Trends Trends in Analytical Chemistry, Vol. 23, No.

3, 2004

Certied reference materials

(CRMs) for quality control of
trace-element determinations in
wastewaters
M. Segura, C. Camara, Y. Madrid, C. Rebollo, J. Azcarate, G.N. Kramer,
B.M. Gawlik, A. Lamberty, Ph. Quevauviller

The needs for new reference materials are constantly growing and become more specic as laboratories raise their
awareness. Particular emphasis is placed on how representative reference materials are.
In the water analysis sector, series of natural water reference materials are already on the market (sea and fresh water).
However, at present, there are no materials that meet the needs for quality control in the analysis of wastewaters.
Recent advances were made possible within the framework of a European Commission research project, the nal aim of
which was to certify three wastewater reference materials for trace-element contents (BCR-713, euent wastewater, BCR-714,
inuent wastewater, and BCR-715, industrial euent wastewater). These CRMs were the result of collaborative work
involving 16 European laboratories.
This article describes the preparation and the certication of these three wastewater reference materials for arsenic,
cadmium, copper, chromium, iron, lead, manganese, nickel, selenium and zinc. Besides information on the preparation of
the CRMs, it also describes the analytical techniques used by the certifying laboratories.
# 2003 Published by Elsevier B.V.

Abbreviations: CRM, Certied reference material; CV, coecient of variation; EC, European Commission; EU, European Union; ET-AAS,
Electrothermal atomic absorption spectrometry; FAAS, Flame atomic absorption spectrometry; HG-AAS, Hydride generation atomic
absorption spectrometry; HG-AFS, Hydride generation atomic uorescence spectrometry; HR-ICP-MS, High-resolution inductively coupled
plasma mass spectrometry; ICP-MS, inductively coupled plasma mass spectrometry; RNAA, Radiochemical neutron activation analysis;
WWTP, Wastewater treatment plant; ZET-AAS, ET-AAS with Zeeman background correction

1. Introduction
M. Segura, C. Camara, Y. Madrid
Universidad Complutense, Departamento de Quimica Analitica, ES-28040 Madrid, Spain
A number of Directives have been
C. Rebollo, J. Azcarate recently adopted in the EU as a legislative
Ayuntamiento de Madrid, Departamento de Agua y Saneamiento, c/ Barcelo 6, 1
, framework on water management, treat-
ES-28004 Madrid, Spain ment and pollution control, introducing
quality standards and objectives. These
G.N. Kramer, B.M. Gawlik, A. Lamberty
European Commission, Institute for Reference Materials and Measurements, Retieseweg,
represent the major instrument for the
B-2440 Geel, Belgium preservation of the aquatic environment
from point and diuse discharges of dan-
Ph. Quevauviller* gerous substances. In this context, monit-
European Commission, DG Environment, rue de la Loi 200, B-1049 Brussels, Belgium oring of industrial and urban wastewater
plays an essential role for environmental
protection to ensure process eciency
*Corresponding author. Tel.: +32 (2) 296-3351; Fax: +32 (2) 295-8072; and to verify the nal quality of the
E-mail: philippe.quevauviller@cec.eu.int euents.

194 0165-9936/03/$ - see front matter # 2003 Published by Elsevier B.V. doi:10.1016/S0165-9936(04)00502-3
Trends in Analytical Chemistry, Vol. 23, No. 3, 2004
Reliable results for the determination of trace ele-
ments in urban and industrial wastewater are of para-
mount importance for both checking the performance
of sewage treatment and detecting possible sources of
urban or industrial contamination. Only accurate ana-
lytical results enable valid conclusions to be drawn
about the quality of dierent types of water, the health
risk that has to be assessed and the actions to be taken.
Sometimes the lack of accuracy at low concentra-
tions of toxic elements (such as As, Se, Cr, Ni, and Pb)
may be attributed to the sensitivity of some analytical
methods, the complexity of the matrix and the accuracy
of the methods (with methods biased because of con-
tamination and/or losses during sample pre-treatment).
Several types of procedures are used to measure and/
or control the analytical accuracy of the results
obtained, the most ecient being the use of CRMs [1,2].
CRMs provide the means to achieve traceability in che-
mical measurements, and, in some instances, to cali-
brate equipment and methods, to monitor laboratory
performance, to validate methods and to permit com-
parison of methods [3^5].
The European Commission (EC) (through the BCR
programme) has developed a series of CRMs for trace
elements representing the most frequently analysed
indicators, such as estuarine water [6], seawater [7]
and groundwater [8]. To complement this series, and
taking not account that the present state of the art of
measurements of the wastewater analysis justied the
need, it has been decided to prepare and to certify was-
tewater reference materials to enable adequate quality
assurance of the analysis performed. Therefore, the
BCR (renamed Measurements and Testing Programme)
was asked to produce three CRMs for the quality control
of trace elements in wastewater.
The samples were chosen for representing the main
components of wastewaters (a range of heavy
metals with dierent concentrations, organic contents,
etc.) and the degree of diculty expected in stabilising
them.
This article describes the preparation as well as the
analytical work performed for the certication of the
elements selected (As; Cd; Cr; Cu; Fe; Mn; Ni; Pb; Se;
and, Zn) in three wastewater reference materials (BCR-
713 (euent wastewater); BCR-714 (inuent waste-
water); and, BCR-715 (industrial euent wastewater)).
2. Preliminary investigations: feasibility study
The optimal conditions for the preparation of waste-
water candidate CRMs were tested in a feasibility study.
This preliminary study involved investigations on
sample homogeneity and stability as well as evaluation
of the analytical techniques employed for the determi-
nation of the selected analytes. This step was especially
Trends
relevant since the results obtained conditioned the
entire project.
For this purpose, three batches were prepared from
two spiked urban wastewater samples and a spiked
industrial wastewater sample, and their homogeneities
were veried to evaluate possible eects of the prepara-
tion procedure on sample composition. The stability
was also checked at +4
C and +20
C over 6 months. No
signicant variation with time was observed for the
investigated elements, although the formation of parti-
culate material was reported.
The initial study was followed by an interlaboratory
study involving 16 European laboratories. The techni-
ques used in the interlaboratory were basically the
same as those applied in certication. The results
obtained in this feasibility study have been described
elsewhere [9]. The short-term stability study demon-
strated that the samples remained stable under
conditions tested [9] and led to the preparation of
a large batch of candidate reference materials for
certication.
3. Preparation of candidate reference materials
3.1. Sample collection
The sampling for the certication campaign was carried
out in November 1999. Volumes of 125 L for each of
the three samples were collected in acid-cleaned poly-
ethylene containers.
Urban wastewater was taken from a WWTP (La
China, Madrid, Spain), which deals with the waste-
water corresponding to a population of 1.3 million
inhabitants. The incoming ow in this plant is approxi-
mately 3 m3/s and almost entirely of urban origin. The
types of treatment performed at the WWTP is conven-
tional (pre-treatment, sand removal, primary sedi-
mentation, activated sludge process, secondary
sedimentation, and ltration).
The raw wastewater sample was collected from an
accessible channel that allowed sampling at a point
with signicant, turbulent ow, favouring homo-
genisation and avoiding the presence of large solids
particles in the sample. This sample (raw wastewater
sample) was called inuent The other urban waste-
water sample (WWTP euent) was collected before the
tertiary ltration stage.
The mixed industrial euent was selected from the
complex network of sewers in an industrial area outside
the city. The selected sewer nished as an open channel
at the entrance of a WWTP (Sur), and did not contain
urban wastewater. The medium ow of this sewer was
0.9 m3/s and it collects the euent of dierent types of
industries (e.g., metal surface treatment, food proces-
sing, and graphic arts). For the certication campaign,
this material was called industrial euent.
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Trends Trends in Analytical Chemistry, Vol. 23, No. 3, 2004

Table 1. Analysis of the wastewater samples
pH COD BOD
(mg/L) (mg/L)
Euent 7.2 67 15
Inuent 7.3 650 285 270
Mixed industrial 6.9 830 340
euent
3.2. Sample preparation and homogenisation
Preliminary characterisation was carried out prior to
sample preparation, using general parameters shown
in Table 1.
The samples were acidied to pH below 2 with HNO3
and were homogenised by stirring for 16 h in open con-
tainers to facilitate gas release. Then, they were ltered
through cartridges: prelter [pore size 1.2 mm OPTICAP
(Millipore p.n. KW1904NP3)] and lter [pore size
0.5 mm OPTICAP (Millipore p.n. KWSC04NP3)].
The ltrate was collected in clean polyethylene con-
tainers of 125 L that were left to stand for 8 months in
closed containers (which were opened periodically to
facilitate gas release). The decision to adopt this
maturation stage was as a result of observations during
the feasibility study about the formation of particulate
matter in the ltered samples after several months of
storage.
Following the decision to spike and the subsequent
selection of the target metal concentration ranges
(Table 2), a screening analysis was carried out to assess
the natural concentration ranges of dierent dissolved
metals in ltered samples. Once spiked, the samples
were homogenized mechanically for 15 min using an
electrical mixer tted with plastic rods. Then, a second
ltration step was performed using a ltration device
equivalent to that described above, in order to eliminate
the biological ocks developed during the maturation
stage. Finally, after a rough analytical verication of
metal concentration, the three samples were labelled
and sent for bottling.
3.3. Bottling
The samples were homogenized for 1 h, under nitrogen
ushing (using Teon tubing), of the container content,
using a home-made stirrer (rod totally covered with
Teon, and two perforated, paddled Teon agitators),
and merged in the receiving container. Filling and seal-
ing took place in an argon/helium mixture (90/10).
The 100 mL aliquots were contained in hand-made
Susp. Solids
Pyrex white glass ampoules of 120 mL capacity. These
(mg/L)
ampoules were designed especially for this project
19 (adapted 60 mm length and 10 mm diameter for the
neck and pre-opened 13 mm wide-mouthed head). The
350
opened empty ampoules were rst cleaned twice with
demineralised water and subsequently dried at 60
C.
The ampouling used the automatic lling and sealing
machine of the ROTA company. During continuous
homogenisation by stirring (agitator speed:  40 rpm)
and nitrogen ushing, the wastewater was transferred
using a Teon-protected stainless steel pump connected
via Teon tubes to the 125 L container and the lling
needle. Prior to ampouling, about 5 L wastewater was
used to eliminate air and to rinse the tubes and pump.
The following lling and sealing procedure was used:
1. lling with a mixture of 90% argon and 10%
helium using a lling needle;
2. lling with 100 ml of wastewater using a lling
needle;
3. lling with a mixture of 90% argon and 10%
helium using a lling needle
4. pre-heating the neck of the ampoule
5. sealing the ampoule and automatically remov-
ing the neck of the ampoule.
4. Homogeneity study
The between-bottles homogeneity was veried by
determination of the elements As, Cd, Cr, Cu, Fe, Mn,
Ni, Pb, Se and Zn by analysing the samples without
treatment in 20 randomly selected ampoules of each
solution (total of 60 samples). The within-bottles
homogeneity was veried by analysing one randomly
chosen bottle with 10 replicate determinations of each
element of the three kind of solutions.
The analytical methods used were ICP-MS (As, Cd,
Cr, Cu, Fe, Mn, Ni, Pb, Zn,) and HG-AFS (Se). The
samples were analysed in randomised order in the most
repeatable manner (same day, same equipment and
same person).
The homogeneity of the elements selected for certi-
cation was tested by comparing the coecient of vari-
ation obtained within bottle (CVib) and between bottle
(CVbb).

Table 2. Metal concentration ranges after spiking (mg/L) for the candidate reference materials
As Cd Cr Cu Fe Mn Ni Pb Se Zn
WWTP Euent 215 215 530 20100 200800 20100 20100 20100 215 100600
WWTP Inuent 1030 1030 50300 100400 5002000 50300 50300 50300 520 8002000
Mixed industrial 2050 2080 5002000 5002000 20005000 100500 5002000 2001000 2050 30006000
euent

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Trends in Analytical Chemistry, Vol. 23, No. 3, 2004
The estimation of the uncertainty Ucv of the coe-
cient of variations (CV) was calculated as follows:
UCV = CV/(2n)1/2, where n is the number of replicate
determinations. The results obtained are available in
the Certication Report [10]. An F-test at the signi-
cance level of 0.05 did not reveal any signicant dier-
ence between the bottles and the method variances. It
was hence concluded that no inhomogeneities were
detected for any of the elements in the three CRMs.
5. Stability study
The stability of the elements contained in BCR-713,
BCR-714 and BCR-715 reference materials was tested
to determine their suitability as reference materials. In
the stability test, selected elements were quantied (As,
Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) by ICP-MS; As and Se
were quantied by HG-AFS. Bottles were kept at +4
C,
+20
C and +40
C, respectively, for 12 months. The ele-
ments considered for the stability study were determined
at regular intervals during the storage period, using the
same analytical procedure as for the homogeneity
study. Tests were made at the beginning of the storage
period, then after 14 days and 1, 3, 6 and 12 months.
Instability would be detected by comparing the con-
tents of dierent elements in samples stored at dierent
temperatures with those stored at low temperature at
the various occasions of analysis. The samples stored
at +4
C were used as reference for those samples stored at
+20
C and +40
C. The ratios (Rt) were calculated by
dividing the mean values (Xt) of 5 measurements made
at +20
C and +40
C with the mean value (X+4
C) from
5 determinations made at the same occasion of analysis
on samples stored at a temperature of +4
C, i.e.:
Rt Xt =X4
C
The uncertainty, Ut, was obtained from the coecient
of variation (CV) of 5 measurements obtained at each
temperature:
Ut CV2t =n CV24
C =n1=2 Rt
Results of the calculations of the ratios of mean
values (Rt) and the uncertainty for the elements are
available in the Certication Report [10]. On the basis
of these results, it was concluded that no instability
could be demonstrated for the tested elements.
6. Analytical techniques used for certication
Various analytical techniques were used for certica-
tion (FAAS, HG-AAS, HG-AFS, ET-AAS, ICP-MS, HR-
ICP-MS and RNAA). Calibration was generally based
Trends
on the used of calibration graph. In most cases, sample
pre-treatment was not required.
Each laboratory that took part in the certication
campaign was requested to make a minimum of six
independent replicate determinations of each element
on at least two dierent bottles of the three CRMs on
two dierent days without mineralising the samples.
The sample pre-treatment and techniques used by the
participating laboratories are summarised in Table 3.
At the technical meeting, it was ensured that the
laboratories participating in the certication exercise
applied their methods correctly and that they veried,
whenever possible, the performance of their methods
using available reference materials.
7. Technical and statistical discussion
The data obtained by all participants were presented in
the form of bar-charts including the laboratory code
with the analytical technique used, the mean of all
individual values with the corresponding standard
deviation and the mean of the mean values with its
corresponding standard deviation (e.g., Fig. 1).
All the results were discussed at a technical eval-
uation meeting to conrm the accuracy of the method
of analysis. The attendance of the participants to the
meeting was considered to be a prerequisite for accep-
tance of results for certication.
7.1. Technical discussion
In general, a reasonable agreement among the results
of almost all the participants was obtained and the
number of dierent techniques used for each analyte
was found to be appropriate. Detected sources of errors
were mainly attributed to calibration, calibrants and
dilution errors and because results too close to the
detection limits of the analytical techniques were used.
Some sets of results were withdrawn because of their
large standard deviation or discrepancies between the
results provided by dierent techniques within a single
laboratory.
Results obtained by one laboratory for all the ele-
ments were signicantly lower than the mean of
laboratory means because of a problem with prepar-
ation of the multi-element stock solution, so its results
were not accepted in any CRMs.
Results too close to the detection limit for ICP-AES
were not retained for arsenic. Divergences between
FAAS and ZET-AAS within a single laboratory could
not be explained and indicated a lack of quality control,
and this justied the withdrawal of sets of results for Cd,
Cu and Ni.
For Fe, a set of results was withdrawn, because of low
sensitivity through the use of a lamp of low energy and
a high background when using FAAS.
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Trends Trends in Analytical Chemistry, Vol. 23, No. 3, 2004

Table 3. Summary of the analytical methods used in the certication

Elements Pre-treatment methods Final determination
As Addition of Ni(NO3)2 modier ET-AAS
Reduction with NaBH4 in acid mixture, use of KI HG-AAS
Reduction with NaBH4 in HCl, use of KI and acid ascorbic HG-AFS
Dilution, Reduction with NaBH4 in HCl, use of KI and acid ascorbic HG-ET-AAS
Dilution, addition of In as internal standard HR-ICP-MS of 75As
No pre-treatment ICP-AES
Dilution, addition of Rh as internal standard ICP-MS of 75As
Radiochemical separation, ion exchange, irradiation RNAA
Addition of Pd+ Mg(NO3)2 as modier ZETAAS
Cd Dilution ET-AAS
No pre-treatment FAAS
Addition of NH4H2PO4+ Mg(NO3)2 as modier ZET-AAS
No pre-treatment ICP-AES
Dilution, addition of Rh or In as internal standard ICP-MS of 111Cd or 112Cd or 114
Cd
Addition of In as internal standard HR-ICP-MS of 114Cd
Radiochemical separation, ion exchange, irradiation RNAA
Cu No pre-treatment FAAS
Dilution ET-AAS
Addition of Pd+ Mg(NO3)2 as modier ZETAAS
No pre-treatment ICP-AES
Dilution, addition of Rh or Sc or In as internal standard ICP-MS of 63Cu or 65Cu
Addition of In as internal standard HR-ICP-MS of 63Cd and 65Cd
Radiochemical separation, ion exchange, irradiation RNAA
Cr No pre-treatment FAAS
Dilution ET-AAS
Dilution, addition of Mg(NO3)2 ZETAAS
No pre-treatment ICP-AES
Dilution, addition of Sc or Rh or In as internal standard ICP-MS of 52Cr and 53
Cr
Dilution, addition of In as internal standard HR-ICP-MS of 52Cr
Radiochemical separation, ion exchange, irradiation RNAA
Fe No pre-treatment FAAS
No pre-treatment and dilution ET-AAS
No pre-treatment and dilution, addition of Yb as internal standard ICP-AES
Dilution, addition of Rh as internal standard ICP-MS of 57Fe
Dilution, addition of In as internal standard HR-ICP-MS of 56Fe
Radiochemical separation, ion exchange, irradiation RNAA
Pb No pre-treatment FAAS
No pre-treatment ET-AAS
Dilution, addition of NH4H2PO4+ Mg(NO3)2 as modier ZET-AAS
No pre-treatment and dilution ICP-AES
Dilution, addition of Rh, In, Bi or Tl as internal standard ICP-MS of 206Pb, 207Pb, 208Pb
Dilution, addition of Tl as internal standard HR-ICP-MS of 208Pb
Dilution, Pb spike TIMS of 206Pb, 207Pb, 208Pb
Mn No pre-treatment FAAS
Dilution ET-AAS
Dilution, addition of Pd+ Mg(NO3)2 as modier ZET-AAS
No pre-treatment and dilution, addition of Yb as internal standard ICP-AES
Dilution, addition of Sc or Rh as internal standard ICP-MS of 55Mn
Dilution, addition of In as internal standard HR-ICP-MS of 55Mn
Ni No pre-treatment FAAS
Dilution ET-AAS
Dilution ZETAAS
No pre-treatment and dilution ICP-AES
Dilution, addition of Sc or Rh or In as internal standard ICP-MS of 58Ni, 60Ni 62Ni
Dilution, addition of In as internal standard HR-ICP-MS of 58Ni 60Ni

(continued on next page)

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Table 3 (continued)

Elements Pre-treatment methods Final determination

Se Pre-reduction with HCl. Derivatization with NaBH4 in HCl HG-AAS
Pre-reduction with HCl. Derivatization with NaBH4 in HCl HG-AFS
Pre-reduction with HCl. Derivatization with NaBH4 in HCl HG-ET-AAS
Addition of Ni(NO3)2 as modier ZETAAS
No pre-treatment ICP-AES
Dilution, addition of Rh or In as internal standard ICP-MS of 78Se, 82Se
Radiochemical separation, ion exchange, irradiation RNAA
Zn Dilution FAAS
No pre-treatment and dilution ICP-AES
Dilution, addition of Rh as internal standard ICP-MS of 66Zn
Dilution, addition of In as internal standard HP-ICP-MS of 66Zn, 68Zn

Figure 1. Cadmium in BCR-714 in mg/L.

Several sets of results for various elements were not
retained because of a large standard deviation, which
was either caused by dilution errors, thus indicating a
lack of quality control, or by results being too close to
the detection limits of the analytical methods used.
As a result of this technical scrutiny, all the elements
were proposed for certication.
7.2. General statistical discussion
Each set of results was submitted to a series of statistical
tests, namely:
 Kolmogorov-Smirnov-Lilliefors (assessment of
the conformity of the distributions of individual
results and of laboratory means to normal
distributions);

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Trends Trends in Analytical Chemistry, Vol. 23, No. 3, 2004

 Nalimov (detection of outlying values in the
population of individual results and in the popu-
lation of laboratory means);
 Bartlett (assessment of the overall consistency of
the variance values obtained in the participating
laboratories); and,
 Cochran test (detection of outlying values in
the laboratory variances (s2i )).
A summary of the statistical data is available in the
Certication Report [10].
The sets of results found acceptable on technical and
statistical grounds were represented in the form of
bar-charts (as shown in Fig. 1), in which the length
of a bar corresponds to the 95% condence interval of
the mean. The certied values were calculated as the
arithmetic means of laboratory means (taking into
account the number of sets accepted for certication
after both statistical and technical scrutiny); they are
featured as vertical dotted lines on the bar-graphs.
The set of variances is often not homogeneous
because each of the dierent analytical methods used
has a dierent repeatability and reproducibility.
8. Certied values and their uncertainties
The evaluation of uncertainties in the context of certi-
cation exercises has evolved over the past decade. Now,
certied values should be accompanied by uncertainty
statements in compliance with the requirements of the
Guide for the Expression of Uncertainties in Measure-
ment (GUM). While the design of new certication pro-
jects considers the needs for a proper estimation of the
various uncertainty sources, such as stability and
homogeneity, older campaigns aimed only at qualita-
tive statements (yes/no decisions) of whether or not a
material was stable and homogeneous. The evaluation
described hereafter is based on a concept described by
Pauwels et al. [11].
Based on the ndings obtained in the stability and
homogeneity studies as well as the scattering of results,
estimates for ubb (homogeneity), ults (long-term stabi-
lity) and uchar (batch characterisation) were obtained
and combined according the following equation:
q
UCRM 2  u2bb u2lts u2char

Table 4. Uncertainty budget for BCR-713, -714 and -715. Concentrations are in mg/L
Material Parameter Mean value uchar (%) sbb (%), u*bb (%), ults (%), UCRM (%) UCRM
n=20 df=9 12 months
BCR-713 As 9.66 2.57 2.71 2.88 3.55 10.49 1.01
Cd 5.09 2.06 */* 3.43 3.64 10.82 0.55
Cr 21.94 2.18 0.96 1.51 4.67 10.74 2.36
Cu 68.38 1.63 0 0.89 1.53 4.81 3.29
Fe 398.3 1.71 */* 2.54 2.6 8.03 32.00
Mn 43.4 1.33 1.44 1.65 2.62 6.74 2.93
Ni 30.36 1.74 2.29 3.43 6.61 15.30 4.64
Pb 46.52 1.45 1.3 1.3 2.59 6.48 3.01
Se 5.58 3.48 */* 4.8 6.62 17.77 0.99
Zn 216.16 5.86 */* 2.4 3.89 14.86 32.13

BCR-714 As 18.33 2.42 */* 1.44 3.35 8.75 1.60

Cd 19.93 1.13 */* 1.03 3.51 7.66 1.53
Cr 122.97 1.01 0 1.1 3.73 8.04 9.88
Cu 309.07 1.17 */* 0.89 3.31 7.24 22.39
Fe 1029.96 1.23 2.13 1.99 4.36 10.01 103.12
Mn 103.11 1.07 0.92 1.37 4.43 9.52 9.81
Ni 108.48 1.2 */* 2.06 6.28 13.43 14.57
Pb 144.89 1.32 */* 1.99 2.5 6.91 10.02
Se 9.76 2.44 1 3.43 4.04 11.67 1.14
Zn 1023.1 1.57 0 0.96 4.28 9.32 95.33

BCR-715 As 28.64 2.2 1.53 1.44 4.55 10.56 3.02

Cd 40.41 1.06 0.75 0.89 5.09 10.55 4.26
Cr 997.6 1.2 0.56 1.03 4.14 8.86 88.42
Cu 895.34 0.91 */* 0.82 7.23 14.67 131.31
Fe 2995.21 1.4 1.55 1.17 3.86 8.78 262.91
Mn 248.06 1.36 */* 1.51 4.5 9.88 24.50
Ni 1206.89 1.03 */* 0.69 3.09 6.66 80.37
Pb 494.06 0.94 */* 1.1 2.93 6.54 32.29
Se 28.77 3.35 */* 1.85 5.53 13.45 3.87
Zn 3999.19 0.82 */* 0.89 4.7 9.71 388.19

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Trends in Analytical Chemistry, Vol. 23, No. 3, 2004 Trends

Table 5. Certied values and uncertainties

Elements BCR-713 BCR-714 BCR-715
As (9.7
1.1) mg/L (18.3
1.6) mg/L (29
4) mg/L
Cd (5.1
0.6) mg/L (19.9
1.6) mg/L (40
5) mg/L
Cr (21.9
2.4) mg/L (123
10) mg/L (1.00
0.09) mg/L
Cu (69
4) mg/L (309
23) mg/L (0.90
0.14) mg/L
Fe (0.40
0.04) mg/L (1.03
0.11) mg/L (3.00
0.27) mg/L
Mn (43.4
3.0) mg/L (103
10) mg/L (248
25) mg/L
Ni (30
5) mg/L (108
15) mg/L (1.20
0.09) mg/L
Pb (47
4) mg/L (145
11) mg/L (0.49
0.04) mg/L
Se (5.6
1.0) mg/L (9.8
1.2) mg/L (29
4) mg/L
Zn (0.22
0.04) mg/L (1.00
0.10) mg/L (4.0
0.4) mg/L

Because of the transport conditions selected for dis- 9. Conclusions

patch, the uncertainty constituent for short-term stabi-
lilty (usts) is negligible and consequently not included in
the overall uncertainty. The estimation of the other
uncertainty sources is described below.
From the homogeneity data, an estimation of ubb was
derived. According to this approach, sbb (the standard
deviation between units) or u*bb (the upper limit of
inhomogeneity that can be hidden by the method
repeatability) is used as the estimate of ubb. Values for
sbb and u*bb were calculated accordingly.
Whereas sbb was estimated from the dierences of the
observed CVs2, values for u*bb were calculated as:
r r
MSwithin 4 2
u bb  Acknowledgements
n MSwithin
where n is the number of replicates per unit and nMSwithin
the degrees of freedom of MSwithin.
If the value of sbb is below the minimum value deter-
mined by the repeatability of the method and the
number of replicates performed, u*bb is used to estimate
ubb. The results of these calculations are shown in Table 4.
Similarly, a quantitative estimate of the uncertainty
related to stability, ults, was obtained. The uncertainty
was estimated for a shelf-life of 12 months only, as there
were insucient data to allow further projection without
seriously compromising the usefulness of the certied
values. Thus, the estimated uncertainty contribution,
ults, can be used to establish expiry dates once
appropriate stability testing data are available, e.g.
after having performed an isochronous experiment.
Finally, an estimate for uchar (batch characterisa-
tion) was derived from the standard error obtained on
the mean of laboratories means, and an uncertainty
budget was calculated (as shown in Table 4).
The certied values were calculated as the arithmetic
means of laboratory means (taking into account the
numbers of sets accepted for certication after both
statistical and technical scrutiny). The certied values
and their associated uncertainties are given in the Table 5.
The three CRMs described in this article clearly full a
demand for quality-control tools for wastewater mon-
itoring. The BCR-713,-714 and-715 CRMs are now
available from the Institute for Reference Materials and
Measurements (IRMM), Geel, Belgium.
More information is available from the IRMM website
(http://www.irmm.jrc.be). A certicate and a report
[11] describing the work performed (preparation of the
material, homogeneity and stability studies, the analy-
tical methods used and the individual results) accom-
pany each bottle and can be obtained upon request.
The project was co-ordinated by the Department of
Analytical Chemistry of the Complutense University
(Spain). The sample collection and preparation were
carried out by the WWTP (La China, Madrid, Spain)
and the IRMM, Geel, Belgium. The Complutense Uni-
versity performed homogeneity and stability studies.
The combined uncertainties of the certied values were
calculated by the IRMM, Belgium. Laboratories that
participated in the certication are gratefully acknowl-
edged, namely: Aguas de Barcelona (Spain); ALcontrol
Laboratories, Rotherham (United Kingdom); Anjou-
Recherche, Saint-Maurice (France); Chalmers Uni-
versity of Technology, Goteborg (Sweden); CNR, Isti-
tuto di Ricerca sulle Acque, Brugherio (Italy); CNRS,
Service Central dAnalyse, Vernaison (France); DVGW,
Abteilung Analytik, Karlsruhe (Germany); ECN, Ener-
gie Research Foundation, Petten (The Netherlands);
ENEA, Casaccia Research Centre, Rome (Italy); Euro-
ns, HSrsholm (Denmark); Instituut voor Nucleaire
Wettenschappen, Gent (Belgium); Lyonnaise des Eaux,
CIRSEE, Le Pecq (France); NIVA, Norwegian Institute
for Water Research, Oslo (Norway); Universitat de les
Illes Balears, Departamento de Quimica, Mallorca
(Spain); Universite de Bordeaux I, LPTC, Talence
(France); UltraTrace Aquitaine, Pau (France).

http://www.elsevier.com/locate/trac 201
Trends
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