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Elemente Din Alimente La ICP MS
Elemente Din Alimente La ICP MS
Original Article
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 27 January 2010
Received in revised form 8 April 2010
Accepted 14 April 2010
Available online 30 July 2010
This paper describes a validation process for the simultaneous analysis of 21 elements: lithium (Li),
aluminium (Al), vanadium (V), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium
(Ga), germanium (Ge), arsenic (As), strontium (Sr), molybdenum (Mo), silver (Ag), cadmium (Cd), tin
(Sn), antimony (Sb), tellurium (Te), barium (Ba), mercury (Hg) and lead (Pb) in food samples by
inductively coupled plasma-mass spectrometry (ICP-MS) after closed-vessel microwave digestion. This
validation was realized in parallel with the analysis of the 1322 food samples of the second French Total
Diet Study (TDS) by the National Reference Laboratory (NRL) of the French Food Safety Agency (AFSSA).
Several criteria such as linearity, limits of quantication (LOQ), specicity, precision under repeatability
conditions and intermediate precision reproducibility were evaluated. Furthermore, the method was
supervised by several internal and external quality controls (IQC and EQC). Results indicate that this
method could be used in the laboratory for the routine determination of these 21 essential and nonessential elements in foodstuffs with acceptable analytical performance.
2010 Published by Elsevier Inc.
Keywords:
Validation process
Essential and non-essential trace elements
ICP-MS
Microwave digestion
Quality controls
Foodstuffs
French Total Diet Study
Dietary exposure
Toxic food contamination levels in a
population
Food analysis
Food and nutrition data
Food composition
Toxicological reference value
1. Introduction
In 2006, the French Food Safety Agency (AFSSA) started the
second French Total Diet Study (TDS) to estimate dietary exposure
to essential and non-essential elements in 1322 different food
samples. The goal of the TDS is an indirect assessment of foods
found in a typical market basket and prepared for normal
consumption. Often used, it is the most reliable way to estimate
the dietary intake and the exposure to toxic chemicals by large
population groups (WHO GEMS/Food, 2006; Zukowska and Biziuk,
2008). First, the TDS assesses the impact of common household
cooking methods on the decomposition of the least stable chemical
compounds and the formation of new chemical compounds (WHO
GEMS/Food, 2006; Zukowska and Biziuk, 2008). Then data on the
concentration of contaminants, minerals and nutrients, combined
with dietary consumption data, make it possible to evaluate the
levels of dietary exposure in population groups. Thus, the
[()TD$FIG]
112
2.2. Samples
Food matrices used for the validation method have been chosen
among the 1322 food composite samples of the second French TDS.
Each of the samples was composed of up to 15 sub-samples of
equal weight of the same food item and was prepared as normally
consumed by the average consumer. These composite samples
were grouped into 41 food groups representative of the French
food habits as, for example, vegetables, fruits, molluscs and
crustaceans, shes, and cooked dishes, etc. (Sirot et al., 2009). The
method was validated by analysing various types of matrices from
different foodstuffs of animal and vegetal origin (salmon, shrimp,
oyster, pork, carrot, spinach, apple, yoghurt, milk, etc.) as
diversied as possible.
2.3. Sample digestion procedure
Samples were digested using a Multiwave 3000 microwave
digestion system (Anton-Paar, Courtaboeuf, France), equipped
with a rotor for eight 80 mL type quartz vessels (operating
pressure, 80 bar).
The sample digestion procedure was performed according to
the NF EN 13805 standard (AFNOR, 2002b). Before use, quartz
vessels were decontaminated in a bath of 10% of nitric acid 67% (v/
v), then rinsed with ultrapure water and dried in a 40 8C oven. From
0.2 to 0.6 g of dietary samples were weighed precisely in quartz
digestion vessels and wet-oxidized with 3 mL ultrapure water and
3 mL ultrapure HNO3 (67%, v/v) in the microwave digestion
system. One randomly selected vessel was lled with reagents only
and taken through the entire procedure as a blank. The digestion
procedure has previously been optimised (Noel et al., 2003). After
cooling at room temperature, sample solutions were quantitatively
transferred into 50 mL polyethylene asks. Then, 100 mL of the
internal standard solution (1 mg L1) was added to a nal
concentration of 2 mg L1; the digested samples were then lled
with ultrapure water to the nal volume before analysis by ICP-MS.
2.4. ICP-MS determination procedure
2.4.1. Instrumentation
ICP-MS measurements were performed using a VG Plasma
Quad ExCell (Thermo Electro, Courtaboeuf, France). The sample
solutions were pumped by a peristaltic pump from tubes arranged
on a CETAC ASX 500 Model 510 auto-sampler (CETAC, Omaha,
Nebraska, USA). Further details of instrumental settings are given
in Table 1.
2.4.2. Optimization
The isotopes 7Li, 27Al, 51V, 55Mn, 59Co, 60Ni, 63Cu, 65Cu, 64Zn,
66
Zn, 71Ga, 74Ge, 75As, 88Sr, 92Mo, 98Mo, 107Ag, 111Cd, 114Cd, 118Sn,
121
Sb, 125Te, 137Ba, 138Ba, 202Hg, 206Pb, 207Pb, 208Pb were selected as
analytical mass in ICP-MS standard mode. For six elements (Cu, Zn,
Mo, Cd, Ba and Pb), several specic isotopes were considered and
monitored according to the sensibility of the element and/or
possible isobaric and polyatomic interferences (Nardi et al., 2009).
For example, 111Cd was analysed rather than 114Cd because of the
isobaric interference of tin (114Sn). Furthermore, interference
correction formulas were included in the software of the ICP-MS
instrument for 75As (Noel et al., 2005).
Torch position, ion lenses and gases output were optimised daily
with the tuning solution (1 mg L1) to carry out a short-term
stability test of the instrument, to maximise ion signals and to
minimise interference effects from polyatomic ions and doubly
charged ions. In all experiments, a relative standard deviation (RSD)
of 3% was achieved. To obtain precise and accurate results, signal of
elements was monitored by real time display (RTD) which showed
113
Table 1
VG PlasmaQuad operating conditions and acquisition parameters.
Operating conditions
Nebulizer
Spray chamber
Sampling cone
Skimmer cone
RF power
Reected power
Standard mode
Plasma gas ow
Nebulizer gas ow
Auxiliary gas ow
Expansion stage
Intermediate stage
Analyser stage
Acquisition parameters
Mass range
Number of channels
Dwell time
Number of sweeps
Total acquisition time
Peak jumping mode
the constant sensitivity over time for the selected masses and the
ratios of masses with three readings, calculated for each sample.
2.4.3. Calibration
Multi-element standard solutions were used for external
calibration. Five standards with weighed linear regression and
internal standardisation were prepared at concentrations ranging
from 0 to 20 mg L1 for Li, V, Co, Ni, Ga, Ge, Mo, Ag, Cd, Sn, Sb, Sr, Te,
Ba, Hg, Pb, from 0 to 50 mg L1 for Mn, Cu, As and from 0 to
100 mg L1 for Al and Zn. The calibration curve was drawn from six
points, including the calibration blank (0 mg L1).
2.5. Calculations and statistical methods
Concentrations were expressed in milligrams of elements per
kg (mg kg1) of fresh material. The various criteria of the method
for these 21 elements were estimated according to the NF EN V03110 (AFNOR, 1998), NF EN V03-115 (AFNOR, 1996), NF EN 13804
(AFNOR, 2002a) and NF ISO 5725 (ISO, 1994) standards. Data were
subjected to linear regression and analysis of variance using
Microsoft Excel software.
3. Results and discussion
Several criteria were evaluated to monitor the linearity on a
range of dened concentrations, to dene LOQ, to follow the
specicity and the absence of interferences, to control the
repeatability (precision under repeatability conditions) and the
trueness and then, to monitor the intermediate precision
reproducibility (Table 2).
3.1. Range of linearity of the calibration graph
The concentration ranges of the analytes were dened
according to our experience as NRL for heavy metals and our
analytical work for the rst French TDS (Leblanc et al., 2005). ICPMS is well known for beneting from a linear broad dynamic range
(about eight orders of magnitude). Although sample dilutions
could reduce matrix effects, it was not feasible to dilute each
sample individually due to the wide range of concentrations
encountered (going to mg kg1 to mg kg1 according to elements)
and the wide variety of studied foodstuffs. Experiments were
performed with standard solutions of ve concentration levels and
internal standardization (Table 2). The statistical tests were
derived from the analysis of variance applied to the least-squares
114
Table 2
Criteria selected for the ICP-MS validation method.
Characteristics to be evaluated
Procedures to be followed
Number of determinations
Linearity
Analysis of standards
Limits of quantication
Analysis of blanks
Table 3
LOQ, values of trueness and precision criteria for validation of a targeted LOQ.
Element
LOQ dened
(NF EN 13804)
(mg kg1
fresh weight)
Trueness
criteria
(critical
value = 10.0)
Precision
criteria
(critical value = 20%)
Targeted LOQ
veried
(XPT 90-210)
(mg kg1
fresh weight)
Li
Al
V
Mn
Co
Ni
Cu
Zn
Ga
Ge
As
Sr
Mo
Ag
Cd
Sn
Sb
Te
Ba
Hg
Pb
0.001
0.472
0.020
0.015
0.002
0.053
0.023
0.100
0.002
0.003
0.010
0.013
0.011
0.084
0.001
0.003
0.001
0.002
0.090
0.010
0.005
7.4
0.4
8.5
1.8
2.5
7.2
0.1
5.5
4.0
0.3
1.5
3.0
5.7
9.5
6.5
0.6
7.3
0.4
0.02
0.4
6.4
8%
4%
4%
12%
4%
7%
19%
12%
8%
16%
4%
6%
2%
1%
6%
18%
4%
15%
9%
7%
14%
0.002a
0.417e
0.017c
0.017c
0.002a
0.083d
0.017c
0.083d
0.002a
0.002a
0.008b
0.017b
0.008b
0.083d
0.002a
0.002a
0.002a
0.002a
0.083d
0.008b
0.005a
Spiked deionized water at 0.02 mg L1 (a), 0.1 mg L1 (b), 0.2 mg L1 (c), 1 mg L1 (d)
and 5 mg L1 (e).
115
Table 4
Results of specicity test.
Li
Al
Mn
Co
Ni
Cu
Zn
Ga
Ge
As
0.981
0.032
0.170
0.327
0.995
0.038
0.739
1.842
1.018
0.028
0.200
0.279
1.013
0.032
0.860
0.768
0.993
0.017
0.188
0.168
0.962
0.027
0.016
0.282
0.964
0.025
0.105
0.571
0.980
0.033
1.849
1.546
0.962
0.016
0.112
0.166
0.972
0.011
0.023
0.123
1.004
0.016
0.392
0.380
3.169
0.608
0.521
3.250
0.139
0.401
3.106
0.635
0.717
3.250
0.414
1.120
3.106
0.391
1.118
3.169
1.370
0.055
3.106
1.431
0.184
3.250
0.620
1.195
3.106
2.293
0.671
3.250
2.457
0.188
3.169
0.237
1.032
Sr
Mo
Ag
Cd
Sn
Sb
Te
Ba
Hg
Pb
Slope
Standard deviation (s) of the slope
Intercept
s of the intercept
0.984
0.033
0.007
0.351
0.954
0.023
0.295
0.229
0.987
0.072
0.195
0.772
0.956
0.024
0.180
0.206
0.960
0.013
0.197
0.135
0.920
0.029
0.465
0.289
0.925
0.038
0.296
0.405
0.915
0.038
0.542
0.387
0.970
0.015
0.153
0.150
0.962
0.025
0.157
0.258
TCritical value
Tobserved hypotheses test of slope 6 1
Tobserved hypotheses test of intercept 6 0
3.250
0.495
0.021
3.106
2.048
1.291
3.250
0.184
0.253
3.250
1.843
0.876
3.106
3.008
1.456
3.106
2.810
1.609
3.250
1.992
0.730
3.106
2.217
1.399
3.106
2.000
1.021
3.169
1.510
0.609
Slope
Standard deviation (s) of the slope
Intercept
s of the intercept
TCritical value
Tobserved hypotheses test of slope 6 1
Tobserved hypotheses test of intercept 6 0
The various matrices analysed for the test of specicity are the following ones: mutton, semi skimmed milk, veal, chocolate drink, corn, cre`me frache, apple compote, melon,
apple, ratatouille, leek, turkey cutlet, coffee, steamed salmon, orange juice, beer, water, dried, fruits, gruyere type cheese, onion, Pollack, canned tuna, turkey, cucumber,
courgette, buns.
spiking was found (by calculation taking into account the various
weights of the three samples).
Added concentrations varied between 2 and 100 mg L1
depending on the element. It was very difcult to obtain
representatively spiked standard solutions on unknown samples
since initial concentration differed greatly from element to
element within a given matrix and from one matrix to another.
The spiked concentration of the element should normally be equal
to 50200% of the initial concentration of the element in the
sample, except when the sample concentration was close to the
LOQ. In the latter case, any added concentration was considered
appropriate. The line of regression was tested against the line of
unity (slope = 1, intercept = 0) by simultaneously testing the
hypotheses of slope different from 1 and intercept different from
0, using Students t-test; for the 21 elements, Tobserved < Tcritical value
(Table 4). The slope and intercept of this regression line were not
different from 1 and 0, respectively. As a consequence, the
specicity of the method was considered acceptable for all
elements. This conclusion was conrmed by IQC because the
analytical sequence included two different spiked standard
solutions on random samples to check the specicity of the
method during the study. At the end of the TDS, more than 90% of
all spiked standards were between 80 and 120% of the target value,
except for Al and Zn (Millour et al., 2010). However, 8897% of
spikings were between 70 and 130% for these two elements.
Furthermore, the ve added internal standards (Sc, Y, In, Re, and Bi)
permitted to correct the drift and to compensate the matrix effects
in ICP-MS. At the end of the TDS, 86% of internal standards (81% of
Sc, 85% of Y, 88% of In and Re and 89% of Bi) were well included in
the range dened by the QC (30% of the theoretical value).
Table 5
Results of repeatability (precision under repeatability conditions) test (mg kg1).
sra
Li
Al
V
Mn
Co
Ni
Cu
Zn
Ge
As
Sr
Mo
Ag
Cd
Sn
Sb
Te
Ba
Hg
Pb
a
0.0004
0.4590
0.0646
0.0037
0.0010
0.0106
0.0214
0.2625
0.0006
0.0031
0.0178
0.0047
0.0317
0.0013
0.0018
0.0003
0.0006
0.0203
0.0016
0.0013
s2r
1.98E
2.11E1
4.18E3
1.39E5
1.02E6
1.12E4
4.59E4
6.89E2
3.04E7
9.69E6
2.35E4
2.19E5
1.01E3
1.76E6
3.31E6
9.11E8
3.51E7
4.11E4
2.57E6
1.59E6
4.7
13.5
3.9
6.7
5.9
5.6
3.7
5.5
9.2
9.0
2.1
6.6
9.8
4.5
10.5
10.5
8.6
4.8
4.3
5.3
Max (s)2
6
1.40E
8.04E1
2.50E2
1.10E4
9.70E6
1.03E3
2.61E3
5.13E1
1.52E6
8.86E5
2.17E3
1.63E4
8.47E3
1.05E5
2.40E5
4.09E7
1.70E6
2.46E3
8.33E6
8.37E6
21 various samples at different levels in the dened linear range for the 21 elements and n = 2 measurement values.
Critical value at the 1% signicance level (p = 21; n = 2).
The various matrices analysed for the test of repeatability are the following ones: liver, cooked ham, boiled mussel, shrimp, cooked Pollack, canned tuna, salmon, foie gras,
mashed potatoes, veal, turnip, potatoes chips, peas, tomato, bean, spinach, whole milk, non fat yoghurt, tebbouleh, chicken, scallop, boiled salmon, smoked salmon, mutton,
juice of pineapple, sh cakes, French fries, corn, fromage blanc, grape juice, cartonned soup, chocolate cake, chocolate biscuit, sweet pancake, mayonnaise, semolina, tomato
sauce, babybel1 type cheese, chocolate mousse, cheese, gruyere cheese, goat cheese, hard-boiled egg, pizza, dried fruits, oyster, dark chocolate, pear, Roquefort type cheese
and pate.
b
116
3.5. Trueness
Table 6
Results of trueness and intermediate precision reproducibility in IAEA 407.
CRM
s (mg kg1)
CVr (%)
CVR (%)
0.040
0.060
6.1
3.2
10.8
0.3770.993a
0.6200.740b
0.8
1.4
7.6
3.4
13.4
7.620.0a
12.415.2b
1.48
1.43
0.06
0.09
4.0
2.1
8.5
1.001.86a
1.341.52b
Theoretical value
Theoretical value
3.46
3.52
0.12
0.08
3.5
0.8
7.2
2.464.58a
3.443.60b
Co
Estimated mean
Theoretical value
0.11
0.10
0.007
0.01
6.4
3.3
10.2
0.070.13a
0.090.11b
Ni
Estimated mean
Theoretical value
0.90
0.60
0.07
0.05
7.6
2.8
14.2
0.330.87a
0.550.65b
Cu
Estimated mean
Theoretical value
3.35
3.28
0.22
0.08
6.7
0.8
9.9
2.304.26a
3.203.36b
Zn
Estimated mean
Theoretical value
64.9
67.1
3.3
0.9
5.2
0.4
5.6
47.087.2a
66.367.9b
As
Estimated mean
Theoretical value
13.7
12.6
0.7
0.3
5.1
0.8
6.1
6.918.3a
12.312.9b
Sr
Estimated mean
Theoretical value
3
5
2.0
1.3
Cd
Estimated mean
Theoretical value
0.184
0.189
0.014
0.004
1.1
0.7
5.8
Sn
Estimated mean
Theoretical value
0.10
0.10
0.01
0.01
8.5
13.3
12.5
0.060.14a
0.060.13b
Sb
Estimated mean
Theoretical value
0.008
0.011
0.001
0.001
6.0
3.0
11.6
0.0060.016a
0.0100.012b
Hg
Estimated mean
Theoretical value
0.224
0.222
0.006
0.006
2.7
0.9
6.2
0.1550.289a
0.2160.228b
7.4
5.6
11.2
Li
Estimated mean
Theoretical value
Al
Estimated mean
Theoretical value
Estimated mean
Theoretical value
Mn
Pb
a
b
0.661
0.685
11.2
13.8
144
130
Estimated mean
0.08
0.006
Theoretical value
0.12
0.020
h
i
CVR M
p with k = 3, n = 1 samples and M = reference value or indicative value for Sn.
: CI M k 100
n
Condence interval of the CRM.
10
91169a
125135b
0.1320.246a
0.1850.193b
0.080.16a
0.100.14b
117
Table 7
Results of trueness and intermediate precision reproducibility in INCT MPH 2.
CRM
s (mg kg1)
CVr (%)
CVR (%)
Al
Estimated mean
Theoretical value
491
670
13.3
55.3
2.7
0.6
12.7
Estimated mean
Theoretical value
0.023
0.082
2.8
5.7
8.5
0.6661.238a
0.7891.115b
Mn
Estimated mean
Theoretical value
8
6
4.3
2.0
7.9
134248a
179203b
Co
Estimated mean
Theoretical value
0.217
0.210
0.013
0.008
5.8
4.0
9.5
0.1470.273a
0.1850.235b
Ni
Estimated mean
Theoretical value
1.44
1.57
0.09
0.08
6.2
3.4
8.3
0.862.28a
1.411.73b
Cu
Estimated mean
Theoretical value
6.98
7.77
0.12
0.27
1.7
2.3
9.2
5.4410.10a
7.248.30b
Zn
Estimated mean
Theoretical value
2.8
1.1
8.5
2.1
9.0
23.543.6a
31.435.6b
As
Estimated mean
Theoretical value
0.01
0.01
6.0
4.0
12.8
0.1050.277a
0.1680.214b
Sr
Estimated mean
Theoretical value
0.97
1.35
3.7
2.4
10.0
26.348.9a
34.940.3b
Mo
Estimated mean
Theoretical value
0.42
0.52
0.016
3.9
6.8
0.360.68a
Cd
Estimated mean
Theoretical value
0.207
0.199
0.01
0.01
4.0
2.7
5.6
0.1400.260a
0.1840.214b
Sb
Estimated mean
Theoretical value
0.058
0.066
0.007
0.005
5.7
5.1
10.5
0.0360.096a
0.0560.075b
Ba
Estimated mean
Theoretical value
0.8
1.3
2.2
2.6
8.9
22.842.3a
30.035.0b
Hg
Estimated mean
Theoretical value
0.002
0.001
6.9
3.0
10.4
0.0130.023a
0.0160.019b
4.2
3.6
7.5
1.512.81a
1.932.39b
0.851
0.952
189
191
33.3
33.5
0.204
0.191
26.1
37.6
34.2
32.5
0.019
0.018
Pb
a
b
Estimated mean
2.02
0.08
Theoretical value
2.16
0.12
h
i
CVR M
p with k = 3, n = 1 samples and M = reference value or indicative value for Mo.
: CI M k 100
n
Table 8
Results of trueness and intermediate precision reproducibility in BCR 278R.
CRM
s (mg kg1)
CVr (%)
CVR (%)
Mn
Estimated mean
Theoretical value
7.04
7.69
0.33
0.12
4.7
1.0
7.0
5.3810.0a
7.467.92b
Cu
Estimated mean
Theoretical value
8.33
9.45
0.34
0.06
4.1
0.5
7.7
6.6212.3a
9.329.58b
Zn
Estimated mean
Theoretical value
1.7
0.9
4.9
0.9
9.0
58.2108a
81.484.8b
As
Estimated mean
Theoretical value
5.49
6.07
0.12
0.07
2.1
0.7
11.1
3.348.80a
5.946.20b
Cd
Estimated mean
Theoretical value
0.324
0.348
0.009
0.003
2.9
0.7
6.3
0.2440.452a
0.3410.355b
Hg
Estimated mean
Theoretical value
0.183
0.196
0.005
0.005
2.6
1.5
5.3
0.1370.255a
0.1870.205b
0.03
0.02
1.7
0.7
8.2
1.402.60a
1.962.04b
Pb
a
b
71.5
83.1
Estimated mean
1.85
Theoretical value
2.00
h
i
CVR M
p
118
Table 9
Results of trueness for Ga, Ge, Ag and Te spiked with 5 and 20 mg L1 on veal, carrot
or corn.
Mean (mg L1)
CI (mg L1)a
s (mg L1)
CVr
Theoretical value
Ga
4.8
20.7
4.35.7
17.322.7
0.05
0.5
1.0
2.4
Ge
4.9
20.5
4.35.7
17.322.7
0.02
0.3
0.4
1.5
Ag
4.9
16.3
4.15.9
16.024.0
0.02
0.5
0.5
3.0
Te
4.9
4.35.7
0.09
1.9
22.3
17.322.7
0.5
2.2
h
i
CVR M
a
p
: CI M k 100
with
k
=
3,
n
=
5
samples,
M
=
theoretical
value
and
n
CVR = 10% for Ga, Ge, Te and 15% for Ag.
Sr, Cd, Sb and Pb) and three in INCT MPH 2 (Al, Cu and Sr). However,
each individual results as well as the measured means were well
included in the CI (n = 1; k = 3; p = 99%) around the reference value,
except for Ni in IAEA 407 and Sr in INCT MPH 2 (slightly below IC).
It should be noted that Ni was overestimated (0.9 mg kg1 instead
of 0.6 mg kg1) due to polyatomic interferences (44Ca16O or
23
Na37Cl) caused by the high concentration of Na and Ca in the
CRM (Nardi et al., 2009). According to Tables 68, the CVr for the 17
elements was 9% and was less than the CVR dened for the
reproducibility (dened in the following paragraph). So, the
trueness was generally satisfactory and a good accordance was
obtained between found and expected values.
For Ga, Ge, Ag and Te without certied or indicative values, the
analysis was carried out with spiked standard solutions (5 and
20 mg L1) on two unknown samples (carrot, veal or corn).
Obtained values were close to the theoretical concentration of
spiked standard solutions on unknown samples and CVr was below
5% for these four elements (Table 9). So, the trueness was
considered acceptable. It should be noted that for Ag, mean
concentrations (5 and 20 mg L1) were underevaluated in comparison with the theoretical value. The major cause was postulated to
be due to chloride in the sample that caused precipitation of silver
chloride (Yang et al., 2002). Similar problems were also reported in
aqueous samples by US EPA which recommended that samples
were digested using mixed acid HNO3 + HCl (2 + 1) in aqueous
samples containing concentrations up to 0.1 mg L1 of Ag (US EPA,
1994). Indeed, Ag is only slightly soluble in the presence of chloride
unless there is a sufcient chloride concentration to form the
soluble chloride complex. However, as compromise, the multielementary analysis requires the use of the unique HNO3 media
and the obtained mean concentrations remained with the CI set for
the study.
3.6. Intermediate precision reproducibility
Based on the NF V03-110 standard (AFNOR, 1998), the
intermediate precision reproducibility was investigated by repeating the analysis (n > 10) of a same homogeneous sample on
different days and several months, with four different analysts and
with two different microwave systems. Intermediate reproducibility variance was calculated as: s2R s2L s2r , where s2L was the
variance that measured sample variations and s2r was the
repeatability variance. This reproducibility was realized with the
same CRMs than it was done previously. For each element, as
expected, CVR > CVr, obtained previously (Tables 68). Calculated
CVR were in the range of 5.314.9%, according to elements and
CRMs. For practical reasons in the context of routine multielemental analysis, two groups of elements have been established
according to the order of magnitude of the intermediate precision:
The rst group is constituted by V, Mn, Co, Cu, Zn, Sr, Mo, Cd, Ba,
Pb and Hg that usually had a CVR lower than or equal to 10%. It
should be noted that this estimation was similar to those
previously reported for Hg in BCR 278R (5.3%) and IAEA 407
(6.2%) and Pb in BCR 278R (8.2%) and INCT MPH 2 (7.5%) (Noel et al.,
2005). However, as expected, the CVR of Hg in INCT MPH 2 was
higher due to its low level near the LOQ (0.01 mg kg1) and a
slightly higher CVR is also observed for Pb in IAEA 407.
A CVR of 15% was set for the second group, which considered the
other elements Li, Al, As, Ni, Sn and Sb, usually exceeding a CVR of
10% but never exceeded 15% in the CRMs tested. IQC put in place
during the TDS, notably through control charts, corroborated these
results and gave a higher percentage of unacceptably found values
in comparison with the reference value for these elements (Millour
et al., 2010).
For Ga, Ge, Ag and Te without certied or indicative values, a
CVR was estimated considering the results obtained for the
trueness and the IQC of the second French TDS (Millour et al.,
2010). Thus, a CVR of 10% will be set for Ga, Ge and Te (less than 8%
of non-conforming spiking) and it will be necessary to apply a less
restrictive CVR of 15% for Ag.
The Z-scores were used as IQC to check these three CRMs, as
previously described (Millour et al., 2010). At the end of the study,
94% of results (2 < Z < 2) were considered acceptable, 2% were
questionable (2 < jZj < 3) and 4% unacceptable (jZj > 3).
To summarize the intermediate precision reproducibility, two
groups of elements have been dened according to the:
A CVR of 10% for V, Mn, Co, Cu, Zn, Ga, Ge, Sr, Mo, Cd, Te, Ba, Pb
and Hg
A CVR of 15% for Li, Al, As, Ni, Ag, Sn and Sb
Based on the set CVR, the uncertainty of each result for all the
elements was dened as:
k CVR M
p
100 n
119
Table 10
Results of EQC with Z-score during the period 20072009 for six elements.
Analyte
Sample (year)
As
Al
Z-scorea
0.051
0.104
11.4
0.125
0.189
7.6
0.343
0.770
11.2
0.732
0.654
0.053
0.126
11.6
0.143
0.209
9.1
0.383
0.849
9.94
0.844
0.755
0.2
1.0
0.2
0.7
0.5
1.6
0.6
0.6
1.0
0.9
0.9
0.992
0.972
1.84
0.977
1.72
1.69
0.1
4.8
0.5
Co
Canned sh (2008)
0.007
0.007
0.2
Cu
Mo
Sn
: Z-score
X f X c
p , where Xf is the actual analytical result, Xc is the
n
sR =
13.7
12.1
15.1
12.4
0.382
0.425
0.389
0.456
214
91.5
255
162
80.8
233
0.9
0.2
0.1
0.4
3.4
1.4
1.2
certied value, sR the reproducibility standard deviation, n the number of independent replicates (n = 1).
and Sn) results were considered acceptable (Table 10) except for Sn
in vegetable puree (Z-score = 3.4) and for Al in infant formula
cereal (Z-score = 4.8). The unacceptable results for Al were due to
problem of random pollution. So, performance in these prociency
tests were regularly considered satisfactory and showed the ability
of the NRL to provide reliable and accurate results.
4. Conclusion and prospects
After this validation, the selected criteria of performance
(linearity, LOQ, specicity, trueness, repeatability, intermediate
precision reproducibility) demonstrated that the use of both
microwave digestion in closed-vessel for sample preparation and
the ICP-MS for detection permitted an accurate determination of
21 elements in several types of food samples (matrices of animal
and vegetal origin). This validation was supported by appropriate
IQC to achieve a satisfactory quality level in the case of routine
analysis. Furthermore, the dened CVR will be used to delimit the
CI for CRMs in future studies. Obviously, it should be noted that this
multi-elemental method is an acceptable compromise and some
elements such as Ag and Sn could be more accurately quantied by
specic method, notably using a mixture of HNO3 and HCl to
stabilize these elements.
This validation will be followed to the accreditation by the
French committee of accreditation (COFRAC) in order to obtain an
extension of the in-house method concerning the analysis of four
elements in matrices of animal origin by ICP-MS. Finally, as NRL,
the laboratory will transfer its method to veterinary departmental
laboratories participating in the various national plans of food
monitoring for health risk assessment.
Acknowledgements
The participants are warmly thanked for their willing cooperation. Thanks are also due to J.-C. Leblanc, AFSSA DERNS,
coordinator of the 2nd French TDS for his helpfulness. The authors
would like to thank the general food directorate of the Ministry of
120
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