cd 228.8 Urine ' - AA; ETA; L Investigationof various matrix modifiers, Sl963
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HN03was preferred
Cd 228.8 Urine 0.1-164 yg 1-' AA; ETA; L +
Samples diluted 1 1 with HzO, standard- Sl966
additions method and L'vov platform
Cd - Teeth - AA; ETA; L Sampleswet digested, solvent extracted into Sl970
CHC13then injected into graphite furnace
Cd 228.8 or Pancreatic tissue - AA; ETA; S Samples incubated at 37 "C with physiological Sl975
326.1 saline, freeze dried, solid samplingof
1-13 pg sample masses into graphite furnace
Cd 228.8 Urine - AA; ETA; L Comparison of calibration procedures 9998
Cd - Liver, renal cortex - AA; ETA; L Investigationof Cd body burden between 86/60
non- ,medium- and heavy-smokers
co - Plasma 0.15-10 1.18I-' AA; ETA; L Samples digested with HN03- HC104; Sl982
solvent extraction with APDC - IBMK;
direct injection into graphite tube
co - Whole blood, - AA; ETA; L Sampleshomogenised then direct injection Sl994
urine into graphite furnace; results compared
with an electrochemicalprocedure
Cr - Hair - AA;-;L See Cd, ref. Sl589 Sl589
Cr - Plasma, urine 0-3 yg 1-1 AA; ETA; L Standard-additions procedure Sl615
Cr - Serum - AA; ETA; L Samples dry ashed with Mg(N03)z, Sl616
re-dissolved in 0.1 M HC1
Cr - Enteral nutritional - AA; -; L Wet ashing of samples Sl789
solutions
Cr 357.9 Faeces - AE; ICP; L Samples digested with H N 0 3- HC104 Sl980
cu 324.7 Plasma protein - AA; ETA; L Comparison of 5 different graphite furnace Sl184
fractions systems
cu - Muscle tissue - AA; F, air - 0.8-12.0 mg of sample extracted with HN03 S1645
CzH2; L
cu 324.7 Liver 0-1000 yg 1-1 AA; F, air - Samples digested with HN03- H2S04for Sl987
C2H2; L 1h at 120 "C, diluted to 500 pl
cu - Liver - AA; -; L Samples digested with concentrated HN03 Sl923
at 60 "C; collaborative study
cu - Serum - AA; ETA; L +
Samples diluted 1 2 1with 1%Triton Sl785
X-100, M HNO, and 30 mM
NH4NO3; platform atomisation plus
peak-area measurement enabled calibration
with acid standards; continuum source
AAS (SIMAAC)
cu 324.7 Serum, urine - AA; F, air - +
Samples diluted 1 20, aspirated into a Sl996
CzH2; L slotted quartz tube; sensitivityimprovement
X 2-3
cu 324.7 Plasma protein - AA; F, air - Comparison of FAAS techniques for the Sl999
fractions C2H2; L determination of Cu and Zn in plasma
protein fractions; techniques included
pulse nebulisation, slotted quartz tube
and Delves cup
Fe - Liver 0-5 yM AA; F; L, or Comparison of 3 analytical methods (FAAS, Sl646
AA; ETA; L ETA-AAS, colorimetric analysis) for the
determination of Fe in liver biopsies
Fe 248.3 Liver 0-1500 yg 1-1 AA; F, air - See Cu, ref. Sl785 Sl785
C2H2; L
Fe - Serum - AA; ETA; L See Cu, ref. Sl987 Sl987
Hg 253.7 Blood, urine 1.7-5 pg 1-1 AA; cold vap. ;L Automated - computerised procedure for Hg Sl2
determination
Hg - Biological - AA; cold vap. ;L Comparison of digestion procedures, semi- 9157
materials closed or closed silica vessels required;
digest with HN03- HC104 at 200 "C,
time required varied from 1.5 to 8 h
depending on sample
Hg - Biological - AA; ETA; S See Cd, ref. Sl182 SO82
materials
- Marine biological - AA; cold vap. ;L See As, ref. Sl590 Sl590
Hi?
tissues
Hg - Blood, fish (Moo pgl-1 AA; cold vap.; L Various digestionprocedures including Sl904
tissue or AE; DCP; L HNO,, HN03- H2S04and
H2SO4 - KMn04
K 404.4 or Biological 1-600 yg ml-1 AA; F, air - Solid samples dry ashed, samples diluted Sl787
766.5 samples C2H2; L 1 + 99 with 1% CsCl
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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1 33R

Table 1. SUMMARY OF ANALYSES OF BODY FLUIDS AND TISSUES--continued

Technique ;
atomisation;
Element hlnm Matrix Concentration analyte form Sample treatment Reference
Mg - Whole blood, - AF; F; L Whole blood and serum deproteinised with s17
serum, urine 1 M HNO,; urine samples acidified with
0.04 M HCI; 200 PI sample aliquots
aspirated into flame; line and continuum
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source AFS
Mg - Muscle - AA;-;L See Ca, ref. Sl647 Sl647
Mg - Serum - AA; F; L See Ca, ref. Sl964 s1964
Mg 323.83 Human stones - AE; ICP; L See Ca, ref. Sl983 Sl981
Mn - Whole blood - AA; ETA; L Dilute 1 + 4 with 0.5% Triton X-100, pyrolytic SIC528
graphite tube, platform atomisation
Mn 279.5 Urine - AA; F, air - Coprecipitate Mn with La(OH)3, re-dissolve; s1977
C2H2; L direct aspiration
Mn 403.08 Urine - AE; ETA; L Samples acidified with 10-2 M HN03, 1 1 + 861211
or 1 + 5 dilution, acidified aqueous
standards for calibration
Na 330.2 or Biological samples 1-600 pg ml-1 AA; F, air - See K. ref. Sl787 9787
589.0 C2H2; L
Ni - Rat tissue AE; ICP; L Study of Ni uptake in the rat Sl187
Ni - Serum AA; ETA; L Matrix modification with NH4 oxalate, Sl196
standard additions for calibration
Ni 232.0 Serum, water AA; ETA; L Minimal sample preparation Sl810
Pb - Blood, melted AA; ETA; L Samples introduced into a pre-heated Sl28
snow furnace on a W-wire probe
Pb 283.3 Blood AA; ETA; L Sample added to solution containing 1M Sl158
HN03 plus 0.1% Triton X-100,
centrifuged; 10 or 20 pl of supernatant
injected into graphite furnace
Pb 220.35 Blood AE; ICP; L See Cd, ref. Sl176 Sl176
Pb - Biological AA; ETA; S See Cd and Hg, ref. Sl182 Sl182
materials
Pb - Blood, serum, AA; ETA; L or S Radiotracer study on the usefulness of S/191
urine, tissues various matrix modifiers; platform
atomisation and NH4H2P04recommended
Pb - Tissue AA; ETA; S Slurry atomisation into graphite furnace SIC246
after homogenisation of tissue samples
Pb - Biological AA; ETA; L See Cd, ref. SIC553 SIC553
materials
Pb - Tissue AA; ETA; S See Cd, ref. SIC555 SIC555
Pb - Hair AA; F; L See Cd, ref. S1589 Sl589
Pb - Whole blood AA; ETA; L Use of O2ashing in the graphite furnace SIC69 1
Pb - Urine AA; ETA; L Determination of Et2Pb in urine, chelation Sl811
with glyoxalbis(2-hydroxyanil), extraction
into IBMK
Pb - Dietary AA; ETA; L See As, ref. Sl863 Sl863
supplements
Pb - Whole blood AA; ETA; L Review on the use of reference samples Sl895
rather than reference methods
Pb 283.3 Whole blood AF; F, air - +
Samples diluted 1 9 with H20, s1995
C2H2; L fluorescence excitation at 283.3 nm,
measured at 405.8 nm, laser-excited FAFS
method
Pb - Whole blood AA; ETA; L Studies on the storage of blood samples for Sl1200
Pb determination
Pt - Animal tissue AA; ETA; L Wet digestion of samples, interference from s1979
HN03 removed by addition of NH3 to the
graphite furnace during the ash stage
Pt - Plasma AA; ETA; L Samples reacted with NaDDC, extracted Sl986
ultrafiltrate, into CHC13,direct insertion into graphite
urine furnace
Rb 780.0 Blood, plasma AE; F, air - Blood diluted 1 + 99, plasma 1 + 9, with a Sl497
C2H2; L solution containing 2.5 g 1-1 Cs, standards
matrix matched with inorganic
constituents
Rb - Erythrocytes, AA; ETA; L - Sl857
Dlasma
S 180.7 Biological samples - AE; ICP; L High-pressure decomposition with HNO, s1921
Se - Whole blood - AA; ETA; L Study on the use of O2 ashing, Ni matrix SIC27 1
modification and the interference of Fe
on Se
Se 196.0 Body fluids 5-100 pg I-' AA; Hy; L Samples digested in HNO, - HC104 - H2S04 s1494
with a final temperature of 310 "C
Se 196.0 Marine biological - AA; Hy; L See As, ref. Sl590 s1590
tissues
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34R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1

Table 1. SUMMARY OF ANALYSES OF BODY FLUIDS AND TISSUES--continued

Technique;
atomisation;
Element hlnm Matrix Concentration analyte form Sample treatment Reference

Se - Liver - AA; Hy; L Samples digested in HNO, - HC104with a SIC680

final temperature of 210 "C
Se - Enteral - AA;-; L See Cr ,ref. Sl789 Sl789
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nutritional
solutions
Se 196.0 Serum 0.01-0.1 pg ml-l AA; ETA; L Addition of 1YO Ni as matrix modifier Sl968
Si 250.7 Serum, urine, 0-100 pg 1-1 AE ;'ICP ;L See Al, ref. 9974 s1974
haemodialysis
fluids
T1 276.8 Blood, urine, 0-200 pg 1-1 AA; ETA; Lor Blood and urine samples diluted with 0.1 M Sl160
hair AA; ETA; S HN03, hair analysed directly by solid
sampling
Tl 276.8 Urine 0-1.65 yg 1-1 AA; ETA; L Urine pH adjusted to pH 7 , NaDDC added, 9643
extracted into toluene
Zn 213.9 Serum - AA; ETA; L Serum proteins separated by gel-filtration s1103
chromatography and affinity
chromatography, Zn associated with az-
macroglobulin
Zn 213.9 Tissue 40-400 pg 1-1 AA; F, air - Samples digested in HNO, s1104
CzHz;L or
AA; ETA; L
Zn 213.9 Red blood cells - AA;-;L Samples diluted 1 + 19 with HzO Sl106
Zn - Plasma protein - AA; ETA; L See Cu, ref. Sl184 Sl184
fractions
Zn - Blood cells - AA; F, air - Blood samples separated on a discontinuous 9617
C2H2; L gradient of colloidal Percoll
Zn 213.9 Muscle - AA; F, air - See Cu, ref. Sl645 Sf645
W z ;L
Zn 213.9 Liver 0-1000 pg 1-1 AA; F, air - See Cu and Fe; ref. Sl785 9785
C2H2; L
Zn - Serum - AA; ETA; L See Cu and Fe, ref. Sl987 9987
Zn 213.9 Serum, urine - AA; F, air - See Cu. ref. Sl996 Sl996
CzHz; L
Zn 213.9 Serum, plasma - AA; F, air - Comparative study of FAAS methods for the s1997
CzH2; L determination of Zn in serum and plasma
Zn 213.9 Plasma - AA; F, air - See Cu, ref. Sl999 s1999
CzH2; L
Various - Biological - AE; DCP; L Optimisation of parameters for d.c. arc S18
(7) materials excitation (Ag, Li, Mn, Ni, Pb, V and Zn)
Various - Animal tissue - AE; ICP; L Samples decomposed by dry ashing at 700- Sl108
(6) 800 "C or wet digested with HN03 - HC104
(Ce, La, Nd, Pr, Sm and Y)
Various - Hair - AA; For ETA; L Multi-element analyses of hair samples Sl156
(11)
Various - Biological - AE; ICP; L Samples digested with HNO, - HC104 s1172
(18) samples
Various - Biological - AE; ICP; L Samples digested with H N 0 3 - HC104, Co s1193
(11) samples used as internal standards
Various - Serum - AA; ETA; L Simultaneous multi-element determination of s1194
(7) trace elements by SIMAAC, 2-ml serum
sample dry ashed with Mg(N03)2, re-
dissolved with 0.5 ml Of 0.5% HNO,,
platform atomisation (Al, C o , Cr, Mn, Mo,
Ni and V)
Various Human placenta AA; F; L Optimisation of digestion procedures; s1195
(5) H2S04,HNO,, H N 0 3 - HZSO4 all
gave good results (Ca, Cu, Fe, Mn and Zn)
Various Brain tissue, AE; ICP; L - SIC455
(11) bone, nails
Various Blood, plasma, AE; ICP; L Advantages of ICP-OES in the clinical SIC417
(12) urine laboratory
Various Biological AE; DCP, Hy; G Continuous-flow hydride or cold vapour SIC473
(4) materials generation with d.c. arc determination
(As, Se, Te and Hg)
Various Hair AE; ICP; L Samples digested in HNO, - H F - HC104 Sl506
(17)
Various Teeth AE; ICP; L Teeth cleaned with H202,digested in Sl592
(13) pressure bomb with HN03
Various Biological AE; ICP; L Review Sl613
material
Various Nails AE; ICP; L International comparison of the SIC679
(21) concentration of 21 elements in human nails
 View Article Online

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1 35R

Table 1. SUMMARY O F ANALYSES O F BODY FLUIDS AND TISSUES-continued

Technique;
atomisation;
Element hlnm Matrix Concentration analyte form Sample treatment Reference

Various - Biological Multi-element analysis in veterinary SIC709

(20) materials medicine, review
Various - Blood, urine - AE; ICP; L Electrothermal vaporisation for ICP-OES, SIC719
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review
Various - Animal tissue - AA; For ETA; L Automated wet digestion of samples 9862
(7) (As, Cd, Cu, Hg, Pb, Se and Zn)
Various - Whole blood, - AA; F, air - General review on the advantages of the S/918
(4) serum, urine CZHZ; L slotted quartz tube and FAAS
(Cd, Cu, Pb and Zn)
Various - Hair, urine AA; ETA; L Pressure digestion of samples with HN03 S1969
(5) in PTFE bomb, platform atomisation and
matrix modification recommended (As, Cd,
Cr ,Pb and Se)
Various - Serum AE; ICP; L Samples digested in HNO, - HCIO, in S1984
(9) pressure bomb, pre-concentrated on ion-
exchange resin, resin digested with
H202- HNO, (As, Cd, Co, Cu, Fe,
Mo, Se ,V and Zn)
Various - Serum, urine - AA; ETA; L Improving analysis time of ETA-AAS Sl993
(4) analytical methods (Al, Cd, Cu and Pb)
Various - Lung tissue - AA;-;L Review of digestion procedures (Al, Ga, SIC1136
(4) Mg and Si)
Various - Platelets - AA; F; L Samples digested in sealed decomposition s11203
(4) bomb, discrete nebulisation (Ca, K, Mg and
zn)
Various - Urine - AE; ICP; L Sample introduced into ICP on a wire loop; 86lC157
(6) sample dried near base of ICP for 30 s
(Al, As, Be, Cd, Pb and Se)
Various - Blood, serum, - AA; F, air - Applications of a slotted quartz tube to the 861193
(4) urine C2H2; L analysis of biological materials; serum
diluted 1 + 20, whole blood deproteinised
with TCA, urine acidified with 0.1% HCI
(Cd, Cu, Pb and Zn)

faster. Again in the pursuit of a rapid, sensitive method for the
determination of Cu and Zn in plasma fractions, Bahreyni-
Toosi et al. (S/184) compared five separate laboratory-built
ETA systems. A conventional Massman furnace was the most
sensitive, but also the slowest. None of the systems were rapid
enough to meet the stipulated requirement (cycle time < 30 s).
Halls (S/993), using a commercial Perkin-Elmer furnace with
uncoated tubes, was able to achieve cycle times of around 60 s
for Cd and Pb in blood after deproteinisation, A1 in water and
Cu in urine; the short programmes accentuated the slowness
of the autosampler (operation time 29 s). Drying of samples
could be achieved in under 10 s and in some analyses (Pb in
blood and Cu in urine) the ashing stage could be omitted
without affecting the performance of the method. Similar
ideas were applied to the determination of A1 in dialysate
fluids (86/65), which resulted in a two-step programme
(combined dry - ash and atomise) of cycle time 56 s.
Development of the stabilised temperature plalform furnace
concept (STPF) continues. Voellkopf and Grobenski (9969)
have applied it to the determination of As, Cd, Cr, Pb and Se
in milk powder, human hair and urine using Zeeman-effect
background correction. Different matrix modifiers were
applied for each element. Stoeppler et al. (S/CSSl) have
described their experience in the use of the STPF concept in
the determination of Al, Cd and Pb in biological and
environmental materials. They concluded that for measure-
ment near detection limits, peak height should be used and
direct comparison made with practically identical control
materials or a matrix-matched standard curve should be used.
This would seem to indicate that the STPF concept, designed
to eliminate interferences and allow direct analysis, may not
always be successful. Another way of ensuring that the
temperature within the furnace is higher than the sample is to
introduce the sample on a wire probe, as Edmonstone and
Van Loon (S/28) have described for the determination of Pb in
blood.
Simultaneous multi-element atomic absorption spectrometry
with continuum source (SIMAAC) and with electrothermal
atomisation has been applied by Lewis et al. to the determina-
tion of Cu, Fe and Zn in serum (S/987) and to Al, Co , Cr ,Mn ,
Mo, Ni and V in serum (S/194). In the first paper, serum
samples were diluted 1 + 20 with a diluent containing
0.1% WVTriton X-100,O.Ol M HN03 and 0.03 M NH4N03. In
the second, a four-fold pre-concentration was achieved by dry
ashing 2 ml of serum with Mg(NO& as an ashing aid - matrix
modifier; the ash was re-dissolved in 0.5 ml of 5% V/V HN03.
While normal levels of Al, Cr, Mn and Ni could be determined
successfully, insufficient sensitivity was available for Co, Mo
and V determination. Day-to-day precision was of the order of
2O-3OYo RSD.
Clinical applications of electrothermal atomisation atomic
emission spectrometry continue to show that for many
analyses, it is at least as sensitive and accurate as ETA-AAS.
Two recent applications are the determination of Mn in urine
by Frech et al. (86/211) and A1 in blood, cortex and liver by
Baxter et al. (86/197).
There have been some interesting developments in solid
sampling for ETA-AAS. Fietkau (S/C246) homogenised
animal tissue in a commercial homogeniser to a median
particle size of about 6 pm, diluted it to 1-10% m/mtotal solids
and pipetted this directly into the graphite furnace. The
problem of smoke causing a high non-specific absorbance was
overcame by using air ashing as part of the furnace pro-
gramme. Lead could be determined down to 60 pg kg-1 in
liver tissue giving results in good agreement with those
obtained after wet ashing. Rosopulo et al. (S/182) used the
graphite-boat technique for sample introduction and a Zee-
man system to overcome the effect of high background.

36R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1
Results obtained on the analysis of SRMs (e.g., bovine liver)
were within the certified range. The precision of solid
sampling analysis was found to equal that of conventional
ETA-AAS determination after wet digestion. The same
approach was applied to the determination of Cd and Pb in
liver tissue from animal carcasses for legal inspection purposes
(S/C555). In situ ashing with 0 2 in the graphite tube has been
used by Mohl et al. (S/C553) for the pre-treatment of difficult
materials, such as cow and human milk, serum and animal
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muscle. Liquid samples were injected directly after addition of
Triton X-100, whereas solid samples were inserted directly
using the Perkin-Elmer solid sampling accessory.
1.3. Progress for Individual Elements
1.3.1. Aluminium
It is a measure of the difficulty of an analysis when a large
number of papers on that determination appear (Table 1)
often with the adjective “improved” in the title. Amidst the
claims and counter-claims of the accuracy of analysis based on
simple aqueous standards, it is refreshing to find a paper that
looks at some of the fundamental problems of serum A1
determination by ETA-AAS and helps to clarify the situation.
Gardiner et al. (86/195) compared signals from A1 standards
and A1 in serum in the presence and absence of various matrix
modifiers for a standard uncoated tube, a pyrolytically-coated
tube and a L‘vov platform in a pyrolytically-coated tube. The
effect of different sheath gases was also examined. Whereas
with uncoated tubes, serum could be analysed directly against
aqueous standards using 0.1% Triton X-100 in 0.001 M H N 0 3
as a diluent with or without the addition of Mg(N03)2 as a
matrix modifier, the use of pyrolytically-coated tubes gave a
matrix effect which was not eliminated by the use of
Mg(N03)2. With the platform, Mg(N03)2 did eliminate the
interference and allowed calibration against standards simil-
arly diluted. Other factors that were considered important in
the choice of tube were sensitivity (the platform is the most
sensitive), sample load and number of firings possible with
each tube. An interesting suggestion was the use of the
alternative 396.2-nm line for analysis, which gave greater
linearity with only about 20% loss in sensitivity.
Brown et al. (S/985) found that the method of Leung and
Henderson (Clin. Chem., 1982, 28, 2139) based on a L’vov
platform and Mg(N03)2as a matrix modifier did not allow the
use of simple aqueous standards as had been claimed. They
found mean slopes of 1.35, 3.44, 2.41 and 1.80 X 10-3
absorbance 1 pg-1 for aqueous standards, normal sera,
uraemic sera (<300 yg 1-1) and uraemic sera (>300 pg l-l),
respectively. By contrast, Bettinelli et al. (S/858), using a very
similar procedure, but with an O2 ashing step, found good
agreement between calibration slopes in aqueous solution and
serum samples. Brown et al. (S/985) recommended the
method of standard additions for calibration or alternatively
the pre-treatment of the serum with H N 0 3 to precipitate the
proteins and then the analysis of the supernatant against
simple aqueous standards. Good agreement was obtained
between the two approaches.
Whether a platform is necessary for A1 determination is
debatable. D’Haese et al. (S/642) using an uncoated graphite
tube, determined A1 in serum against simple aqueous stan-
dards using H 2 0 only as a diluent. Identical results were
obtained with direct and standard-additions calibration and
excellent results in the Trace Elements Quality Assurance
Scheme run by the University of Surrey were obtained. The
mean serum A1 concentration for ten healthy controls was 2.0
k 0.4 pg 1-1. Zirconium-coated tubes have been used by a
number of workers (9479, S/642, S/967).
Whole blood analysis by ETA-AAS using dilution of
samples 1 + 3 with 2 g 1-1 Triton X-100 and direct analysis
against standards also in Triton X-100 was examined by
D’Haese et al. (S/642). For patients on haemodialysis, serum
View Article Online
and whole blood concentrations were not significantly differ-
ent, although whole blood concentrations for healthy subjects
(12.1 k 1.5 pg 1-1) were higher than for serum (see above).
Dialysate fluids cause a negative matrix interference in the
determination of A1 in an uncoated graphite tube. Fagioli et al.
(S/118) used a L’vov platform to overcome this and found
good recoveries both with and without the addition of
Mg(N03)2 as a matrix modifier. Total furnace programme
time was 97 s. Halls and Fell (86/65) overcame the interference
by acidifying to 2% V/V with H N 0 3 and used a two-stage
programme (combined dry - ash and atomise) to achieve a
furnace programme time of only 30 s. Nitric acid was also used
by Allain et al. (S/965) as a modifier for the analysis of
haemodialysis concentrates by ETA-AAS.
Even faster throughput of samples is undoubtedly possible
with inductively coupled plasma optical emission spectrometry.
Mauras and Allain (86/47) have described their automated
method for A1 in plasma, dialysate fluid and water using Ga as
an internal standard and Cs as a matrix modifier. Good
correlation of results was obtained with ETA-AAS for plasma
and water samples. As this direct approach is possible, the use
of ICP-OES combined with electrothermal atomisation pro-
posed by Matusiewicz and Barnes (S/974) for the determina-
tion of A1 in these matrices seems unnecessarily complicated.
An alternative approach to A1 determination is the use of
electrothermal atomisation atomic emission spectrometry.
Baxter et al. (861197) applied this technique with a constant-
temperature furnace to the analysis of whole blood, cortex and
liver samples after digestion with HN03. Good agreement was
found with results obtained using a conventional ETA-AAS
system and the L’vov platform.
Other biological samples that have been examined are hair
(S/967), soft tissues (S/642) and bone (S/480, S/642).
Homogeneity of material can be a problem as found by
Kratchovil et al. (86/C160) who examined a reference
material, TORT-1 (marine biological material), and found
that when sample aliquot size was decreased from 300 to 30
mg, the between-aliquot variation increased. This was blamed
on inhomogeneity caused by microparticulates of Al.
1.3.2. Arsenic
For the hydride generation AAS analysis of marine biological
tissue, Welz et al. (S/590) applied a digestion with HN03,
H2S04 and HC104 at a final temperature of 310 “C. Good
agreement was found with results obtained after combustion
of the sample in a stream of 02.Webb and Carter (S/976)
preferred a digestion with HN03, H2S04and K2Cr207to give
a quantitative breakdown of dimethylarsonic acid. They
applied their method to the determination of As in water,
urine, faeces and whole blood with recoveries in the range
92-105%.
More important often than a knowledge of total As is to
know the proportions of the various species. Stoeppler and
Ape1 (S/166) differentiated between toxic inorganic As and its
metabolites and the more stable and much less toxic arseno-
betaines (which occur in fish). Wet digestion with HN03,
HC104 and H2S04was used followed by hydride generation
AAS.
1.3.3. Cadmium
In tissue analysis for Cd, possibilities of solid sampling have
been explored. Nilsson and Berggren (S/975) freeze-dried
pancreatic tissue and then analysed 1-13 yg amounts directly
in a Varian CRA90 furnace. For Cd in liver tissue, Rosopulo et
al. (S/C553) used direct solid analysis with Zeeman AAS and
found good agreement with results after wet digestion. More
conventional wet digestion - AAS procedures have been used
for Cd in prostate glands (S/920), teeth (S/970) and liver and
renal cortex (86/60). The last study, an estimate of the Cd
body burden of an occupationally non-exposed population in

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1
Southern Bavaria, again confirmed the great increase in body
burden caused by smoking.
Determination of Cd in urine by ETA-AAS continues to be
a problem. Feitsma et al. (S/963) concluded that of the various
matrix modifiers they examined , HN03 was preferable. Nitric
acid was also used by Dungs and Neidhart (S/998) in the
determination of Cd in urine on the L'vov platform by a
standard-additions procedure. A graphics display, giving both
corrected and uncorrected signals, was considered of great
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importance and was shown to be of value when examining a
reference material (Lanonorm Control Urine). This sample
gave problems with background correction, even with a
Zeeman system, which were not seen with natural urines.
Further modification of the method was needed for this
sample. McAughey and Smith (S/966) tried a combination of
the L'vov platform and (NH4)2HP04, but found that the
modifier could only be used after time-consuming purification
to reduce blank levels. Instead they developed a method based
on selective volatilisation of Cd at 800 "C from a L'vov
platform. Calibration was by standard additions and a
detection limit of 0.06 pg 1-1 was achieved. A similar method
based on standard additions but using an uncoated graphite
tube was used by De Groot et al. (S/159).
1.3.4. Calcium and magnesium
Although Ca and Mg determinations in serum, urine and
tissues are well established, there is still some development in
the measurement of Ca and Mg levels in blood cells, some at
very low levels. Gerlach et al. (S/C531) determined low levels
of Ca in erythrocytes (<1 pg g-1) by ETA-AAS. All steps in
the analysis were verified by the use of a 47Ca tracer. Dust-free
conditions had to be used to reduce contamination. Mono-
nuclear cells were separated on a discontinuous Ficoll -
Hypaque gradient by Elin and Hosseini (S/922). After lysing
and dilution with La solution, the Mg content was determined
by FAAS. Makino (S/1203) separated platelets by differential
centrifugation and digested them in a PTFE bomb. Discrete
nebulisation FAAS was used for the measurement of Ca and
Mg*
1.3.5. Chromium
To determine Cr in serum by ETA-AAS, Veillon et al. (S/616)
used Mg(NO& as an ashing aid and matrix modifier. Samples
with Mg(N03)2 added were lyophilised and dry ashed in
silanised quartz tubes. Chromium was determined after the
ash had been re-dissolved in 0.1 M HC1. A mean normal Cr
concentration of 0.11 k 0.07 pg 1-1 was found for 15 adults.
Very strict control of contamination was necessary. The
method has been applied to studies of the effect of Cr
supplementation and glucose loading (S/927), from which it
was concluded that serum Cr concentration does not appear to
be a meaningful indicator of Cr status. The same dry-ashing
procedure was used by Lewis et al. (S/194) to give a four-fold
pre-concentration for determination by ETA-SIMAAC.
Their mean value for 30 normal subjects was 0.24 1-18 1-1.
Morris and Kemp (S/615) determined Cr in plasma and urine
by ETA-AAS with a W lamp source for background correc-
tion. Samples were diluted 1 + 1 with 0.3% V/VTriton X-100
and analysed by use of standard additions. Mean normal
values of 0.82 k 0.52 yg 1-1 for plasma Cr and <1.0 pg 1-1 for
urine were obtained. Since the value for plasma is higher than
what is now regarded as a realistic value (<0.5 pg 1-I), it can
be concluded that insufficient precautions were taken in
sample collection (e.g., stainless-steel needles were used).
1.3.6. Cobalt
The problem of determining the low levels of Co in serum by
ETA-AAS was approached by Anderson and Hoegetveit
(S/982) through the use of solvent extraction of digested
plasma with APDC into IBMK. Recovery was checked with a
View Article Online
37R
~ C tracer.
O A detection limit of 0.05 pg 1-1 and a mean
normal concentration of 0.15 yg 1-1 was obtained. The
application of the ETA-SIMAAC system to the determination
of Co (S/194) gave a detection limit of 0.57 pg l-l, which was
insufficient to give reliable values for normal levels.
Similar problems of insufficient sensitivity were encoun-
tered by Heinrich and Angerer (S/C525) in the development
of a method for Co in whole blood. To remove matrix
interferences in ETA-AAS , samples were diluted eight-fold
and a multi-stage ashing procedure was used. The method was
suitable for occupational levels, but not for natural levels.
Urine was analysed after solvent extraction.
1.3.7. Copper and zinc
As with Ca and Mg, developments for Cu and Zn are mainly in
studies of the cellular components of blood and the distribution
in plasma. Milne et al. (S/617) separated platelets, mono-
nucleated cells, polymorphonucleated cells and erythrocytes
by use of a discontinuous Percoll gradient and measured the
Zn content of the cells by H N 0 3 digestion and FAAS using
pulse nebulisation. Because of the high Zn concentration of
platelets, the values for mononuncleated cells depended
greatly on the extent of contamination from platelets. Makino
(S/1203) measured Zn in platelets using separation by
differential centrifugation, digestion in a PTFE bomb and
analysis by FAAS using pulse nebulisation. Red cells were
analysed by Chen and Zhao (S/106) for Zn by FAAS after
dilution 1 + 19 with distilled water. Their conclusion that
erythrocyte Zn was a better index than plasma or serum for
nutritional and metabolic studies is one that few are likely to
agree with. Using gel-filtration chromatography combined
with affinity chromatography (to separate albumin) and
ETA-AAS, Foote and Delves (S/103) found that most of the
Zn in the globulin fraction of human serum was bound to
a*-macroglobulin; no Zn was associated with transferrin.
Although tissue analysis for Cu and Zn seems straight-
forward, it is apparent from a collaborative study on the
determination of Cu by Osheim and Ross (S/923) that
agreement between laboratories could still be improved. In
this study, 11 laboratories analysed four blind duplicate pairs
of bovine liver samples by digestion with H N 0 3 at 60 "C and
determination by AAS. Within-laboratory variation ranged
from 5.6 to 19% RSD and between-laboratory variation was
7.1-21% RSD. Most methods for tissue analysis use acid
digestion followed by FAAS determination and similar
methods have been applied to Cu and Zn in liver biopsies
(S/785), Zn in prostate tissue (S/920) and Zn in rat intestine,
kidney and liver (S/104). For determinations of Cu and Zn in
human placenta, Imaeda et al. (S/195) used acid extraction
with 0.5 M H2SO4 or 1 M HN03. Results compared well with
those obtained after wet digestion in a PTFE bomb.
1.3.8. Iron
Kreeftenberg et al. (S/646) have compared the determination
of Fe in liver biopsies by the three different methods:
colorimetry using thiocyanate as a complexing agent, FAAS
and ETA-AAS. A good correlation was found between all
three methods. Of the three, the FAAS method was quickest,
but the ETA-AAS method was more suited to small sample
masses.
Serum Fe has been determined after deproteinisation with
TCA by Zhong et al. (S/105). Triton X-100 and NH4N03were
used as matrix modifiers in the final determination by
ETA-AAS with Zeeman-effect background correction. Li et
al. (S/971) used FAAS with tartaric acid as a matrix modifier
to increase the sensitivity and reduce interferences.
1.3.9. Lead
Direct determination of Pb in whole blood by ETA-AAS has
been frequently described in previous years. Oxygen ashing

38R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1
has been used by Shiowatana and Matousek (S/C691) to help
resolve Pb peaks from the interfering background absorption.
Direct calibration with aqueous standards was possible.
Schmid and Krivan (S/191) investigated the behaviour of Pb in
the graphite furnace during ashing with 203Pb as a radiotracer
for a number of matrices including blood, serum and urine.
Optimum elimination of matrix effects was achieved by
simultaneous use of a L'vov platform and NH4H2P04 as a
matrix modifier. Stoeppler et al. (S/158) have described a
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modified version of the original Stoeppler , Brandt and Rains
method for Pb in blood (Analyst, 1978, 103,714). Samples
were diluted with 1 M H N 0 3 containing 0.1% Triton X-100.
After centrifuging off precipitated cells and proteins, the
supernatant was analysed by ETA-AAS. Comparison of
results was made with isotope dilution MS and differential
pulse ASV. Blood samples for Pb determination were shown
by Wang and Frank (S/1200) to be stable for at least ten weeks
whether stored at 22, 4 or -20 "C using either EDTA or
heparin as an anticoagulant.
Omenetto et al. (S/995) showed that the determination of Pb
in blood was possible by laser-excited atomic fluorescence
spectrometry. Samples diluted ten-fold were nebulised into an
air - C2H2 flame. Excitation at 283.3 nm by a frequency-
doubled pulsed tunable dye laser stimulated fluorescence
which was measured at 405.8 nm. A detection limit of 4 pg 1-1
was achieved and results were in good agreement with those
obtained by ASV and Delves cup AAS.
Extracted tetramethyllead from whole blood was deter-
mined by combining high-resolution GC with ETA-AAS
(S/978). A detection limit of 10 pg 1-1 as tetramethyllead was
obtained. Diethyllead in urine can be measured by chelation
with glyoxal-bis-(2-hydroxyanil) and extraction into IBMK, as
Turlakiewicz et al. have shown (SBll). Determination of Pb
in the extract was made by ETA-AAS. The method success-
fully discriminated against both triethyllead and inorganic
lead.
1.3.10. Manganese
The technique of ETA-AES has been applied to the determi-
nation of Mn in urine by Frech et al. (86/211). Urines diluted
+
1 5 with 0.01 M H N 0 3 were analysed at the 403.1-nm line
directly against standards in 0.01 M HN03. The results
correlated well with those obtained using an ETA-AAS
method. Pre-concentration of Mn in urine by co-precipitation
with La(OH)3 formed the basis of an FAAS method elabor-
ated by Holler et al. (S/977).
Bayer (S/C528) proposed that, since over 90% of Mn in
blood is present in red cells, whole blood Mn determination
may be more appropriate than serum analysis. Blood (200 pl)
was diluted with 500 pl of 0.5% V/VTriton X-100 and the Mn
determined by standard additions on a L'vov platform in an
ETA-AAS system. The ETA-SIMAAC system of O'Haver
and co-workers (S/194) gave a mean normal Mn concentration
of 0.48 pg 1-1 for serum; measurements were close to the
detection limit (0.11 pg 1-1).
As a result of hair Mn measurements on newborns and their
mothers, Saner et al. (86/3) concluded that determination of
Mn in prenatal maternal hair may prove to be a reliable
indicator of the risk of intrauterine malformations. Hair
samples were dry ashed, dissolved in HCl and analysed by
ETA-AAS.
1.3.11. Mercury
Since Hg is so volatile, losses can easily occur during the
sample pre-treatment stage. May and Stoeppler (S/157)
avoided losses by digestion with H N 0 3 and HClO4 in partly
closed or completely closed silica vessels heating cautiously
from 20 to 200 "C over 1&15 min. Welz and Melcher (S/590)
recommended pressure digestion with H N 0 3 in a PTFE bomb
for marine biological tissues.
View Article Online
Cold-vapour AAS is still the most popular technique for
measurement of Hg. Welz and Melcher (S/590) combined it
with an amalgamation technique to achieve greater sensitivity.
Einarsson et al. (S/2) automated the determination so that the
digested samples (blood, urine or other biological material)
were introduced by an automatic sampler into a computer-
controlled cold-vapour AAS system. Comparison of cold-
vapour AAS with DCP-OES for the determination of Hg in
blood and fish samples has been made by Lajunen et al.
(S/904).
Mercury -containing drugs have been analysed by Holak
(S/1088) using HPLC with cold-vapour AAS.
1.3.12. Nickel
Drazniowsky et al. (S/810) determined Ni in serum by
+
ETA-AAS after dilution 1 1 with 0.2% V/VTriton X-100
using matrix-matched standards. For 71 normal subjects a
median normal value of 1.0 pg 1-1 was obtained; patients on
haemodialysis had much higher levels (predialysis median
value 7.4 pg 1-1). Wei and Qi (9196) in their ETA-AAS
method used ammonium oxalate to eliminate interference
from chlorides. Their mean normal value (21.6 pg 1-1) is very
high and suggests that inadequate care was taken to minimise
contamination.
1.3.13. Platinum
Most determinations are concerned with the use of cis-
diamminodichloroplatinum as an anti-tumour agent. In their
study of rats, Wagner and Engelmann (S/C522) diluted serum
+
samples 1 1 with 10-4 M H N 0 3 for analysis by ETA-AAS
using matrix-matched standards. Drummer et al. (S/986) used
an HPLC assay for human serum ultrafiltrate and compared it
with an ETA-AAS method.
Nitric acid causes an interference in the determination of Pt
in tissues by ETA-AAS. Matsumato et al. (S/979) removed it
by adding NH3 to vaporise it in the ashing stage as NH4N03.
Their method was applied to rat organs.
1.3.14. Rubidium
Flame atomic emission spectrometry was used by Allain et al.
(S/497) to determine Rb in plasma and whole blood after
dilution 10- and 100-fold, respectively, with a 2.5 g 1-1 Cs
solution as an ionisation suppressor. A standard AA spec-
trometer was used in the emission mode with an air - C2H2
flame and a red-sensitive photomultiplier. Mean normal
values for plasma of 2.29 k 0.29 pmol l-1 for 27 males and 1.96
k 0.46 pmol 1-1 for 17 females were obtained. Hallis et al.
(S/857) used ETA-AAS for the determination of Rb in plasma
and erythrocytes using a 20- and 50-fold dilution, respectively.
Calibration was by standard additions. Their normal values
were 3.1 pmol l-1 for plasma and 61 pmol l-1 for erythrocytes.
1.3.15. Selenium
Successful Se determination in body fluids and tissues by
hydride generation depends greatly on the prior digestion.
Welz et al. (S/494, S/590) have shown that the use of H N 0 3
alone gave low recoveries. They recommended a digestion
with HN03, H2S04and HC104 at a final temperature of 310
"C to give complete breakdown of organoselenium com-
pounds. This has been applied to serum, whole blood and
urine (S/494), and to marine biological tissue (S/590). In their
method for Se in liver, Kompiang and Coates (S/C680) used
an H N 0 3 - HC104 digestion. This gave good results with NBS
bovine liver.
The now well-established ETA-AAS procedure for serum
analysis using Ni as a matrix modifier has been applied to
sheep serum by Prosbova et al. (S/789). This approach has
been found to fail when tried with whole blood because of
spectral interference from Fe. According to Droessler and
Holcombe (S/C271),this interference is due to a molecular

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1
iron oxide band formed by the combination of Fe with
entrained air.
1.3.16. Thallium
Chandler and Scott (S/643) determined T1 in urine by
extraction with NaDDC at pH 7 into toluene. The toluene
extracts were analysed by ETA-AAS for concentrations of
0-1.65 pg 1-1. The method is suitable for determining T1 levels
in persons not normally exposed to T1. Direct determination
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by ETA-AAS for both blood and urine after dilution with 0.1
M HN03 was shown to be possible by Matsuno et al. (S/160).
Good agreement was found with solvent extraction methods.
Wakid and Cortas (S/992) have compared a spectrophoto-
metric procedure and an FAAS method after solvent extrac-
tion for the determination of T1 in urine.
Hair analysis has been proposed as a suitable marker for
following TI poisoning (S/C529). Matsuno et al. (S/160)
analysed hair directly by insertion into a graphite cup of an
ETA-AAS system.
1.3.17. Vanadium
Mousty et al. (S/988) reported that up to 20% of V is retained
by the graphite tube after atomisation in ETA-AAS. Despite
this, the determination of V in ten urine samples showed good
agreement with NAA results. Chen and Angerer (S/989)
2. ANALYSIS OF FOODS AND BEVERAGES
The use of atomic spectrometry for trace element analysis of
foods and beverages is now well established and few papers
describing new or novel approaches have been published
recently. Owing to this rather static situation more attention
has been given to analytical accuracy, which is reflected in the
increasing number of papers reporting results from inter-
laboratory quality control programmes. An important trend,
however, is the use of direct introduction of samples into
flames, plasmas and graphite furnaces as slurries, suspensions
or emulsions. As in the majority of application areas,
speciation is another topic of interest. A major area of concern
in the food industry is the possible contamination of foods
from wrapping or container materials.
2.1. Sample Preparation
In most reports, sample preparation was achieved by acid
digestion but in a comparative study this technique was found
to give inconsistent results for As, Hg and Se (S/590). Pressure
decomposition in a PTFE bomb led to low results for As and
Se (3590) although other workers obtained satisfactory
results for similar samples with this procedure (S/936). The
comparative study obtained best results following combustion
in a stream of O2 (S/590). Extraction of trace elements from
foods merely by leaching with concentrated acid was found to
be as effective as acid digestion or dry ashing but was simpler
and faster (YC362). With suitable nebulisers tolerant to high
suspended or dissolved solids, slurries and homogenates have
been assayed (S/C298, S/C321).
Some interest in speciation was evident with the publication
of recommendations from the Trace Element Speciation in
Foodstuffs Sub-committee of the Analytical Methods Com-
mittee of the Royal Society of Chemistry (S/926). This
Sub-Committee proposed that enzyme digestion at body
temperature should be used for fractionation studies. They
considered that the work was of sufficient importance to
suggest the establishment of a full-time team of scientists.
View Article Online
39R
preferred a solvent extraction step with APDC into diiso-
propyl ketone and xylol in their ETA-AAS method.
1.4. Conclusions
With time, some of the less realistic applications of ICP-OES
will disappear and it will find its true place in the clinical
laboratory. The technique can have an important role, as the
pioneering work of Allain and Mauras (S/C417) has shown.
For Al, although ETA-AAS methods continue to be
developed that work in the authors' laboratories, the scene
must seem very confusing to a newcomer. The work of
Gardiner et al. (86/195) has helped to clarify the situation, but
more needs to be done.
All developments that produce easier and quicker methods
are welcome and some were featured in section 1.2. The
amazing accuracy produced by direct solid sampling ETA-
AAS and the use of O2 ashing for in situ pre-treatment of
samples in the graphite tube are of particular interest.
For elements at low concentrations in clinical samples, it is
apparent that the ideas expressed by Versieck and Cornelis
(Anal. Chim. Acfa, 1980, 116, 217) in the comparison of
normal levels in establishing accuracy are becoming recog-
nised. Unfortunately, there are still papers appearing in which
previous literature on sample contamination and handling is
ignored and which result in normal values that are far too high.
Separation of HgC12, MeHgCl and EtHgCl by HPLC with
on-line formation of Hg vapour and detection by ICP-OES
was described. This method resulted in detection limits of
50-75 p.p.b. and was applied to the analysis of fish samples
(S/C334). Extraction of inorganic As from acid solution
allowed the selective determination of inorganic and organic
As compounds; further solvent extraction separated the
dimethylarsenic acid from phenylarsonic acid (S/180). Sample
collection and storage was considered in a study of the
determination of Pb in drinking water (S/832). Acidification
was shown to be necessary but that this could be delayed for up
to 14 d after collection without irreversible loss of Pb.
2.2. Analytical Techniques
The most commonly employed analytical technique was AAS
although a wide range of other procedures were also used.
Inductively coupled plasma optical emission spectrometry was
adopted for a number of studies (Table 2) including inter-
laboratory comparisons (S/482, S/938) and the determination
of trace elements in reference materials (S/lO, S/C366, S/482,
9897, S/937). Unusual or novel techniques included the
complexometric determination of Ca in cheese (86/1), dithi-
zone colorimetry (S/9), the determination of Pb in beer using
the slotted quartz tube and FAAS (S/893) and hydride
generation AAS for the determination of As, Sb and Se in a
single-cell protein. This last report referred to the use of a
liquid N2 trap to collect and concentrate the hydrides and an
air - H2 flame within the quartz atomiser tube to increase
atomisation efficiency (86/C146). Detection limits of 0.1-0.5
ng were obtained with this technique. A procedure to measure
the proportion of residual bone within beef products was
described that involved the preparation of homogenised
sample, to contain 5% solids, which was immediately aspir-
ated into a slurry nebuliser for Ca emission analysis with an air
- C2H2 flame (S/C298).
Studies for the certification of reference materials involved
many other techniques (Table 2).
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40R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1

~~

Table 2. SUMMARY OF ANALYSES OF FOODS AND BEVERAGES

Technique;
atomisation;
Element Unm Matrix Concentration analyte form Sample treatment Reference
As Foods AA; Hy; L 5-10 g sample homogenised with 20 ml30% S/180
HC1 and 2 ml2O0/0 ascorbic acid, extracted
into CH2C12for As(II1) determination;
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organo-As compounds determined after

decompositionof HCl phase with HN03
As 193.7 Marine tissue - AA; Hy; L Comparison of 3 digestion procedures: St590
pressure decomposition with HN03,
decompositionwith HN03- H2S04-
HClO,, decomposition in O2stream.
Pressure decomposition with H N 0 3for Hg,
followed by H2S04 - HClO, treatment
for As and Se recommended
As Single-cell 10-500 pg 1-1 AA; Hy; L Wet digestion of samples; hydride collected in 86lC146
protein liquid N2trap, released by rapid heating;
T-shaped quartz tube with internal air -
H2flame as atomiser
Ca - Foods AA; F, air - Digest in HN03- NaOAc s/110
,C2H2;L
Ca 422.7 Animal feedstuffs AA; F, air - 1-5 g sample ashed at 550 "C, re-dissolvedin St242
C2H2; L concentrated HC1, evaporated to dryness,
residue dissolved in 6 M HC1 and filtered
Ca 622.5 Beef 50-200 mg 1-1 AE; F, air - Sample treated for 2 min in Polytron, SIC298
C2H2;slurry homogenised, diluted with 2% HN03 to
5% solids range, shaken for 10 s, aspirated
via slurry nebuliser into flame
Ca Fruit juice AA; F, air - Sl1211
C2H2; L
Cd Baby foods AA; ETA; L IBMK solvent extraction procedure St863
Cd Food packaging AA; ETA; L 100-200 mg sample digested with H N 0 3- Sl1207
papers H2S04at 140 "C for 30 min
Cd Breast milk AA; -; L Breast milk from 10 women analysed for Cd 86/59
and Pb; samples examined at regular
intervals over a 3-month period
co Foods AA; F; L Wet digestion of sample, Fe removed by 86/52
liquid - liquid extraction
Cr Beer 0.246 pg 1-1 AA; ETA; L Samples digested with H N 0 3 St243
Cr Enteral - AA;-; L Sampleswet ashed St789
formulations
cu Meats, frozen AA; -; L Nutritional survey of various foods 9111
vejetables
cu Milk AA; ETA; L Lipids and proteins removed by shaking Sl593
with H2S04- CCl,; no interferences
found; residual C removed from furnace by
O2introduction during tube clean phase
Foods AA; cold vap.; L Accuracy comparison between dithizone s/9
method of Hg determination and cold-
vapour AAS
Shark or swordfish 50-75 pg 1-1 AE; ICP, cold Speciationof HgC12,MeHgCl and EtHgCl SIC334
vap.; L by an HPLC - cold vapour-ICP technique;
separation using C18reversed-phase column
with mobile phase containing
2-mercaptoethanol
Marine tissue - AA; coldvap.; L See As, ref. Sl590 St590
Vegetation - -; cold vap .; Solid sample (300 mg) mixed with mixture of SIC692
gold film analyser A1203- MgO, heated in O2stream; Hg
collected in acidified permanganate -
dichromate solution
Fish tissue 0.79-2.1Opgg-' AA;coldvap.; L Comparison of two different cold-vapour StC693
AAS instruments; comparison of 8 different
digestion methods
Fish tissue 0-600pg 1-1 AA; cold vap. ;L Comparison of different digestion procedures St904
or AE; d.c. arc; using HN03- H2S04and H2SO4 -
L KMnO, mixtures; comparison of cold-
vapour AAS and DCP-OES
Foodstuffs - AA; F; Lor 5-50 g sample digested in HN03 - H2S04 861201
AE; F; L
Foods - AA; F, air - See Ca, ref. S/110 s/110
C2H2; L
Wine - AA;-;L Studies on Ni content in wine pre- and post St925
storage in stainless-steeltanks and glass
bottles
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JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1 41R

Table 2. SUMMARY OF ANALYSES OF FOODS AND BEVERAGES-continued

Technique;
atomisation;
Element Matrix Concentration analyte form Sample treatment Reference
P Foods - AA; F, air - Phospho - vanado - molybdate amplification s/110
C2H2; L procedure for P determination (see Ca,
ref. S/110)
-
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Pb Milk AA; ETA; L SIC94

Pb Baby food AA; ETA; L See Cd, ref. S1863 S1863
Pb Beer AA; F, air - Samplesdegassed by rapid shaking, S/893
C2H2; L acidified with 1%HC1, aspirated directly
into a slotted quartz tube mounted above
a conventional burner
Pb Infant formulas AA; ETA; L Round-robin study for the determination S1940
of Pb in 3 infant formulas
Pb Tin coatings AA; F; L Samplesplaced in solution of CuS04- s/1206
HCl, HNO, added to dissolve precipitated
Cu, solution analysed for Pb by FAAS
Pb Milk - AA; -; L See Cd, ref. 86/59 86/59
Sb Single-cellprotein 10-500 pg 1-1 AA; Hy; L See As, ref. 86lC146 86lC146
Se Beer 0.2-15 pg 1-1 AA; ETA; L Digest with H N 0 3- HC104(see Cr, ref. S1243
9243)
Se Marine tissues - AA; Hy; L See As, ref. Sl590 S1590
Se Foods - AA; Hy; L Digest sampleswith HNO, - HClO, - S1786
HC104;results compared with alternative
procedures
Se Enteral AA;-;L See Cr, ref. 9789 9789
formulations
Se Single-cellprotein 10-500 pg 1-1 AA; Hy; L See As, ref. 86lC146 86lC146
Si Food - AA; -; L Samples dry ashed, fused with Na2B407, 9197
re-dissolved in dilute HNO,
Sn Canned foods 10-450 pg g-' AA; F, N20 - Samplesdigested in HNO, - HC1 S1861
C2H2; L
Zn Meat, frozen AA; -; L See Cu, ref. S/111 Sllll
vegetables
Zn Fruit juice AA; F, air - Samples digested in concentrated HNO,, Sl648
C2H2; L evaporated to dryness, re-dissolvedin 2 M
HCl, concentrated on anion-exchange resin
eluted with 0.01 M HCl, evaporated to
dryness, re-dissolved in 1% H N 0 3
Various - Skim milk Various Certification of a skim milk powder s/10
(5) powder reference material (Ca, K, Mg, Na and P)
Various - Rhubarb AA; F, air - Samples mineralised with HN03- HC104 S116
(7) C2H2; L (Co, Cu, Fe, Mn, Ni, Pb and Zn)
Various - Canned food AA;-; L Acid - peroxide wet ashing of samples s/49
Various - Breast milk AA; F; L Study of the variation of element Sl50
(5) concentrations in the milk of lactating
women (Ca, Cu, Fe, Mg and Zn)
Various - Foods Trace metals AA;-;L Concentration of trace-heavy elements in S/109
(10) foods with chelating resins (Ca, Cd, Co,
Cu, Fe, Mg, Mn, Ni, Pb and Zn)
Various - Maternal diet <25 pg I-' to AE; ICP; L Wet digestion of sampleswith H N 0 3- s/112
(9) solutions >lo0 mg 1-1 HC104- H2S04or HN03- HC104
(Ca, Cu, Fe, K, Mg ,Mn, Na, P and Zn)
Various - Nutritional AE; d.c. arc; L Dilution of sample (Ca, Cu, Fe, K, Mg, Mn, SIC321
(9) formulations Na, P and Zn)
Various - Foods Trace elements AA; F; L Acid leach of sample (2-10 g) with 20 ml of SIC362
(11) 1 + 9 concentrated HC1- HN03,heated at
82-93 "C for 30 min, filtered through
Whatman No. 541 paper, aspirated directly
Various - Diet reference Trace elements AA; For ETA; L Certification of trace element content by a SIC366
(17) material variety of analyticaltechniques
Various - Orange and AE; ICP; L Study involvingthe leaching of trace SIC367
(22) grapefruit juice elements from various containers
Various - Skim milk powder Various Certification of trace elements in 3 samples S/482
of skim milk powder by a variety of
analytical techniques (Cd, Cu, Fe, Hg and
Pb)
Various - Fish tissue AA; ETA; L Zeeman background correction (Cd, Hg, Pb SIC548
(4) and Zn)
Various - Tuna fish AA; For ETA; L Study of toxic and essential trace elements SIC549
(6) pre- and post-canning(Cd, Cr, Cu, Ni, Pb
and Zn)
Various - Foods and AE; ICP; L General review on the use of ZCP-OESto SIC727
beverages solve problems related to the food-
processing industry
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42R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1

Table 2. SUMMARY O F ANALYSES OF FOODS AND BEVERAGES-continued

Technique ;
atomisation;
Element Unm Matrix Concentration anal@ form Sample treatment Reference

Various - Milk and infant - AA; ETA; L Study of the levels of trace elements in Sf788
(6) formulas human milk, cow milk and infant formulas
(Co, Cr, Fe, Mn, Mo and Ni)
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Various - Peanuts and - AA;-;L Study of the differences in the concentration Sf814
(7) peanut oil of trace elements in two different varieties
of peanut (Ca, Co, Cu, Fe, Mg, Pb and Zn)
Various - Skim milk powder - AE; ICP; L Pressure digestion with HN03 (Ca, Mg, Sf897
(4) Na and P)
Various - Food - AA;-;- Report on the work and recommendations of Sf926
the Trace Element Speciation in Foodstuffs
Sub-committee of the Analytical Methods
Committee of the RSC
Various - Food Various A review on the determination of mineral St932
and trace elements in foods
Various - Food Various A review with 90 references st933
Various - Food -.-.-
3 , A review with 29 references on sampling Sf934
methods and data evaluation and handling
in the food industry
Various - Foods Various A review with 91 references on principles Sf935
and instrumentation of atomic spectrometry
with particular reference to the food
industry
Various - Food and biological AE; ICP; Lor A new low-contamination digestion bomb is Sf936
materials AA; F; L described
Various - Foods - -. -. -
7 , Development of a quality assurance Sf937
programme for the determination of 12
elements in raw foodstuffs and crops
Various - Spinach - AE; ICP; L Sample introduction into the ICP by Sf939
a graphite cup direct insertion technique
Various - Foods - AE; ICP; L Wet digestion with HN03 - HC104 Sf1208
(14) recommended

2.3. Reference Materials and Quality Control Programmes
Preparation of materials for reference purposes were des-
cribed for skim milk (S/lO, S/482), vegetables (S/937) and a
freeze-dried “diet” (S/C366). Suggested concentrations were
set out for Ca, C1, K, Mg, Na, Ni and P (S/lO) and Cd, Cu, Fe,
Hg and Pb (S/482) in milk, for 12 elements in vegetables
(S/937) and for 17 elements in the lyophilised diet (S/C366).
Analytical quality assurance was comprehensively reviewed
(S/934) and an inter-laboratory quality assessment programme
for trace elements in infant formulas (S/938) was described.
Between-laboratory coefficients of variation for the nine
elements in the infant formula study were less than 9% with
two-thirds of the samples. This programme had six partici-
pants and all used the same analytical procedure (S/938).
2.4. Topical Applications
Two areas of particular concern are evident from recent work:
firstly, the effect of food packaging upon the trace element
concentrations of their contents; and secondly, the assessment
of likely intakes of trace elements by neonates from milk and
infant food formulas.
The concentrations of Cr, Cu, Ni and Pb in tuna fish,
analysed before and one year after canning, showed no
significant change, but the mean Cd and Zn concentrations
were significantly increased from 0.05 and 16.49 to 0.07 and
18.45p.p.m., respectively (S/C549). In a second study, many
metals were measured in a wide range of canned foods, fruit
juices and syrups and in the alloy of the container (S/49). The
pH of the contents was an important factor in the dissolution
of metal from the can and the authors made various
recommendations concerning packaging and storage (S/49).
Nikdel and Carter (S/C367) found that orange and grapefruit
juices showed minimal changes in trace element concen-
trations even after prolonged periods of storage in various
containers. Defective packaging, however, resulted in major
contamination from the container materials (S/C367). Glass
was shown to adsorb Ni from wines (S/925). Papers used for
wrapping foods, for bags and for kitchen towels contained Cd
at concentrations too low to be of toxicological importance
(S/1207).
Improved methods to determine Pb in tin coatings (S/1206)
and Sn in foodstuffs (S/861) were described while, as an
example of the versatility of ICP-OES, the determination of
trace elements in foods and containers following customer
complaints was cited (SK727).
The concentrations of Co, Cr, Fe, Mn, Mo and Ni were
measured in human milk, cow milk and infant formulas. The
levels in formulas were at least those found in breast milk with
much greater concentrations of Fe and Mn noted (S/788).
Samples of human milk and colostrum from Nigerian women
were analysed for Ca, Cu, Fe, Mg and Zn to determine
changes with lactation age. The concentrations of all of the
elements studied, but especially Zn, steadily decreased during
at least nine months of lactation and intakes were inadequate
when compared with recommended dietary intakes (S/50). In
other studies Cd (S/863, 86/59), Cu (S/593) and Pb (S/C94,
S/863, 86/59) were also determined in human and cow milk
and in infant foods. Intakes of Cd and Pb by breast-fed infants
were higher in urban compared with rural areas (86/59). Four
review articles with particular emphasis on the methods of
analysis for the determination of inorganic elements in foods
were published (S/932, S/933, S/934, S/935).

JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1
2.5. Conclusions
In addition to methods applied to a general range of food types
or to reference materials (Table 2) and the measurements in
milk and formulas, the more specific applications during the
year have included analyses of enteral products, animal feeds
(laboratory and farm), oils and fats, fruit juices, wine and
beer and a novel single-cell protein source, pruteen. The
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View Article Online
43R
determination of Hg in fish continued to receive much
attention. The proportion of papers reporting multi-element
analysis has increased, reflecting the growth of ICP-OES in
this area.
Results from inter-laboratory quality control programmes
indicated that with a selected group of centres, acceptable
analytical performance was possible, but this scheme was too
limited for more useful conclusions to be reached.
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44R JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, APRIL 1986, VOL. 1

Glossary of Abbreviations
Whenever suitable, elements may be referred to by their chemical symbols and compounds by their formulae. The following
abbreviations are used extensively in the Atomic Spectrometry Updates.

a.c. alternating current ICP inductively coupled plasma

AA atomic absorption IR infrared
AAS atomic absorption spectrometry LC liquid chromatography
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AE atomic emission LTE local thermal equilibrium

AES atomic emission spectrometry MECA molecular emission cavity analysis
AF atomic fluorescence MIP microwave-induced plasma
AFS atomic fluorescence spectrometry MS mass spectrometry
APDC ammonium pyrrolidinedithiocarbamate NAA neutron-activation analysis
(ammonium tetramethylenedithio- NaDDC sodium diethyldithiocarbamate
carbamate) NTA nitrilotriacetic acid
ASV anodic-stripping voltammetry OES optical emission spectrometry
CMP capacitively coupled microwave plasma PMT photomultiplier tube
CRM certified reference material p.p.b. parts per billion
cw continuous wave p.p.m. parts per million
d.c. direct current PTFE polytetrafluoroethylene
DCP d.c. plasma r.f. radiofrequency
DMF N,N-dimethylformamide REE rare earth element
DNA deoxyribonucleic acid RM reference material
EDL electrodeless discharge lamp RSD relative standard deviation
EDTA et hy lenediamine t etraacetic acid SBR signal to background ratio
ETA electrothermal atomisation SEM scanning electron microscopy
FAAS flame AAS SNR signal to noise ratio
FAES flame AES SSMS spark-source mass spectrometry
FAFS flame AFS TCA trichloroacetic acid
FI flow injection TLC thin-layer chromatography
GC gas chromatography TOP0 triocty lphosp hine oxide
GDL glow discharge lamp u.h.f. ultra-high-frequency
HCL hollow-cathode lamp uv ultraviolet
h.f. high-frequency VDU visual display unit
HPLC high-performance liquid chromatography vuv vacuum ultraviolet
IBMK is0but yl methyl ketone (4-meth y lpent an- XRF X-ray fluorescence
2-one)