CRM 146R

ISSN 1018-5593
European Commission
ber information
REFERENCE MATERIALS
THE CERTIFICATION OF THE TOTAL CONTENTS

(MASS FRACTIONS) OF Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb
AND Zn AND THE AQUA REGIA SOLUBLE CONTENTS
(MASS FRACTIONS) OF Cd, Co, Cr, Cu, Hg, Mn, Ni,
Pb AND Zn IN A SEWAGE SLUDGE
FROM INDUSTRIAL ORIGIN
CRM 146 R
Report
EUR 16892 EN
European Commission
ber information
REFERENCE MATERIALS
THE CERTIFICATION OF THE TOTAL CONTENTS

(MASS FRACTIONS) OF Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb
AND Zn AND THE AQUA REGIA SOLUBLE CONTENTS
(MASS FRACTIONS) OF Cd, Co, Cr, Cu, Hg, Mn, Ni,
Pb AND Zn IN A SEWAGE SLUDGE
FROM INDUSTRIAL ORIGIN
CRM 146 R
Ph. QUEVAUVILLER('), H. MUNTAU(2), U. FORTUNATI^), K. VERCOUTEREf)
(') European Commission
Standards, Measurements and Testing Programme
B-Brussels
Belgium
(2) Joint Research Centre
European Commission
l-lspra
Italy
(3) Studio di Ingeneria Ambientale
l-Milan
Italy
C) Laboratory for Analytical Chemistry
University of Gent
B-Gent
Belgium
Directorate-General
Science, Research and Development
1996
EUR 16892 EN
EUROPEAN COMMISSION
LEGAL NOTICE
Neither the European Commission nor any person acting on
behalf of the Commission is responsible for the use which might be made of the
following information
Cataloguing data can be found at the end of this publication
Luxembourg: Office for Official Publications of the European Communities, 1995

ISBN 92-827-7415-5
ECSC-EC-EAEC, Brussels Luxembourg, 1996.
Printed in Belgium
GLOSSARY OF ABBREVIATIONS
Throughout the report (including the annexes) the following abbreviations are used:
AR
Aqua regia soluble fraction
CV
Coefficient of variation
C VAAS
Cold vapour atomic absorption spectrometry
DPASV
Differential pulse anodic stripping voltammetry
DPCSV
Differential pulse cathodic stripping voltammetry
EDXRF
Energy dispersive X-ray fluorescence spectrometry
ET AAS
Electrothermal atomic absorption spectrometry
FAAS
Flame atomic absorption spectrometry
ICPAES
Inductively coupled plasma atomic emission spectrometry
ICPMS
Inductively coupled plasma atomic mass spectrometry
ID ICPMS
Isotope dilution inductively coupled plasma mass spectrometry
IDMS
Isotope dilution mass spectrometry
INAA
Instrumental neutron activation analysis
MIBK
Methyl isobutylketone
NaDDTC
Sodium diethyldithiocarbamate
PTFE
Polytetrafluoroethylene
RNAA
Radiochemical neutron activation analysis
CONTENTS
Page
1.
Introduction
2.
Participating laboratories
3.
Preparation of the material
Homogeneity study
5.
Stability study
6.
Aqua regia soluble contents
10
7.
Analytical methods
11
8.
Technical and statistical discussion
9.
Certified values
54
10.
Informative values
55
11.
Instructions for users
57
ANNEX I
Tables of individual results and graphical presentations
61
1.
INTRODUCTION
The certified reference material described in this report is intended to replace the BCR CRM 146
sewage sludge from industrial origin (referred to as "original sludge CRM" in this report) of
which, due to its success in environmental and pollution control, the present supply is exhausted.
In view of the strong demand the Commission has decided to replace it. This sludge reference
material belongs to a set of 3 materials: BCR CRM 144 R sewage sludge from domestic origin,
BCR CRM 145 R sewage sludge from mixed origin and BCR 146 R sewage sludge from mainly
industrial origin, covering different concentrations of trace elements and different matrices.
These materials are intended mainly for the verification of accuracy in trace element
determinations of nutrititional or environmental importance in soils or other materials with
similar matrices.
Care was taken to find a material with a composition close to that of the original sludge CRM
but taking into account the evolution during the 10 years that separate their collection.
The
content of some trace elements is lower in the present material as a consequence of measures
taken to minimise environmental pollution by local and national authorities. The material will
therefore be more relevant to actual situations encountered in the laboratories.
As the information on the aqua regia soluble content of some elements was a very useful tool
for the users of the exhausted reference material, certification of this quantity was also decided
upon. The determination of this parameter is often requested to estimate the impact of sewage
sludge amending soils.
2.
PARTICIPATING LABORATORIES
2.1.
Preparation
European Commission, JRC-Environment Institute, Ispra
2.2.
Homogeneity study
GSF Forschungszentrum fr Umwelt und Gesundheit, Oberschleiheim
2.3.
DE
Stability study
ECN Energieonderzoekcentrum Nederland, Petten
2.4.
IT
NL
Analyses
Agricultural Research Centre of Finland, Jokionen
SF
Agriculture & Food Development Authority, Wexford
IE
Service Central d'Analyse, CNRS, Vernaison
FR
ECN Energieonderzoekcentrum Nederland, Petten
NL
Ecole Europenne des Hautes Etudes des Industries Chimiques,

Strasbourg, Lab. de Chimie Analytique
FR
GSF Forschungszentrum fr Umwelt und Gesundheit, Oberschleiheim
DE
INTRA, Station d'Agronomie, Villenave d'Ornon
FR
Institute for Soil Fertility, Haren
NL
Institut fr Analytische Chemie, Technische Universitt Wien
AT
IFA, Tulln
AT
Laboratorium voor Analytische Scheikunde, INW, Universiteit Gent
BE
Ris National Laboratory, Roskilde
DK
Universidad de Barcelona, Dept. de Qumica Analtica
ES
Universit di Pavia, Centro de Chimica Nuclearia
IT
3.
PREPARATION OF THE MATERIAL
A sewage sludge with an interesting high content of metals under regulation was collected in
Maison Lafitte in the region of Paris, (France). A preliminary analysis of the sludge revealed
that the heavy metal concentrations are lower than in the original sludge CRM thus reflecting
the present waste water conditions as a consequence of the pollution measures taken. The matrix
composition meets quite well that of the original sludge CRM considering the natural variability
of sludges.
A comparison of the composition of the 2 sludges is given in table 3.1; the
determinations of major components were performed by X-ray fluorescence spectrometry.

Table 3.1:
Comparison of the composition (expressed as mass fraction (g/kg) of the original

sludge CRM 146 with the sludge intended for replacement, BCR CRM 146 R
Material
BCR 146
BCR 146 R
Si0 2
228.0
221.5
MgO
A1203
Ti0 2
Fe^
p2o5
33
24
90
87
29.1
41.0
26.5
19.5
59.0
76.5
5.8
7.0
250 kg of sludge containing about 50 % of solid material was collected. The sludge was air
dried in thin layers and continuously moved and mixed to avoid fungi development.
The
material was passed through a 2 mm sieve discarding the fraction > 2 mm and eliminating
extraneous particles such as stones, roots, fragments of plastic and metal. The fraction < 2 mm
was divided into 10 batches of 10 kg which all underwent gamma irradiation at a dose of 25
KGy (sufficient to sterilise the material). The batches were pooled together for further processing
which consisted of crushing with a Retsch SR3 mill with an inner 0.75 mm sieve.
crushing, the material was further sieved mechanically to obtain the fraction <
After
90 . This
material was inserted in a rigid mixing drum with out-of axis-fins. The drum was kept rotating
for 170 hours at 40 rpm until a sufficiently homogeneous material with particle size <
90 m
was obtained; the optimal homogenization time was based on previous experience with this type
of material.
The final material was bottled in 50 g portions in clean brown glass bottles closed with a plastic
insert and screw cap; the bottling procedure was carried out in a stepwise manner: twenty bottles
were filled while the drum was stationary, then the drum was operated again for 3 minutes and
20 other bottles were filled; the operation was repeated until the whole material was bottled.
4.
HOMOGENEITY STUDY
Materials such as sewage sludges and soils consist of numerous solid phases, all of them
differing with respect to their morphological, physical and chemical properties. The geometrical
shape of the particles varies from fibres of a few diameter but several 100 in length,
over thin leaf-like particles (kaolinite, mica, etc.) to isometric compact particles such as rounded
silica grains and rhombohedric calcite cleavage particles with different mass densities.
Keeping in mind that all the different phases show distinct trace element concentrations,
sometimes differing over orders of magnitude, it is likely that any segregation of particles, for
example through vibrations during transport could lead to considerable inhomogeneities with
respect to the trace elements. Re-homogenisation prior to subsampling is therefore mandatory.
For more information the reader is referred to section 11 of this report: "Instructions for users".
A homogeneity study was performed for the elements Al, , Ba, Ca, Cd, Co, Cr, Cu, Fe, K,
Mg, Mn, Mo, Ni, , Pb, S, Sn, Sr, V and Zn. This includes elements intended for certification
as well as some "key elements" that are specific for the phase distribution; e.g. is associated
with the phosphate phase, while Ni and Cr are determined to control possible contamination
which might have occurred during the processing of the soil. The chosen elements also cover
a large mass fraction range (from the lower mg/kg to several g/kg).
4.1.
Method
The within and between bottle homogeneity of the elements mentioned above was studied using
simultaneous ICPAES at different levels of sample intake, i.e. 50, 100 and 250 mg. After rehomogenisation, the material was digested using pressurised wet ashing with HN0 3 in quartz
vessels for 10 h at a temperature of 170 C for the 50 and 100 mg sample intake. Aqua regia
dissolution was used for the 250 mg sample intake, following the procedure described in section
6 of this report.
The within bottle homogeneity was studied by 10 replicate determinations on the content of one
randomly selected bottle whereas the between bottle homogeneity was determined by a single
determination in each of 10 different bottles. The CV of the final detection method could be
calculated on the basis of 10 replicates of one sample digest.
4.2.
Results
The CV's within and between bottles obtained for the different sample intakes and the CV of
the final detection method are summarised in table 4 . 1 .
Table 4.1:
Results for the within-and between-bottle homogeneity of BCR CRM 146 R at 50

and 100 mg levels of intake (total element contents)
Sample
mass
Element
CV (%)
between bottles*
CV (%)
within bottles**
CV (%)
method***
50 mg
Al
Ba
Ca
Cd
Co
Cr
Cu
Fe
Mg
Mn
Mo
Ni
Pb
S
Sr
V
Zn
2.6
2.7
2.9
2.4
2.7
4.8
3.4
2.7
3.9
2.5
2.4
2.3
2.3
3.6
4.3
2.6
1.6
2.1
3.1
2.8
2.7
3.7
1.6
1.7
1.8
3.0
3.0
2.4
4.2
1.5
1.0
1.3
2.9
3.8
3.3
1.9
1.2
1.5
1.9
1.3
3.0
1.0
0.4
1.0
0.8
2.0
0.9
0.7
2.5
1.6
0.5
0.5
2.0
2.1
1.4
1.3
0.5
0.4
0.5
1.7
100 mg
Al
B
Ba
Ca
Cd
Cr
Cu
Fe
K
Mg
Mn
Mo
Ni
Pb
S
Sr
V
Zn
3.0
6.5
1.6
3.4
1.8
2.0
1.9
4.3
1.7
1.3
1.7
5.3
3.0
3.1
1.7
1.4
1.7
1.6
1.8
2.6
9.2
1.9
4.5
2.0
2.3
2.1
3.8
1.7
1.7
1.7
4.7
2.7
2.3
2.3
1.8
1.6
1.7
1.8
3.0
1.0
0.4
1.0
0.8
0.9
0.7
2.5
1.6
0.5
0.5
2.0
2.1
1.4
1.3
0.5
0.4
0.5
1.7
Table 4.1:
Results for the within-and between-bottle homogeneity of BCR CRM 146 R at

250 level of intake (aqua regia soluble element contents)
Sample
mass
Element
CV (%)
between bottles*
CV (%)
within bottles**
CV (%)
method***
250 mg
Al
Ba
Ca
Cd
Co
Cr
Cu
Fe
4.6
7.7
3.2
0.9
3.0
4.8
2.5
2.0
0.5
5.3
1.9
1.5
4.7
5.9
1.4
2.4
2.0
2.5
1.4
3.7
2.1
3.6
5.2
4.2
1.4
2.6
2.6
3.8
1.5
3.9
5.5
1.9
2.1
4.1
4.6
2.2
3.1
1.9
2.3
1.7
4.1
2.1
3.0
1.0
0.4
1.0
0.8
2.0
0.9
0.7
2.5
1.6
0.5
0.5
2.0
2.1
1.4
1.3
0.5
1.8
0.4
0.5
1.7
Mg
Mn
Mo
Ni
Pb
S
Sn
Sr
V
Zn
*
***
single determination on the content of each of 10 bottles

10 replicate determinations on the content of one bottle
10 replicates on one digest solution
An approximation of the uncertainty on the CV's, (U), was calculated using the following
formula: U = CVfr/2n. Such a way of calculation leads to a symmetric uncertainty as can be
seen in the figures. An F test was applied on the CV's and revealed no systematic differences
between within and between bottle homogeneity even for sample intakes as low as 100 mg (for
total contents). The CRM is considered to be homogeneous at a minimum of 250 mg, and of
course at 3 g level (following the DIN standard).
5.
STABILITY STUDY
The stability of the contents of some major and trace elements was tested to determine the
suitability of the chosen sludge as a candidate certified reference material.
Three series of
bottles were stored respectively at -20 C, +20 C and +40 C. The elements C, Cd, Cu, N,
Ni and Pb were determined at the beginning of the period and after 6 months. Analyses were
carried out in 6 fold.
5.1.
Methods
C and N were determined using an automatic C-N analyzer. After flash burning of 5 mg of
sample in a tin cup at 1800 to 2000 C the nitrogen oxides are reduced to nitrogen while the
carbon monoxide is oxidized to carbon dioxide.
They are separated by chromatography
(Poropax column) and are determined through thermal conductivity.

The stability of Cd, Cu, Ni and Pb was assessed with ICPAES. This method was applied after
digestion of the material in a PTFE-lined bomb at 190 C for 10 h with HN0 3 /HF/HC10 4
(5/3/0.25 ml).
5.2.
Results
Any change of results on element composition with time indicates instability, provided that a
good long-term analytical reproducibility has been achieved. At -20 C changes of any kind
proceed slowly, whereas at +40 C instability is more likely. Assuming that the samples stored
at -20 C in the dark are stable, these samples can serve as a comparator for the samples stored
at the other temperatures.
The results obtained for the stability study are given in table 5.1 as the relative variations
observed:
R, = /_20 . c
where (RJ is the ratio of the mean value of six measurements made at +20 C and +40 C
respectively, (X,), versus the mean of the determinations made at the same occasion of analysis
on samples stored at -20 C, (X.20c)
The uncertainty U t of the ratio Rt has been obtained from the coefficient of variation of each set
of measurements:
Ut = (CVt2 + CV. 20 . C 2 ) 1/2 . R,
where CV, and CV.20 c are the coefficients of variation of X, and X.20 c respectively.
In the case of ideal stability, R, should be 1.
In reality however there are some random
variations due to the uncertainty of the measurement. The value 1 is comprised between Rt U, and Rt + Ut in all cases except for Cd and for Cu and Ni at 40 C.
On the basis of these results, it was concluded that no instability could be detected.
Table 5.1:
Normalised results of the stability study of CRM 146 R after 6 months storage
at different temperatures (-20 C, +20 C and + 4 0 C).
Element
Time
(months)
+ 40 C/-20 C
+ 20 C/-20 C
Value of R,
u,
Value of R,
u,
0.997
0.007
0.989
0.010
Cd
1.060
0.058
1.099
0.038
Cu
0.991
0.012
0.987
0.010
0.992
0.011
0.993
0.011
Ni
1.016
0.024
1.029
0.026
Pb
1.021
0.048
1.014
0.047
The long term stability of this material is assumed to be very good, considering that the CRM
146 was stable over 10 years. The aqua-regia procedure dissolves all "mobile" and lithogenic
fractions which are assumed to remain constant and fairly stable over time.
6.
AQUA REGIA SOLUBLE CONTENTS
Many laboratories performing in agricultural analysis frequently determine the aqua regia soluble
fraction of certain elements instead of the total content. In many countries (D, NL, DK, F), the
determination of the aqua regia soluble part is requested by the national regulations. Therefore
it is also certified for the elements of interest.
For such certification purposes it is mandatory that the participants follow exactly the same
extraction procedure. The digestion method according to the German Norm (DIN 38414-S7)
was adopted as the common method for the certification campaign. The protocol is given below.
Weigh approximately 3 g of material in a round bottom flask. (The material should be
dried for 30 min at 105 C and, following cooling in a desiccator, weighed to the nearest
0.01 g.)
Add a little bidistilled water to obtain a slurry. Then mix with 21 ml of HCl (mass density
1.19) and 7 ml ofHN03 (mass density 1.40).
Add 10 ml of HNO3 (0.5 molli*) to the absorption vessel, connect the vessel to the reflux
condenser and place both on top of the reaction flask.
Allow to stand at room temperature for several hours (at least 12 h)
Heat until boiling and continue to boil gently under reflux for 2 h. (The condensation
zone should not rise above the lower third of the reflux condenser.)
Allow to cool slowly to room temperature.
Pass the content of the absorption vessel through the condenser tube into the reaction
vessel, rinse both with HN03 (0.5 molli*) and collect the HN03 in the reaction vessel.
Transfer the content of the reaction vessel quantitatively to a 100 ml graduated flask.
Rinse the reaction vessel with HN03 (0.5 molli*) and transfer as well. Fill the graduated
flask with bidistilled water up to the mark, close with stopper and shake.
After the undissolved content has settled, the supernatant solution shall be used for the
final determination of the elements.
If the undissolved components settle too slowly or unsatisfactorily, then centrifuge or
filter through a membrane filter with a pore size of 0.45 m after filling the graduated
flask up to the mark.
The reagents used should be of best purity. If necessary their purity should be checked
by performing a blank test. Glassware should be thoroughly cleaned before use with hot
HN03 (0.5 molli*) and then rinsed with bidistilled water. In this exercise the participants
were free in choosing of glassware for the digestion.
* 35 ml of HNO3 (mass density 1.4) diluted with bidistilled water to make 1 I.
10
The methods of final determination used were generally the same as those for the total contents.
The description of the methods and precautions to eliminate systematic errors can be found in
section 7 of this report. The tables 7.1 and 7.2 summarise the data for both total and aqua regia
determination.
7.
ANALYTICAL METHODS
Each laboratory which participated in the certification was requested to make a minimum of five
independent replicate determinations (from subsampling and weighing to the final determination).
This section summarises the main observations made in the analytical campaign and the methods
used for certification. The techniques used by the participating laboratories are summarised in
table 7.2 for both total and aqua regia determinations.
To obtain the accuracy and the reliability required for certification it is necessary to ensure that
no substantial systematic error is left undetected. This means that special attention was paid to
ascertain the accuracy of the results. To achieve this the following steps were taken :
1)
elimination of causes of systematic errors in the various steps of the analytical process.
Possible sources of error and measures taken to eliminate them were discussed in a
meeting with the participating laboratories and are shown in table 7.1. No systematic
difference between the different methods could be detected.
2)
The laboratories participating in the certification used at least the following quality
control steps:
a)
The determinations were performed with methods which were under statistical
control.
b)
Wherever possible, the performance of the method, as carried out by the

laboratory, was verified by analysing available reference materials.
11
Results of different methods as applied in different laboratories were compared for the detection
of methodological error sources. The technically accepted results (satisfying criteria 1 and 2)
are given in Annex I (tables a). No method bias was detected. As a conclusion one can say that
where the above requirements are met, the certified values are free of substantial systematic
error within the present state of the art.
12
Table 7.1:
Some possible sources of error and their elimination

Destructive methods
Analytical step
Systematic error by
Contribution
Elimination by
weighing
+ /-
calibrated balance
volumetric manipula
tion
+ /-
dilutions etc carried out with calibrated

glassware, temperature control
moisture
adsorption/desorption
+ /-
correction to dry mass according to

procedure in chapter 11
digestion/oxidation
incomplete
preparation
volatilisation
+ /-
adsorption/desorption
sample preparation/
clean u p /
preconcentration
adsorption/irreversible
precipitation
incomplete conversion
+ /-
reagent contamination
contamination by
tools/vials
contamination from lab

air
+ /-
calibration
13
participants used H F treatment with

acid digestion or alkaline fusion to
obtain complete digestion
for volatile elements e.g. Hg treatments
carried out in closed systems
acid washed containers of hard glass,
P T F E or H D P E prerinsed surfaces
pH-control and/or addition of complexing agents if necessary
excess of reagents; methods a priori
verified
reagents of appropriate purity; veri
fication with blank determinations
acid washing as appropriate; when
contents below 1 -g/g were determined:
steaming; verification with blank deter
minations
use of clean benches or clean rooms;
care in performing methods under cover
or in closed systems; verification with
blank determinations
different calibration methods were

chosen when possible: calibration
graphs, when necessary matrix mat
ched, and standard additions within the
limits of this method
Non destructive methods

Analytical step
irradiation
counting
Systematic error by
Contribution
self-shielding
Elimination by
contents are such that for the elements
investigated shielding does not occur
changes of flux
+ /-
flux monitors were added in the irradiation process
peak overlap intrinsic

irradiation; high background
+ /-
deconvolution; selection of proper

decay times; R N A A as an alternative
geometry
+ /-
calibrants and unknowns were both in

the same form e.g. solution or powder;
they were measured in identical vials at
the same distance of the detector etc
+ /-
the same remarks as for destructive

methods are valid; additional care was
given to the stability on irradiation of
the calibrant
calibration
14
Table 7.2:
Summary of the methods and the sample masses used for CRM 146 R
Total Cd
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
100
Pressurised digestion using HNO3 (1 ml) for 10 h at

170 C followed by H F (0.5 ml) for 10 h at 170 C
and H 3 B 0 4 (5 ml) for 10 h at 100 C; dilution with
Milli-Q H 2 0
Calibrant: commercial solution of Cd
ETAAS
100
As above
Calibrant: as above
ICPAES
100
As above
Calibrant: as above
I C P M S of Cd mass
111
60-80
High pressure ashing in quartz vessels with H N 0 3 (2

ml) and HC10 4 (0.3 ml) for 3 h at 280 C; treated
with H F and H N 0 3 i n Pt crucibles; residue taken up
in HCl (0.4 ml) and diluted with Milli-Q H 2 0
Calibrant: as above
DPASV
500
Pressurised microwave digestion with H F (4 ml),

HNO3 (5 ml) and HCl (1 ml) for 30 min; addition of
H 3 B 0 4 (2 g); dilution with H 2 0
Calibrant: commercial solution of Cd in H N O , CO.5
m o l . l ' ) checked against Cd metal (purity 99.99 %)
FAAS
500
Open digestion with H N 0 3 / H C 1 0 , / H F for 16 h at 20

C ; evporation to dryness at 170 C; repeated with
H F (5 ml); dissolution in HCl (10 ml)(6mol.l')
Calibrant: commercial solution of Cd in HCl
checked against other calibrant solution
ETAAS
15
Table 7.2:
Total Cd (ctd)
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
250
Digestion with aqua regia (1 ml) and H F (10 ml) for

12 h at 20 C; evaporation during 4 h at 100 C;
addition of aqua regia (10 ml) and heating in
microwave for 2 min at 180 W , 5 min at 600 W and
80 min at 510 W; addition of NH 2 OH.HCl (2.5 ml);
dilution with Milli-Q H 2 0 ; mixing with pentane
dione at p H 3 and extraction of Fe into CHC1 3 ;
addition of N a D D T C and extraction of Cd into
MIBK
Calibrant: commercial solution of Cd in H N O ,
FAAS
180-300
Programmed dry ashing upto 450 C in Pt crucible;

followed by digestion with HF/HNOj/HClO., for 3 h
at room temperature and evaporation to dryness at
150 C; dissolution in H N 0 3 at 100 C for 15 min
ICPMS of Cd mass
111
180-300
As above
Calibrant: as above
DPASV
1000
Addition of " 2 C d spike; digestion in PTFE lined

bomb with H N 0 3 / H F (10 ml/5 ml) for 2 d at 180
C; evaporation to dryness; further with
H N 0 3 / H C 1 0 4 (5 ml/2 ml); evaporation to dryness;
addition of HCl (10 ml)(2 mol.l' 1 ); anion exchange
procedure; elution with H N 0 3 (2 mol.l" 1 );
evaporation to dryness; addition of NH 3 buffer;
electrodeposition
Calibrant: calibration of spike with 2 different Cd
solutions; Cd metal (purity S 99.999 % ) ; natural
isotopie ratio
IDMS (thermal
ionisation) of Cd
masses 111, 112
and 114
13
i6
Table 7.2:
Total Co
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
200
Open digestion in Pt crucibles with H F / H C 1 0 4 (10

ml/1 ml) for 3 h to dryness; residue taken up in HCl
(3 mol.l" 1 ); dilution with H 2 0
Calibrant: commercial solution of Co in H N O ,
checked against Co metal (purity 99.99 %)
FAAS
80
Irradiation with thermal neutrons ( 4 x l 0 ' 3 c m ' 2 s ' ) for

5 h; decay time 2-3 weeks; transfer to un-irradiated
polyvial; counting for 4 h
Calibrant: Co metal (purity 99.98 %) in 10 % H N O ,
Gamma
spectrometry of
Co
500
Open digestion with HNCyHCIO,, / H F for 16 h at

20 C; evaporation to dryness at 170 C; repeated
with H F (5 ml); dissolution in HCl (10 ml)
(6 mol.l-')
Calibrant: commercial solution of Co in HCl
ETAAS
100-150
Material pressed into pellet; irradiation with thermal

neutrons (1.8xl0' 2 cm" 2 s"') for 7 h; decay time 4
weeks; counting for 16 h
Calibrant: Co metal (purity > 99.99 %)(etched with
H N 0 3 ) in H N 0 3 ; as well as a commercial solution
of Co in H N 0 3
Gamma
spectrometry of
Co
180-300

followed by digestion with HF/HNC^/HCIO for 3 h
Calibrant: commercial solution of Co in HNO,
I C P M S of Co mass
59
200
Pressurised digestion with H N 0 3 / H F (3 ml/1 ml) for

2 h at 180 C
ETAAS
11
17
Table 7.2:
Total Co (ctd)
Sample mass
(mg)
700
Sample pretreatment
Final
determination
Irradiation with thermal neutrons (3xl0"cm"2s~') for

7 h; decay time 8 weeks; counting for 5 h
Calibrant: commercial solution of Co checked bv
titration
18
Gamma
spectrometry of
Co
Series
in tables
Annex I
13
Table 7.2:
Total Cr
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
100
Pressurised digestion using HNOj (1 ml) for 10 h at

170 C followed by HF (0.5 ml) for 10 h at 170 C
and H3BO (5 ml) for 10 h at 100 C; dilution with
Milli-Q H 2 0
Calibrant: commercial solution of Cr
ICPAES
500
Pressurised microwave digestion with HF (4 ml),

H N 0 3 (5 ml) and HCl (1 ml) for 30 min; addition of
H3BO (2 g); dilution with H 2 0
Calibrant: commercial solution of Cr in HNO,
checked against Cr crystallites (purity 99.998 %)
FAAS
80
Irradiation with thermal neutrons (4xl013cm"2s"') for

Calibrant: K,Cr,0, (purity 99.98 %) in ,; NIST
SRM 1362
Gamma
spectrometry of
5l
Cr
500
Open digestion with HN0 3 /HC10 4 /HF for 16 h at 20

C
C; evaporation to dryness at 170 C; repeated with
HF (5 ml); dissolution in HCl (10 ml)(6 mol.l 1 )
Calibrant: commercial solution of Cr in HCl checked
against other calibrant solution
ICPAES
100

neutrons (1.8xl0' 2 cm" 2 s') for 7 h; decay time 4
Calibrant: Cr metal in HCl (purity >99.99 %)
(etched with HCl (3 mol.l 1 )); verified against CRM
146
Gamma
spectrometry of
51
Cr
180-300

followed by digestion with HF/HNO,/HC10 4 for 3 h
Calibrant: commercial solution of Cr in HN0 3
ICPMS of Cr mass
52
19
Table 7.2:
Total Cr (ctd)
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
200
Pressurised digestion with HNOj/HF (3 ml/1 ml) for

2 h at 180 C
Calibrant: commercial solution of Cr in HCl
FAAS
11
1000
Addition of " Cr spike; digestion in P T F E lined

bomb with H N 0 3 / H F (10 ml/3 ml) for 3 d at 180
C; evaporation to dryness; further with
H F (5 ml); evaporation to dryness; dissolution in
HCl (10 ml)(6 mol.l"'); anion exchange procedure;
evaporation of the eluate; redissolution in acetic acid
(1 mol.l"'); oxidation with potassiumbromate; ion
exchange procedure
Calibrant: calibration of spike using 2 different Cr
solutions; Cr metal (purity 99.996 % ) ; etched with
H F before use
IDMS (thermal
ionisation) of
masses 52, 53 and
54
13
700
Irradiation with thermal neutrons (3xlO u cm" 2 s"') for

7 h; decay time 8 weeks; counting for 5 h
Calibrant: commercial solution of Cr verified bv
titration
Gamma
spectrometry of
5l
Cr
13
300
Open digestion with HNOj (5 ml) for 2 h at 80-100

C ; followed by aqua regia (6 ml) for 4 h at 100
C; addition of H 2 0 2 (4 ml) and left at room
temperature for 2-3 h; addition of H F (10 ml) and
left overnight; addition of H 2 S 0 4 (2 ml) and
evaporation to dryness at 200 C; addition of H N 0 3
and evaporation to dryness; taken up in H N 0 3 ;
filtered through Whatman filter
Calibrant: ICCr,0 7 (purity 99.98 %) in diluted
H N 0 3 ; NIST SRM 1362
FAAS
16
20
Table 7.2:
Total Cu
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
100
Pressurised digestion using HNO, (1 ml) for 10 h at

and H 3 B0 4 (5 ml) for 10 h at 100 C; dilution with
Milli-Q H 2 0
Calibrant: commercial solution of Cu
ICPAES
60-80

ml) and HC104 (0.3 ml) for 3 h at 280 C; treated
with HF and HN0 3 in Pt crucibles; residue taken up
Calibrant: as above
DPASV
500

H 3 B0 4 (2 g); dilution with H 2 0
Calibrant: CuSO.5H 7 0 (purity > 99.5 %) checked
against Cu wire (purity 99.99 %)
FAAS
500
Open digestion with HN0 3 /HC10 4 /HF for 16 h at

20 C; evaporation to dryness at 170 C; repeated
with HF (5 ml); dissolution in HCl (10 ml)
(6 mol.l 1 )
Calibrant: commercial solution of Cu in HCl
ICPAES
180-300

followed by digestion with HF/HNC^/HCIO,, for 3 h
Calibrant: commercial solution of Cu in HNO,
ICPMS of Cu
masses 63 and 65
200
Material pressed into pellets; measured for 2000 s at

45 kV; 5 mA
Calibrant: addition of known amounts of pure metals
(Cr, Cu, Mn, Ni, Pb and Zn) for calibration to 3
separate pellets; all elements added as acid solutions
of metals (purity >99.5 %)
EDXRF
10
21
Table 7.2:
Total Cu (ctd)
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
200
Pressurised digestion with HNOj/HF (3 ml/1 ml) for

2 h at 180 C
Calibrant: commercial solution of Cu in H N O ,
FAAS
11
500
Addition of " C u spike; digestion in P T F E lined

bomb with H N O j / H F (10 ml/5 ml) for 2 d at 180
C ; evaporation to dryness; addition of H F (5 ml);
evaporation to dryness; further with H N 0 3 / H C 1 0 4 (5
ml/2 ml); evaporation to dryness; uptake in HCl (0.2
mol.l" 1 ); separation by electrodeposition
Calibrant: calibration of spike with 2 different Cu
solutions; Cu metal (purity ^ 99.999 % ) ; metal was
etched before use; natural isotopie ratio
I D M S (thermal
ionisation) of Cu
masses 63 and 65
13
22
Table 7.2:
Total Hg
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
100
Pressurised digestion using H N O , (1 ml) for 10 h at

Milli-Q H 2 0 ; addition of SnCl 2 ; addition of H N 0 3
Calibrant: commercial solution of Hg
CVAAS
100
Pressurised digestion using H N 0 3 (1 ml) for 10 h at

Milli-Q H 2 0
Calibrant: as above
I C P M S of Hg
mass 202
200-400
Digestion with HNOj/HClO., (2 ml/4 ml) under

reflux; digestion at room temperature for 20 h and
heating for 1 h at 130 C ; filtration; dilution
Calibrant: commercial solution of H g in H N O ,
I C P M S of H g
masses 200, 201
and 202
500
Irradiation with thermal neutrons ( 3 x l 0 " c m " 2 s ' ) for

8 h; decay time 4 weeks; digestion with H N O , / H F
(7 ml/3 ml) in P T F E lined bomb for 2 d at 180 C;
addition of HCl (20 ml)(0.1 mol.l"'); adsorption on
ion exchange resin; counting for 15 h
Calibrant: commercial solution of H g
Gamma
spectrometry of
13
23
Table 7.2:
Total Mn
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
100
Pressurised digestion using HNO, (1 ml) for 10 h at

Milli-Q H 2 0
Calibrant: commercial solution of Mn
ICPAES
500

Calibrant: commercial solution of Mn in HNO,
checked against Mn metal (purity > 99.9 %)
FAAS
100
Irradiation with thermal neutrons (2xl0' 3 cm' 2 s') for

30 s; decay time 2-3 h; counting for 20 min
Calibrant: Mn metal (purity 99.98 %) in 10%
HN0 3 ; NIST SRM 3132
Gamma
spectrometry of
*Mn
500
Open digestion with HN0 3 /HC10 4 /HF for 16 h at

20 C; evaporation to dryness at 170 C C; repeated
with HF (5 ml); dissolution in HCl (10 ml)(6mol.l')
Calibrant: commercial solution of Mn in HCl
ICPAES
100-150

neutrons (2.6xl0' 2 cm" 2 s') for 5 min; decay time 2 h;
counting for 10 min
Calibrant: MnSO.H,0 (purity > 99.9 %) in -,;
verified against CRM 146
Gamma
spectrometry of
56
Mn
180-300

ICPAES
24
Table 7.2:
Total Mn (ctd)
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
200
Material pressed into pellets; measured for 2000 s at

45 kV; 5 mA
of metals (purity > 99.5 %)
EDXRF
10
200
Pressurised digestion with HN0 3 /HF (3 ml/1 ml) for

2 h at 180 C
FAAS
11
300
Irradiation with thermal neutrons (3xl0"cm" 2 s ') for

2 min; decay time 164 min; counting for 2 min
Calibrant: commercial solution of Mn checked bv
titration
Gamma
spectrometry of
56
Mn
13
100-150
Irradiation with thermal neutrons (10' 3 cm" 2 s') for 60

s; decay time 300 s; counting for 300 s
Calibrant: KMn0 4 (purity > 99.99 %")
Gamma
spectrometry of
56
Mn
14
25
Table 7.2:
Total Ni
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
100
Pressurised digestion using HN03 (1 ml) for 10 h at

Milli-Q H 2 0
Calibrant: commercial solution of Ni
ICPAES
60-80

with HF and H N 0 3 in Pt crucibles; residue taken up
Calibrant: as above
DPCSV
500
Pressurised micro wave digestion with HF (4 ml),

HNO-, (5 ml) and HCl (1 ml) for 30 min; addition of
Calibrant: commercial solution of Ni in HNO,
checked against Ni metal (purity 99.99 %)
FAAS
500

HF (5 ml); dissolution in HCl (10 ml)(6 mol.l')
Calibrant: commercial solution of Ni in HCl checked
ICPAES
180-300

followed by digestion with HF/HNOj/HClO,, for 3 h
Calibrant: commercial solution of Ni metal in HNO,
ICPAES
26
Table 7.2:
Total Ni (ctd)
Sample mass
(mg)
1000
Sample pretreatment
Final
determination
Addition of e 2 Ni spike; digestion in P T F E lined

b o m b with HNO3/HF (10 m l / 5 ml) for 2 d at 180
C ; evaporation to dryness; further with
HNO3/HCIO4 (5 ml/2 ml); evaporation to dryness;
dissolution in HCl (6 mol.l" 1 ); anion exchange
procedure; evaporation of eluate; dissolution in H C l
(0.02 mol.l" 1 ); cation exchange procedure; elution
with HCl (2 mol.l"'); evaporation to dryness;
addition of N H 3 buffer; electrodeposition
Calibrant: calibration of spike with 2 different Ni
solutions; Ni metal (purity ^ 99.99 %) etched
before use; natural isotopie ratio
I D M S (thermal
ionisation) of Ni
masses 5 8 , 60 and
62
27
Series
in tables
Annex I
13
Table 7.2:
Total Pb
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
100
Pressurised digestion using H N 0 3 (1 ml) for 10 h at

Milli-Q H 2 0
Calibrant: commercial solution of Pb
ETAAS
100
As above
Calibrant: as above
ICPAES
100
As above
Calibrant: as above
ICPMS of Pb
mass 208
60-80

Calibrant: as above
DPASV
500
Pressurised microwave digestion with 4 ml HF, 5 ml

H N 0 3 and 1 ml HCl for 30 min; addition of 2 g
H 3 B0 4 ; dilution with H 2 0
Calibrant: commercial solution of Pb in HNO, (0.5
mol.l"1) checked against Pb metal (purity 99.99 %)
FAAS
500

HF (5 ml); dissolution in HCl (10 ml)(6 mol.l')
Calibrant: commercial solution of Pb in HN0 3
ICPAES
180-300

Calibrant: commercial solution of Pb in HNO,
ICPMS of Pb
masses 206, 207
and 208
28
Table 7.2:
Total Pb (ctd)
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
180-300
As above
Calibrant: as above
DPASV
200
Material pressed in to pellets; measured for 2000 s

at 45 kV, 5 mA
EDXRF
10
200
Pressurised digestion with HNO5/HF (3 ml/1 ml) for

2 h a t 180 C
FAAS
11
200
Addition of 204Pb spike; digestion in PTFE lined

bomb with HNOj/HF (10 ml/5 ml) for 2 d at 180
C; evaporation to dryness; addition of HF (5 ml);
addition of HNO3/HCIO (5 ml/2 ml); fuming;
evaporation to dryness; dissolution in HBr
(1 mol.l"'); separation on anion exchange resin
Calibrant: calibration of spike with 2 different
solutions; Pb metal (purity S 99.999 %); metal
etched before use
IDMS (thermal
ionisation) of Pb
masses 204, 206,
207 and 208
13
29
Table 7.2:
Total Zn
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
100
Pressurised digestion using HNOj (1 ml) for 10 h at

Milli-Q H 2 0
Calibrant: commercial solution of Zn
ICPAES
60-80

ml) and HCI0 4 (0.3 ml) for 3 h at 280 C; treated
Calibrant: as above
DPASV
500

H3BO (2 g); dilution with H 2 0
Calibrant: commercial solution of Zn in HNO, (0.5
mol.l1) checked against Zn metal (purity 99.99 %)
FAAS
80
Irradiation with thermal neutrons (4xl0' 3 cm' 2 s 1 ) for

Calibrant: Zn metal (purity 99.99%) in 1 mol.l"'
HN0 3 ; NIST SRM 728
Gamma
spectrometry of
"Zn
500

HF (5 ml); dissolution in HCl (10 ml)(6 mol.l"1)
Calibrant: commercial solution of Zn in HCl
ICPAES
100

neutrons (1.8xl0 12 c m ' V ) for 7 h; decay time 4
Calibrant: Zn metal (purity > 99.99 %). etched
with H N 0 3 (3 mol.l"'); verified against CRM 146
Gamma
spectrometry of
Zn
30
Table 7.2:
Total Zn (ctd)
Sample mass
(mg)
Final
determination
Sample pretreatment
Series
in tables
Annex I
180-300
Programmed dry ahing up to 450 C in Pt crucible;

followed by digestion with HF/HNQ,/HC10 4 for 3 h
Calibrant: commercial solution of Zn metal in HNO,
ICPMS of Zn
masses 64 and 66
200
Material pressed into pellets; measured for 2 000 s

at 45 kV, 5 mA
EDXRF
10
200
Pressurised digestion with HNO3/HF (3 ml/1 ml) for

2 h at 180 C
FAAS
11
200
Addition of ^Zn spike; digestion in PTFE lined

bomb with H N Q / H F (10 ml/5 ml) for 2 d at 180
C; evaporation to dryness; addition of HF (5 ml);
evaporation to dryness; further with
HN0 3 /HC10 4 (5 ml/2 ml); evaporation; dissolution
in HCl (2 mol.l' 1 ); anion exchange procedure;
elution with HCl (0.1 mol.l"'); electrodeposition
Calibrant: calibration of spike with 2 different
solutions; Zn metal (purity 99.99 %); etched before
use; natural isotopie ratio
IDMS (thermal
ionisation) of Zn
masses 64, 66 and
68
13
300
Open digestion with HNCX, (5 ml) for 2 h at 80-100

C; followed by aqua regia (6 ml) for 4 h at 100
C; addition of H 2 0 2 (4 ml) and left at room
temperature for 2-3 h; addition of HF (10 ml) and
left overnight; addition of H 2 S0 4 (2 ml) and
evaporation to dryness at 200 C; addition of H N 0 3
and evaporation to dryness; taken up in HN0 3 ;
filtered through Whatman filter
Calibrant: commercial solution of Zn verified against
Zn metal (purity > 99.99 %)
FAAS
16
31
Table 7.2:
Aqua regia soluble Cd
(according to DIN 38414-S7)
Final
determination
Sample pretreatment
Series
in tables
Annex I
Calibrant: commercial solution of Cd
ETAAS
Calibrant: as above
ICPAES
Calibrant: as above
ICPMS of Cd
mass 111
Calibrant: commercial solution of Cd in HNO, (0.5

mol.l') checked against Cd metal (purity 99.99 %)
FAAS

ETAAS
Ten fold dilution with H N 0 3 (0.14 mol.l"1); addition

of In as internal standard
Calibrant: commercial solution of Cd in HNO,
verified against Cd metal in H N 0 3 (purity 99.95 %)
ICPMS of Cd
mass 111
ICPMS of Cd
masses 111, 112
and 114
Addition of " 2 Cd spike to extract; evaporation to

dryness; addition of HCl (10 ml)(2 mol.l' 1 ); anion
exchange procedure; elution with H N 0 3 (2 mol.l"');
evaporation to dryness; addition of NH 3 buffer;
electrodeposition
Calibrant: calibration of spike with 2 different Cd
solutions; Cd metal (purity 99.999 %), etched before
use
IDMS (thermal
ionisation) of Cd
masses 111, 112
and 114
13
32
Table 7.2:
Aqua regia soluble Co
Final
determination
Sample pretreatment
Series
in tables
Annex I
Calibrant: commercial solution of Co
ICPAES

checked against Co metal (purity 99.99 %)
FAAS
Centrifugation to separate residue from extract;

residue dried for 18 h at 110 C until constant
weight; residue mixed and 0.8 g is irradiated with
thermal neutrons (4xl0 13 c m ' V ) for 5 h; decay time
2-3 weeks; transfer to un-irradiated polyvial;
counting for 12 h; aqua regia soluble content
calculated through difference
Calibrant: Co metal (purity 99.98 %i in 10 % HNO,
Gamma
spectrometry of
Co

ICPAES
Spiked on Whatman 41 filterpaper; irradiation with

thermal neutrons (1.8xl0 12 c m ' V ) for 7 h; decay
time 4 weeks; counting for 2 0 h
Calibrant: Co metal in H N 0 3 (purity 99.99 %)
(etched in HN0 3 ) as well as a commercial solution
of Co in H N 0 3
Gamma
spectrometry of
Co
5 ml of extract treated with HF (1 ml)(50 %) and

HNOj (5 ml)(14 mol.l' 1 ); heated at 70 C overnight
and evaporated to near dryness; residue taken up in
diluted HN0 3 ; addition of Ge as internal standard
checked against Co metal (purity 99.99 %) in H N 0 3
ICPMS of Co
mass 59
33
Table 7.2:
Aqua regia soluble Co (ctd)
Sample pretreatment
Final
determination
Series
in tables
Annex I
Calibrant: commercial solution of Co in H N 0 3
ICPMS of Co
mass 59
ETAAS
11
34
Table 7.2:
Aqua regia soluble Cr
Final
determination
Sample pretreatment
Series
in tables
Annex I
Calibrant: commercial solution of Cr
ICPAES

checked against Cr crystallites (purity 99.998 %)
FAAS

weight; residue mixed and 0.8 g is irradiation with
thermal neutrons (4xl0 13 c m ' V ) for 5 h; decay time
Calibrant: K 7 Cr,0 7 (purity 99.98 %) in ,: NIST
SRM 1362
Gamma
spectrometry of
51
Cr

ICPAES
ICPMS of Cr
mass 52
Calibrant: commercial solution of Cr in HCl
FAAS
11

against CRM
FAAS
12
35
Table 7.2:
Aqua regia soluble Cr (ctd)
Series
in tables
Annex I
Sample pretreatment
Final
determination
Addition of 53Cr spike to extract; evaporation to

dryness; dissolution in HCl (6 mol.l"1); anion
exchange procedure; evaporation of eluate;
dissolution in HOAc (1 mol.l' 1 ); oxidation of Cr(III)
to Cr(VI) with potassiumbromate; anion exchange
procedure
Calibrant: calibration of spike with 2 different Cr
solutions; Cr metal (purity 99.999 %); etched before
use with HCl
IDMS (thermal
ionisation) of Cr
masses 52, 53 and
54
13
Extraction carried out in closed teflon tubes with

aqua regia (10 ml) at room temperature for 12 h;
followed by heating for 3 h at 130 C; centrifugation
at 3000 rpm; filtered through Whatman No 54
Calibrant: K,Cr,0, (purity 99.98 %Y. NIST SRM
1362
FAAS
16
36
Table 7.2:
Aqua regia soluble Cu
Final
determination
Sample pretreatment
Series
in tables
Annex I
Calibrant: commercial solution of Cu
ICPAES
Calibrant: CuSO.5H,0 (puritv > 99.5 %Y. checked

against Cu wire (purity 99.99 %)
FAAS
ICPAES
5 ml of extract treated with H F (1 ml)(50 %) and

HNO3 (5 ml)(14 mol.l"1); heated at 70 C overnight
diluted H N 0 3 ; addition of Ge as internal standard
Calibrant: commercial solution of Cu in HNO ?
checked against Cu metal (purity 99.99 %) in H N 0 3
ICPMS of Cu
masses 63 and 65
Calibrant: commercial solution of Cu in HNO,
ICPMS of Cu
masses and 65
Solution spiked on polypropylene film; measured for

2 000 s at 45 kV; 5 mA
( Cr, Cu, Mn, Ni, Pb and Zn) for calibration to 3
EDXRF
10
Calibrant: commercial solution of Cu in H N 0 3
FAAS
11

checked against CRM
FAAS
12
37
Table 7.2:
Aqua regia soluble Cu (ctd)
Final
determination
Sample pretreatment
DIN 38414-S7; addition of " C u spike to extract;

evaporation to dryness; dissolution in HCl (0.2
mol.l' 1 ); separation by electrodeposition
Calibrant: calibration of spike with 2 different Cu
solutions; Cu metal (purity 99.999 % ) ; etched before
use
38
IDMS (thermal
ionisation) of Cu
masses 63 and 65
Series
in tables
Annex I
13
Table 7.2:
Aqua regia soluble Hg
Final
determination
Sample pretreatment
Series
in tables
Annex I
Calibrant: commercial solution of Hg
CVAAS
Calibrant: as above
ICPMS of Hg
mass 202
Calibrant: commercial solution of Hg in H N 0 3

checked against Hg metal (purity 99.999 %)
CVAAS
Addition of SnCl; addition of HCl

Calibrant: commercial solution of Hg in HCl
CVAAS
5 fold dilution; addition of Tl as internal standard

Calibrant: addition of known amount of Isoflex
Hg(201) enriched standard
ID ICPMS of Hg
masses 202 and
201
39
Table 7.2:
Aqua regia soluble Mn
Final
determination
Sample pretreatment
Series
in tables
Annex I
Calibrant: commercial solution of M n
ICPAES
Calibrant: commercial solution of M n in H N O ,

checked against M n metal (purity > 99.9 %)
FAAS

residue dried for 1 8 h a t l l O C until constant
thermal neutrons ( 2 x l 0 1 3 c m ' V ) for 30 sec; decay
time 2-3 h; counting for 20 min; aqua regia soluble
content calculated through difference
Calibrant: M n metal (purity 99.98 %) in 10 %
H N 0 3 ; N I S T S R M 3132
Gamma
spectrometry of
3<s
Mn
Calibrant: commercial solution of M n in HCl

ICPAES
5 ml of extract treated with H F (1 ml)(50 %) and

H N 0 3 (5 ml)(14 m o l . l 1 ) ; heated at 70 C overnight
diluted H N 0 3 ; addition of G e as internal standard
Calibrant: commercial solution of M n in H N O ,
checked against M n powder (purity > 99 %) in
HNO3
I C P M S of M n
mass 5 5
Calibrant: commercial solution of M n in HCl
ICPAES
40
Table 7.2:
Aqua regia soluble M n (ctd)
Final
determination
Sample pretreatment
Series
in tables
Annex I

2 000 s at 45 kV; 5 mA
of metals (purity > 99.5%)
EDXRF
10
FAAS
11

checked against CRM
FAAS
12
41
Table 7.2:
Aqua regia soluble Ni
Final
determination
Sample pretreatment
Series
in tables
Annex I
Calibrant: commercial solution of Ni
ICPAES
Calibrant: commercial solution of Ni in HNO,

checked against Ni metal (purity 99.99 %)
FAAS

against other standard solution
ICPAES
5 ml of extract treated with HF (1 ml)(50 %) and

HNOj (5 ml)(14 mol.l'); heated at 70 e C overnight
Calibrant: commercial solution of Ni in H N 0 3
checked against Ni metal (purity 99.99 %) in H N 0 3
ICPMS of Ni
masses 60 and 62
Addition of NH 2 OH.HCl before filling up to the

mark; mixing with pentane dione at pH 3 and
extraction of Fe into CHC13; addition of NaDDTC;
extraction into MIBK
Calibrant: commercial solution of Ni in H N 0 3
FAAS
Calibrant: commercial solution of Ni metal in H N 0 3
ICPAES

against CRM
FAAS
12
42
Table 7.2:
Aqua regia soluble Ni (ctd)
Final
determination
Sample pretreatment
Addition of "Ni spike to extract; evaporation to

dryness; dissolution in HCl (6 mol.l' 1 ); anion
exchange procedure; evaporation of eluate;
dissolution in HCl (0.02 mol.l' 1 ); cation exchange
procedure; elution with HCl (2 mol.l"'); evaporation
to dryness; electrodeposition from NH 3 buffer
Calibrant: calibration of spike with 2 different Ni
solutions; Ni metal (purity 99.99 %); etched before
use
43
IDMS (thermal
ionisation) of Ni
masses 58, 60 and
62
Series
in tables
Annex I
13
Table 7.2:
Aqua regia soluble Pb
Final
determination
Sample pretreatment
Series
in tables
Annex I
Calibrant: commercial solution of Pb
ETAAS
Calibrant: as above
ICPAES
Calibrant: as above
ICPMS of Pb
mass 208
Calibrant: commercial solution of Pb in HNO, (0.5

mol.l' 1 ) checked against Pb metal (purity 99.99 %)
FAAS

ICPAES
20 to 40 fold dilution; addition of as internal

standard
Calibrant: known amount of NIST SRM 983
standard (purity 99.9 %) enriched in Pb(206)
ID ICPMS of Pb
masses 208 and
206
Calibrant: commercial solution of Pb in HNCL,
ICPMS of Pb
masses 206, 207
and 208
Calibrant: commercial solution of Pb in HNOj

checked against CRM
FAAS
12
Addition of ^ P b spike to extract; evaporation to

dryness; dissolution in HBr (1 mol.l"'); anion
exchange procedure
Calibrant: calibration of spike with 2 different Pb
solutions; Pb metal (purity 99.999 %); etched before
use with HOAc
IDMS (thermal
ionisation) of Pb
masses 204, 206,
207 and 208
13
44
Table 7.2:
Aqua regia soluble Zn
Final
determination
Sample pretreatment
Series
in tables
Annex I
Calibrant: commercial solution of Zn
ICPAES
Calibrant: commercial solution of Zn in HNO, (0.5

mol.l') checked against Zn metal (purity 99.99 %)
FAAS

thermal neutrons (4xl0 1 3 c m ' V ) for 5 h; decay time
Calibrant: Zn metal (purity 99.99 %) in 1 mol.l"1
H N 0 3 ; NIST SRM 728
Gamma
spectrometry of
"Zn

ICPAES
5 ml of extract treated wii HF (1 ml)(50 %) and

HNOj (5 ml)(14 mol.l 1 ); heated at 70 C overnight
Calibrant: commercial solution of Zn in HNO,
checked against Zn metal (purity 99.99 %) in H N 0 3
ICPMS of Zn
masses 66 and 68
Calibrant: commercial solution of Zn metal in HNO,
ICPMS of Zn
masses 64 and 66
45
Table 7.2:
Aqua regia soluble Zn (ctd)
Final
determination
Sample pretreatment
Series
in tables
Annex I

2 000 s at 45 kV; 5 mA
EDXRF
10
FAAS
11

checked against CRM
FAAS
12
Addition of Z n spike to extract; evaporation to

dryness; dissolution in HCl (2 mol.l"1); anion
exchange procedure; elution with HCl (0.1 mol.l"1);
electrolytic deposition
Calibrant: calibration of spike with 2 different Zn
solutions; Zn metal (purity 99.999 %); etched before
use
IDMS (thermal
ionisation) of Zn
masses 64, 66 and
68
13
46
8.
TECHNICAL AND STATISTICAL DISCUSSION
All the results accepted for certification by the participating laboratories are given in the tables
1-18 in Annex I. Each set of results is identified by the code number of the laboratory.
The
details of the analytical methods used by each laboratory are given in the table 7.2 for both total
and aqua regia soluble fractions (section 7).
All the results were discussed at a technical evaluation meeting to confirm the performance of
the methods of analysis and their respective values.
All data accepted for certification were obtained from laboratories which had demonstrated good
analytical quality control and had fully implemented the analytical precautions outlined in section
7.
8.1.
Technical evaluation
Since the CRM is rich in silicates or alumino silicates to which some trace elements may be
bound, the application of an alkaline fusion or the use of H F in acid digestions is recommended
for the determination of the total contents of the elements.
Some remarks made for individual elements during the technical discussion are summarised
below as guidelines for the user.
Cobalt
Laboratory 2 determined Co by DPASV and came to the conclusion that it is not the most
appropriate technique for this element. The results were consequently withdrawn.
Nickel
Laboratories using INAA for the determination of Ni, via the 58Ni (n,p)
take into account the possible nuclear interference from
leading to an overestimation of the Ni content.
47
59
58
Co reaction, should
Co (n,2n) 58 Co, also yielding
58
Co, thus
Zinc
Laboratory 4 (INAA) was confident that it was possible to separate the 65Zn peak from a much
larger, possibly interfering, ^Sc peak in the INAA spectrum since the same results were
obtained with different deconvolution programs. Nevertheless, laboratories using INAA should
take into account the high Sc content.
8.2
General statistical discussion
For each set of results in the tables 1-18 of Annex I the mean value and the standard deviation
are calculated.
The sets of results have further been submitted to the following statistical tests:
Kolmogorov-Smirnov-Lilliefors tests to assess the conformity of the distributions of
individual results and of laboratory means to normal distributions;
Nalimov test to detect "outlying" values in the population of individual results and in
the population of laboratory means;
Bartlett test to assess the overall consistency of the variance values obtained in the
participating laboratories;
Cochran test to detect "outlying" values in the laboratory variances (s2);
One way analysis of variance (F-test) to compare and estimate the between- and the
within-laboratory components of the overall variance of all individual results.
For Cochran and Nalimov tests, a value is called an "outlier" when the hypothesis that it belongs
to the population of results considered can be rejected with a 0.01 risk of error. For a
"straggler", the risk lies between 0.01 and 0.05. The criterion was adopted that an "outlier" of
variance would be eliminated only if the standard error of the mean (sA/n) of the set exceeded
the standard deviation of the distribution of all laboratory means.
A summary of the statistical data, as obtained from computing, is given in the tables 8.1 and 8.2
respectively for total and aqua regia soluble contents. They are reported only for the certified
values (presented in the tables 9.1 and 9.2). The data are discussed in section 8.3.
48
The sets of results found acceptable on technical and statistical grounds are represented in the
form of "bar-charts" in the figures 1-18 of Annex I.
In the figures the length of a bar
corresponds to the 95 % confidence interval of the mean. The certified values were calculated
as the arithmetic means of the laboratory means (taking into account the number of sets accepted
for certification after both statistical and technical scrutiny); they are featured as vertical dotted
lines on the bar-graphs. The uncertainty is given by the half width of the 95 % confidence
interval of the mean of laboratory means.
8.3.
Statistical evaluation of the results
The within-laboratory standard deviation (S w ) and the between-laboratory standard deviation (SB)
as derived from one way analysis of variance (presented in tables 8.1 and 8.2) demonstrate that
the between-laboratory variation was the major source of variability (between results) in almost
all cases. For Co and Hg, S w was higher than SB which would indicate that the calculation of
the overall mean of the results should involve all individual values. As the differences between
the means (obtained by averaging the laboratory means or by averaging the individual values)
were only small, and for reasons of uniformity, it was decided to base the certification of these
elements on the laboratory means rather than on all individual results.
As in all cases the population of results accepted for certification had a normal distribution
(Kolmogorov-Smirnov-Lilliefors tests) and did not contain outlying mean values (Nalimov test),
the 95 % confidence interval of the means of the laboratory means was calculated.
The set of variances is often not homogeneous which is due to the fact that different methods
are used each having a different repeatability and reproducibility.
If one single method were
used then a homogeneous set of laboratory variances would be required. Consequently the S w
(within-laboratory standard deviation) calculated is not applicable to any particular method
because it is a composite value for all the methods used in this certification.
49
The variance proved to be homogeneous for Cu, Co(AR), Hg(AR), Pb(AR) and Zn(AR), not
homogeneous with 0.05 > > 0.01 for Cd, Cr(AR) and Ni(AR) and not homogeneous with
0.01 > for Co, Cr, Hg, Mn, Ni, Pb, Zn, Cd(AR), Cu(AR) and Mn(AR).
The sets of data of lab 16 (FAAS) for Cr, lab 10 (EDXRF) and lab 4 (INAA) for Mn and
Mn(AR), lab 2 (DPASV) for Pb and Zn as well as lab 2 (ICPAES) for Co(AR) were identified
as stragglers or outliers of variance (Cochran test).
Since they satisfied the criterion for
acceptance (section 8.2) they could be retained for calculation of the certified value. The sets
of results of lab 2 (ICPAES) for Cd, of lab 3 (FAAS) as well as lab 5 (ETAAS) for Cd(AR) and
the set of results of lab 7 (FAAS) for Ni(AR) had to be rejected because they did not satisfy the
same criterion.
50
Table 8.1:
Summary of statistical data for the total content of Cd, Co, Cr, Cu, Hg, Mn, Ni,
Pb and Zn in BCR CRM 146 R (expressed as mg/kg)
Elements
Cd
Co
Cr
Cu
Hg
Number of data sets
10
Number of accepted replicates
48
35
53
41
20
All data sets compatible two by
yes
yes
yes
yes
yes
no
no
no
no
no
no
no
yes
no
no
Mean of means
18.76015
7.39194
195.98800
837.85920
8.62150
sw
sb
0.46500
0.40326
8.97310
15.61579
0.34295
0.49469
0.22097
7.79842
16.55579
0.13405
yes
yes
yes
yes
no
about
no
no
yes
no
0.54735
0.28522
8.68012
18.09169
0.20370
yes
yes
yes
yes
yes
0.42073
0.26378
6.20943
15.12512
0.32412
two? (Scheff's multiple t-test)

Outlying data sets? (Dixon's test,
Nalimov t-test and Grubbs test)
Outlying variances? (Cochran
test)
Between data SD significant?

(Snedecor test)
Variances homogeneous?
SD of means
Data sets means normally
distributed? (KomogorovSmirnov-Lilliefors test)
95 % CI of the mean of means
51
Table 8.1:
continued
Mn
Ni
Pb
Zn
Number of data sets
10
11
11
54
31
59
58
yes
yes
yes
yes
no
no
no
yes
no
yes
323.44850
69.63490
608.71770
3061.3790
8.72792
2.77116
16.40069
58.90373
8.33227
3.61404
19.52996
83.98067
yes
yes
yes
yes
no
no
no
9.22985
3.82738
20.80651
yes
yes
yes
6.60269
4.01652
13.97809
Elements

test)
Mean of means
sw
sb
(Snedecor test)
SD of means
88.16988

CI
Confidence interval
SD
Standard deviation
Sw
Within-laboratory standard deviation
Sb
Between-laboratory standard deviation
52
59.23364
Table 8.2:
Summary of statistical data for the aqua regia soluble content of Cd, Co, Cr, Cu,
Hg, Mn, Ni, Pb and Zn in BCR CRM 146 R (expressed as mg/kg)
Elements
Cd
Co
Cr
Cu
Hg
Number of data sets
31
41
47
46
25
yes
yes
yes
yes
yes
no
no
no
no
no
no
yes
no
no
no
Mean of means
18.44816
6.50139
173.74110
831.26760
8.39200
sw
s
0.27966
0.34673
3.91544
14.77243
0.19341
0.30620
0.32611
8.78213
19.26049
0.17617
yes
yes
yes
yes
yes
no
yes
about
no
yes
0.33224
0.36475
9.06246
20.53455
0.19625
yes
yes
yes
yes
yes
0.34866
0.30494
6.96608
15.78442
0.24368

test)

(Snedecor test)
SD of means
53
Table 8.2:
continued
Mn
Ni
Pb
Zn
Number of data sets
10
45
35
46
51
yes
yes
yes
yes
no
no
no
no
yes
no
no
no
297.98330
65.01475
583.19360
3042.3490
8.65127
1.76719
9.65874
62.85468
10.70838
3.12949
21.41793
75.10096
yes
yes
yes
yes
no
about
yes
yes
11.38587
3.22774
22.04627
80.77613
yes
yes
yes
yes
8.75204
2.98516
16.94641
57.78418
Elements

test)
Mean of means
sw
sb
(Snedecor test)
SD of means
CI
Confidence interval
SD
Standard deviation
Sw
Within-laboratory standard deviation
Sb
Between-laboratory standard deviation
54
9.
CERTD7D2D VALUES
The certified values for the total contents and the aqua regia soluble fraction (both expressed
as the mass fractions based on dry mass (see chapter 11)) are presented in tables 9 . 1 . and 9.2
respectively. The certified value is the unweighted mean of accepted sets of results. The
half width of the 95 % confidence interval of the mean is used as the estimate of the
uncertainty.
Table 9 . 1 :
Certified total mass fractions of Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb and Zn in
BCR CRM 146 R (expressed as mg/kg)
Element
Certified
value
Uncertainty
Number of accepted
results (p)
Treatment in Tables
of Annex I
Cd
Co
Cr
Cu
Hg
Mn
Ni
Pb
Zn
18.8
7.39
196
838
8.62
324
69.7
609
3061
0.5
0.27
7
16
0.33
7
4.0
14
59
9
7
10
8
4
10
6
11
11
la
2a
3a
4a
5a
6a
7a
8a
9a
Table 9.2:
Certified a q u a regia soluble mass fractions of Cd, Co, Cr, Cu, Hg, Mn, Ni,
Pb and Zn in BCR CRM 146 R (expressed as mg/kg)
Element
Certified
value
Uncertainty
Number of accepted
results (p)
Treatment in Tables
of Annex I
Cd
Co
Cr
Cu
18.5
6.50
174
831
8.39
298
65.0
583
3043
0.4
0.31
7
16
0.25
9
3.0
17
58
6
8
9
9
5
9
7
9
10
10a
11a
12a
13a
14a
15a
16a
17a
18a
Hg
Mn
Ni
Pb
Zn
55
10.
ADDITIONAL INFORMATION
During the course of the certification exercise some laboratories individually determined
other elements.
These results are given in table 10.1 as additional information.
emphasised that these values are not certified.

Table 10.1:
Informative values for BCR CRM 146 R (total element contents)

Element
Al(g/kg)
As (mg/kg)
Ba (mg/kg)
Br
Ca
Cl
Fe
(mg/kg)
(g/kg)
(mg/kg)
(g/kg)
I (mg/kg)
K (g/kg)
La (mg/kg)
Mg (g/kg)
Na (g/kg)
P (g/kg)
S (g/kg)
Sb (mg/kg)
Sn (mg/kg)
Sr (mg/kg)
Ti (mg/kg)
Th (mg/kg)
Tl (Mg/kg)
U (mg/kg)
V (mg/kg)
W (mg/kg)
Mean value
25.13
6.30
786
683.6
7.36
154.6
371.0
17.7
14.38
2.57
5.66
4.82
19.8
10.46
1.915
1.692
25.6
10.62
18.8
13.7
95.8
1179
2771
4.25
578
2.22
42.7
5.13
S.D.*
1.37
1.01
19
57.2
0.66
5.9
29.28
0.5
0.37
0.30
1.7
0.3
0.83
0.25
0.2
0.03
1.7
0.22
0.4
0.23
2.2
43
85
0.17
9
0.037
1.7
0.18
56
Techniques used
ICPAES
INAA
ICPAES
INAA
INAA
ICPAES
INAA
ICPAES
INAA
INAA
ICPAES
INAA
INAA
ICPAES
ICPAES
INAA
ICPAES
ICPAES
ICPMS
INAA
ICPMS
ICPAES
ICPAES
INAA
ICPMS
INAA
ICPAES
INAA
It is
Table 10.2:
Informative values for BCR CRM 146 R (aqua-regia soluble contents)

Element
Al (g/kg)
(mg/kg)
Ba (mg/kg)
Ca (g/kg)
Fe (g/kg)
(mg/kg)
Mg (g/kg)
Na (mg/kg)
P (g/kg)
S (g/kg)
Sb (mg/kg)
Sn (mg/kg)
Sr (mg/kg)
Ti (mg/kg)
Tl (Mg/kg)
V (mg/kg)
p:
*:
Mean value
17.45
92.1
632
148.3
15.82
1825
8.87
555
28.0
8.80
12.0
81.6
1131
124
514
33.3
S.D.*
0.22
5.5
5
1.1
0.14
36
0.04
14
0.3
0.05
0.2
1.0
7
13
4
2.4
sets of results (mean value of at least 4 replicates)

S.D. is calculated for the individual results
57
Techniques used
ICPAES
ICPAES
ICPAES
ICPAES
ICPAES
ICPAES
ICPAES
ICPAES
ICPAES
ICPAES
ICPMS
ICPMS
ICPAES
ICPAES
ICPMS
ICPAES
11.
INSTRUCTIONS FOR USERS
The following notes are a guide to the user of this reference material for the determination
of trace elements in sewage sludge from industrial origin.
PLEASE CONSULT THESE NOTES PRIOR TO OPENING THE BOTTLE.
The sample consists of approximately 50 g of sewage sludge (particle size < 90 ) in a
brown glass bottle provided with PTFE ball for re-homogenisation and closed with a
polyethylene insert and a screw cap.
The material should be used as it is from the bottle. However, upon mailing or storage, the
sample may partly segregate as pointed out in section 4 of this report. This is due to the fact
that the sample contains particles of different size and relative density.
Therefore re-
homogenisation before subsampling is mandatory. This can be done by manual shaking for
at least 5 minutes. The minimum intake is 50 mg.
The closed bottles may be kept in a dry and cool atmosphere. Once opened, the bottles
should be stored closed in a dry desiccator; direct prolonged exposure to sunlight should be
avoided.
The correction to dry mass must be determined on a separate portion taken at the same time
of the analysis from the same bottle.
It can be done by drying in an oven at 105 C until
constant mass is attained (successive weighings should not differ by more than 0.2 g).
In selecting a method of sample treatment, the user should take into account that part of some
elements present may be bound to the inorganic part of the matrix which might be difficult
to dissolve.
Therefore these elements are not completely soluble in oxidizing acids.
Treatment with HF is recommended for the determination of total contents.

For the digestion method used for the determination of the aqua regia soluble part, the reader
is referred to the section 6 of this report. The results in this report are expressed in dry mass
on a mass per mass basis which is different from the way to express results as indicated by
the norm.
58
This reference material is intended to verify the performance of a method and not to
calibrate the method. The more the concentrations and the matrices of sample and chosen
reference materials are similar, the more it is likely that errors can be detected.
When using the reference material for checking an analytical procedure or the performance
of the method, the user can refer to the results of this certification campaign after having
ascertained that the repeatability of his method is satisfactory.
59
The user may assess the bias of his results from the difference between the certified value
() and the mean value of his replicate measurements (x). The criterion for acceptance is
given in ISO-guide 33 (1988) as follows:
-a2 - 2a L < X-/X < a, + 2a L
in which ax and a2 are adjustment values, chosen by the user according to economic or
technical limitations or stipulations, and aL is the long term within laboratory standard
deviation of the user's method (e.g. as reflected on a SHEW ART Quality Control Chart).
Although these materials are not intended for use as a calibrant, they can be used for further
assessment of the calibration. In such a case, the value to be used for each quantity is the
certified mean value with the uncertainty at the 95 % confidence level.
60
ANNEX I
TABLES OF INDIVIDUAL RESULTS AND
GRAPHICAL PRESENTATIONS
61
Cadmium in CRM 146 R - total mass fraction (mg/kg)

Table 1
DATA SET
NUM
REPLICATES.
MEAN
ST.DEV
02 ETAAS
18.1000
17.7000
19.4000
17.3000
17.6000
18.0200
.8228
05 ETAAS
17.4700
18.5600
18.2000
18.2100
18.2600
18.1400
.4026
03 FAAS
18.7700
18.5200
18.7800
19.0300
18.4400
18.7080
.2345
07 FAAS
19.7000
20.0000
19.8000
20.0000
19.8000
19.8600
.1342
02 ICPAES
17.7000
18.9000
16.8000
19.5000
16.2000
17.8200
1.3846
02 ICPMS
18.4000
18.5000
18.8000
18.8000
18.9000
18.6800
.2168
09 ICPMS
19.3000
19.0000
18.6000
18.5000
18.8000
18.6000
18.8000
.3033
13 IDMS
19.4000
19.3000
19.5000
18.9000
18.7000
18.9000
19.1167
.3251
02 DPASV
18.5000
19.7000
19.7000
18.9000
18.2000
19.0000
.6856
09 DPASV
18.4000
18.9000
18.0000
18.6000
17.8000
19.4000
18.5167
.5879
Figure 1
BAR-GRAPHS FOR LABORATORY MEANS AND 95% CI
16.000
+ ..
17.000
... +
18.000
+
19.000
+
20.000
+ ....
02 ETAAS
05 ETAAS
03 FAAS
<..*..>
07 FAAS
02 ICPMS
<...*.
09 ICPMS
<
13 IDMS
02 DPASV
09 DPASV
MEANS'
-M
63
>
>
Cobalt in CRM 146 R - total mass fraction (mg/kg)

Table 2
MEAN
ST.DEV
05 ETAAS
7.06000
6.82500
7.29800
7.14100
7.20400
7.10560
.17942
11 ETAAS
7.21000
7.18000
8.15000
6.64000
7.49000
7.33400
.55021
03 FAAS
7.16000
7.17000
7.39000
7.39000
5.92000
7.00600
.61744
09 ICPMS
7.36000
8.50000
8.30000
7.70000
7.10000
7.79200
.59860
04 INAA
7.59000
7.48000
7.36000
7.46000
7.55000
7.48800
.08871
06 INAA
7.20000
7.30000
7.20000
7.50000
7.50000
7.34000
.15166
13 INAA
7.52000
7.49000
7.66000
7.81000
7.91000
7.67800
.18158
Figure 2
5.500
05 ETAAS
6.500
7.500
<
>
11 ETAAS
03 FAAS
09 ICPMS
04 INAA
06 INAA
<--.*.
13 INAA
MEANS!
64
8.500
Chromium in CRM 146 R - total mass fraction (mg/kg)

Table 3
NUM
t EPLICATES
03 FAAS
191.900
188.800
194.900
184.300
11 FAAS
196.400
183.300
166.700
207.000
170.000
201.000
02 ICPAES
194.000
05 ICPAES
MEAN
ST.DEV
206.500
193.280
8.367
169.400
176.300
178.420
11.941
201.000
165.000
174.000
186.333
18.608
197.000
219.000
196.000
201.500
11.733
191.000
187.000
193.300
200.000
197.500
193.760
5.159
195.000
197.000
195.000
195.000
201.000
194.000
196.167
2.563
197.800
198.000
199.900
200.500
199.800
196.000
198.667
1.701
04 INAA
204.900
204.900
200.800
197.900
203.100
202.320
2.990
06 INAA
193.000
197.000
203.000
203.000
207.000
200.600
5.550
214.000
209.000
214.000
199.000
207.000
210.000
208.833
5.565
A "A SET
16 FAAS
09 ICPMS
13 IDMS
13 INAA
Figure 3
160.0
180.0
200.0
03 FAAS
11 FAAS
16 FAAS
02 ICPAES
05 ICPAES
09 ICPMS
13 IDMS
04 INAA
<-*>
<..*--->
06 INAA
13 INAA
MEANS|
65
220.0
Copper in CRM 146 R - total mass fraction (mg/kg)

Table 4
NUM
DATA SET
REPLICATES..
MEAN
ST.DEV
03 FAAS
800.400
807.600
807.600
773.600
821.200
802.080
17.610
11 FAAS
824.800
827.400
823.200
815.900
816.900
821.640
5.025
02 ICPAES
866.000
843.000
823.000
828.000
853.000
842.600
17.700
05 ICPAES
858.900
849.300
868.200
847.800
849.200
854.680
8.759
09 ICPMS
826.000
844.000
842.000
858.000
875.000
849.000
18.439
13 IDMS
828.000
839.400
826.400
838.700
834.100
833.320
5.973
02 DPASV
839.000
887.000
842.000
843.000
851.000
852.400
19.844
847.330
845.460
872.920
835.250
816.660
865.300
847.153
20.335
10 EDXRF
Figure 4
780.0
03 FAAS
800.0
820.0
840.0
<-
11 FAAS
02 ICPAES
05 ICPAES
09 ICPMS
13 IDMS
02 DPASV
10 EDXRF
MEANS
66
860.0
880.0
Mercury in CRM 146 R - total mass fraction (mg/kg)

Table 5
MEAN
ST.DEV
8.22000
8.57200
.24994
8.73000
8.19000
8.42600
.26463
8.45000
8.53000
8.56000
8.90800
.57941
8.61000
8.58000
8.50000
8.58000
.04743
DATA SET
NUM
02 CVAAS
8.67000
8.59000
8.90000
8.48000
02 ICPMS
8.32000
8.69000
8.20000
09 ICPMS
9.21000
9.79000
13 RNAA
8.62000
8.59000
REPLICATES..
Figure 5
8.000
8.400
8.800
9.200
02 CVAAS
02 ICPMS
09 ICPMS
13 RNAA
MEANS
67
9.600
Manganese in CRM 146 R - total mass fraction (mg/kg)

Table 6
MEAN
ST.DEV
326.100
329.700
3.988
315.800
313.700
318.320
3.757
316.000
313.000
316.000
315.800
2.168
325.900
323.700
327.400
328.000
326.160
1.671
326.000
315.000
326.000
323.000
316.000
315.000
320.167
5.419
341.100
348.500
318.400
330.300
318.600
331.380
13.422
329.000
315.000
325.000
328.000
316.000
313.000
321.000
7.127
340.000
332.000
329.000
337.000
339.000
338.000
335.833
4.355
316.400
307.300
300.000
304.700
296.300
304.940
7.681
303.060
348.040
320.360
338.950
324.310
352.390
331.185
18.706
NUM
REPLICATES
03 FAAS
329.700
326.800
329.700
336.200
11 FAAS
322.100
322.100
317.900
02 ICPAES
319.000
315.000
05 ICPAES
325.800
DATA SET
09 ICPAES
04 INAA
06 INAA
13 INAA
14 INAA
10 EDXRF
Figure 6
280.0
300.0
... +
320.0
+
03 FAAS
<-__*
11 FAAS
<
02 ICPAES
<--->
>
>
05 ICPAES
09 ICPAES
04 INAA
06 INAA
13 INAA
14 INAA
10 EDXRF
MEANS!
<
340.0
..+ ..
+ ..
>
68
360.0
Nickel in CRM 146 R - total mass fraction (mg/kg)

Table 7
NUM
SET
REPLICATES..
MEAN
ST.DEV
03 FAAS
63.9000
63.7000
63.9000
64.5000
64.5000
64.1000
.3742
02 ICPAES
74.2000
73.8000
73.5000
75.6000
74.0000
74.2200
.8136
05 ICPAES
64.1200
66.3600
64.5500
74.6400
71.1700
68.1680
4.5728
70.3000
74.5000
72.1000
70.5000
76.3000
73.0000
72.7833
2.3327
13 IDMS
66.1600
66.5600
66.4100
67.3900
69.0700
67.1180
1.1848
02 DPCSV
73.7000
67.1000
77.7000
69.4000
69.2000
71.4200
4.2517
09 ICPAES
Figure 7
60.0
64.0
68.0
72.0
.. + ..
03 FAAS
<-*->
02 ICPAES
05 ICPAES
09 ICPAES
13 IDMS
02 DPCSV
MEANS
69
76.0
.. + ..
..+ . .
Lead in CRM 146 R - total mass fraction (mg/kg)

Table 8
MEAN
ST.DEV
02 ETAAS
630.000
634.000
619.000
613.000
609.000
621.000
10.747
03 FAAS
579.800
578.300
578.300
585.500
574.100
579.200
4.113
11 FAAS
586.500
618.000
625.300
595.000
606.400
606.240
15.950
02 ICPAES
640.000
638.000
610.000
655.000
656.000
639.800
18.606
05 ICPAES
601.200
604.300
591.300
593.400
600.200
598.080
5.495
02 ICPMS
635.000
618.000
626.000
619.000
613.000
622.200
8.526
584.000
573.000
570.000
607.000
580.000
574.000
581.333
13.560
613.000
608.600
614.800
606.300
608.600
604.100
609.233
4.023
686.000
632.000
614.000
595.000
630.000
631.400
33.953
586.000
566.000
618.000
576.000
563.000
599.000
584.667
21.030
658.490
615.300
627.520
611.910
608.180
615.050
622.742
18.680
09 ICPMS
13 IDMS
02 DPASV
09 DPASV
10 EDXRF
Figure 8
540.0
.+
580.0
+
620.0
+
02 ETAAS
03 FAAS
<--*->
11 FAAS
02 ICPAES
05 ICPAES
<---->
02 ICPMS
09 ICPMS
13 IDMS
02 DPASV
09 DPASV
10 EDXRF
MEANS
>
70
+.
660.0
Zinc in CRM 146 R - total mass fraction (mg/kg)

Table 9
DATA SET
ST.DEV
NUM
REPLICATES
03 FAAS
3036.00
3003.00
3106.00
3133.00
3106.00
3076.80
54.71
11 FAAS
3192.00
3187.00
3173.00
3228.00
3211.00
3198.20
21.51
3008.00
3005.00
2962.00
2874.00
2882.00
2951.00
2947.00
58.10
02 ICPAES
3024.00
3058.00
2966.00
2968.00
3044.00
3012.00
42.83
05 ICPAES
3049.00
3028.00
3068.00
3095.00
3138.00
3075.60
42.72
09 ICPMS
3083.00
3037.00
3089.00
3075.00
3065.00
3069.80
20.43
3210.00
3047.00
3016.00
3181.00
3158.00
3169.00
3130.17
78.98
02 DPASV
3360.00
3140.00
3270.00
3100.00
3030.00
3180.00
133.23
04 INAA
2927.00
2966.00
2940.00
2887.00
2889.00
2921.80
33.91
06 INAA
2969.00
3019.00
3035.00
2939.00
3005.00
2993.40
38.97
3069.93
3078.69
3108.53
3067.11
3029.66
3068.47
3070.40
25.29
16 FAAS
13 IDMS
10 EDXRF
Figure 9
2800.0
+ ..
2900.0
.. + ..
3000.0
3100.0
.. + ..
03 FAAS
11 FAAS
16 FAAS
02 ICPAES
05 ICPAES
09 ICPHS
13 IDMS
02 DPASV
04 INAA
06 INAA
->
10 EDXRF
MEANS
--M--
71
.+
3200.0
+ ....
3300.0
Cadmium in CRM 146 R - aqua regia soluble fraction (mg/kg)

Table 10
MEAN
ST.DEV
18.8000
18.6600
.2408
19.8500
20.6300
18.9860
1.3287
19.7000
17.8700
17.8700
18.4680
.8424
18.4000
18.3000
18.6000
19.3000
18.5400
.4615
18.7000
18.3000
19.1000
19.1000
18.4000
18.7200
.3768
17.9160
18.0460
18.5610
18.2270
18.1780
18.1856
.2423
17.9000
18.0000
17.8000
17.9000
17.9000
17.9000
.0707
18.8000
18.6000
18.7000
18.8000
18.6000
18.6000
18.6833
.0983
REPLICATES..
DATA SET
NUM
02 ETAAS
18.4000
18.6000
19.0000
18.5000
05 ETAAS
17.5600
17.7400
19.1500
03 FAAS
19.0000
17.9000
02 ICPAES
18.1000
02 ICPMS
06 ICPMS
09 ICPMS
13 IDMS
Figure 10
17.800
18.200
18.600
.. + ..
02 ETAAS
02 ICPAES
02 ICPMS
00 ICPMS
09 ICPMS
13 IDMS
MEANS!
72
19.000
.. +
Cobalt in CRM 146 R - aqua regia soluble fraction (mg/kg)

Table 11
MEAN
ST.DEV
5.80000
6.14000
.24083
7.07000
6.66000
6.85200
.18006
6.70000
6.60000
7.10000
6.46000
.68044
6.17400
5.60800
5.95100
6.50800
6.07720
.33001
6.57550
6.71630
6.37520
6.47100
6.22880
6.47336
.18635
7.56000
7.37000
6.57000
7.35000
7.08000
7.18600
.38449
6.52500
6.42900
6.16100
6.27900
6.30200
6.33920
.14084
6.90000
6.00000
6.60000
6.40000
6.30000
6.70000
6.48333
.31885
DATA SET
NUM
11 ETAAS
6.40000
6.20000
6.30000
6.00000
03 FAAS
6.67000
6.93000
6.93000
02 ICPAES
6.60000
5.30000
05 ICPAES
6.14500
06 ICPMS
09 ICPMS
04 INAA
06 INAA
REPLICATES..
Figure 11
5.000
7.000
6.000
11 ETAAS
03 FAAS
8.000
...+
+ ...
<
02 ICPAES
05 ICPAES
06 ICPMS
09 ICPMS
04 INAA
06 INAA
MEANS!
73
>
Chromium in CRM 146 R - aqua regia soluble fraction (mg/kg)

Table 12
NUM
DATA SET
REPLICATES..
MEAN
ST.DEV
03 FAAS
173.300
170.000
163.300
170.000
170.000
169.320
3.656
11 FAAS
168.600
168.600
167.800
170.500
170.400
169.180
1.205
12 FAAS
190.154
188.928
190.931
193.263
193.482
191.352
1.980
173.000
164.000
163.000
172.000
166.000
163.000
166.833
4.535
16 FAAS
02
ICPAES
179.000
174.000
184.000
172.000
189.000
179.600
7.021
05
ICPAES
172.200
172.000
175.500
179.000
182.200
176.180
4.415
09
ICPMS
163.000
157.000
159.000
156.000
162.000
159.400
3.050
179.100
174.900
176.100
179.500
177.900
175.900
177.233
1.875
178.920
178.990
172.610
169.000
173.340
174.572
4.325
13 IDMS
04
INAA
Figure 12
150.0
160.0
170.0
180.0
,..+
+.
190.0
...+...
03 FAAS
11 FAAS
12 FAAS
<-.* >
16 FAAS
02 ICPAES
05 ICPAES
09 ICPMS
13 IDMS
<-.*_->
04 INAA
MEANS!
74
Copper in CRM 146 R - aqua regia soluble fraction (mg/kg)

Table 13
DATA SET
NUM
REPLICATES..
MEAN
ST.DEV
03 FAAS
784.000
789.200
779.300
810.000
800.000
792.500
12.449
11 FAAS
802.200
804.400
807.300
811.100
805.700
806.140
3.343
12 FAAS
849.258
839.042
846.639
844.719
850.477
846.027
4.503
02 ICPAES
829.000
837.000
831.000
858.000
862.000
843.400
15.502
05 ICPAES
845.300
846.900
848.300
844.000
841.600
845.220
2.594
06 ICPMS
855.680
893.600
852.760
838.160
832.950
854.630
23.794
09 ICPMS
857.000
823.000
830.000
815.000
876.000
840.200
25.489
815.000
826.100
823.400
828.500
827.300
825.500
824.300
4.871
832.810
836.800
844.170
834.210
796.970
828.992
18.429
13 IDMS
10 EDXRF
Figure 13
760.0
.+
800.0
+ ...
840.0
03 FAAS
11 FAAS
<-_*_.>
12 FAAS
02 ICPAES
05 ICPAES
06 ICPMS
09 ICPMS
13 IDMS
<-*-->!
10 EDXRF
MEANS;
75
880.0
Mercury in CRM 146 R - aqua regia soluble fraction (mg/kg)

Table 14
MEAN
ST.DEV
8.28000
8.10800
.19942
8.35000
8.68000
8.50000
.25583
8.52300
8.58200
8.53600
8.63420
.12907
8.36000
8.47000
8.48000
8.09000
8.38000
.17103
8.11000
8.56300
8.50300
8.27200
8.33780
.18947
DAI A SET
NUM
02 CVAAS
8.02000
7.80000
8.19000
8.25000
03 CVAAS
8.12000
8.65000
8.70000
05 CVAAS
8.70300
8.82700
02 ICPMS
8.50000
06 ID ICPMS
8.24100
REPLICATES...
Figure 14
7.800
8.000
... +
8.200
+
02 CVAAS
8.400
+
<
<
02 ICPMS
<
06 ID ICPMS
*
>
*
<
8.800
... +
*--
05 CVAAS
MEANS!
+ .. .. + ..
>
03 CVAAS
8.600
>
M
>
76
>
Manganese in CRM 146 R - aqua regia soluble fraction (mg/kg)

Table 15
NUM
REPLICATES
03 FAAS
290.000
284.700
289.000
287.300
11 FAAS
282.700
282.800
286.500
12 FAAS
307.785
307.363
02 ICPAES
294.000
05 ICPAES
09 ICPAES
DATA SET
MEAN
ST.DEV
285.700
287.340
2.207
282.800
280.500
283.060
2.159
307.143
308.564
308.287
307.828
.600
287.000
284.000
290.000
280.000
287.000
5.385
296.500
298.600
303.900
305.700
308.500
302.640
4.983
296.000
289.000
290.000
290.000
289.000
290.800
2.950
06 ICPMS
306.180
302.780
302.520
305.000
298.460
302.988
2.958
04 INAA
319.400
321.650
289.530
299.230
286.810
303.324
16.386
10 EDXRF
302.170
311.390
347.110
305.340
318.340
316.870
17.998
Figure 15
270.0
+
.+
290.0
+
310.0
+
03 FAAS
11 FAAS
<-..->
12 FAAS
02 ICPAES
05 ICPAES
09 ICPAES
06 ICPMS
<-_.*_->
<__-*-._>
04 INAA
10 EDXRF
MEANS!
77
330.0
+ ..
Nickel in CRM 146 R - aqua regia soluble fraction (mg/kg)

Table 16
DATA SET
NUM
REPLICATES...
MEAN
ST.DEV
03 FAAS
63.6000
65.1000
62.0000
57.9000
59.5000
61.6200
2.9372
0 7 FAAS
78.4000
63.2000
75.6000
58.8000
59.9000
67.1800
9.1631
12 FAAS
65.5710
64.6900
64.4260
65.0860
64.9250
64.9396
.4320
02 ICPAES
71.6000
71.4000
72.0000
66.9000
73.0000
70.9800
2.3626
05
ICPAES
63.5700
63.9300
65.1000
65.9200
66.3100
64.9660
1.1996
0 9 ICPAES
61.5000
61.7000
59.8000
60.5000
62.8000
61.2600
1.1546
06 ICPMS
67.5780
67.3830
67.1960
64.6880
63.8430
66.1376
1.7402
13 IDMS
64.4000
64.4000
66.5000
64.0000
66.7000
65.2000
1.2903
Figure 16
54.0
58.0
62.0
.. + ..
66.0
03 FAAS
12 FAAS
02 ICPAES
05 ICPAES
09 ICPAES
06 ICPMS
13 IDMS
MEANS
78
70.0
74.0
Lead in CRM 146 R - aqua regia soluble fraction (mg/kg)

Table 17
MEAN
ST.DEV
611.000
621.400
15.093
536.700
545.300
542.940
11.050
560.400
569.150
568.787
567.549
4.095
587.000
597.000
619.000
597.000
597.000
13.491
569.600
570.600
580.400
586.900
579.600
577.420
7.266
585.000
613.000
596.000
590.000
602.000
597.200
10.895
09 ICPMS
587.000
585.000
567.000
585.000
569.000
578.600
9.737
06 ID ICPMS
578.650
576.210
576.830
580.450
565.360
575.500
5.906
595.600
586.700
590.800
593.200
592.100
588.400
591.133
3.237
DATA SET
NUM
REPLICATES
02 ETAAS
634.000
600.000
632.000
630.000
03 FAAS
561.300
536.700
534.700
12 FAAS
568.567
570.840
02 ICPAES
585.000
05 ICPAES
02 ICPMS
13 IMDS
Figure 17
500.0
580.0
540.0
...+
02 ETAAS
03 FAAS
12 FAAS
<--*->
02 ICPAES
05 ICPAES
<-..*-
02 ICPMS
09 ICPMS
<
*.
06 ID ICPMS
13 IM0S
MEANS;
79
620.0
+ ...
.+
660.0
+
Zinc in CRM 146 R - aqua regia soluble fraction (mg/kg)

Table 18
NUM
DATA SET
REPLICATES...
MEAN
ST.DEV
03 FAAS
2940.00
2940.00
3067.00
2967.00
2980.00
2978.80
52.28
11 FAAS
2985.00
2980.00
3001.00
3067.00
3106.00
3027.80
55.87
12 FAAS
3012.03
3091.12
3151.26
3282.30
3138.02
3134.95
98.76
02 ICPAES
3042.00
3101.00
3078.00
3137.00
3066.00
3084.80
36.12
05 ICPAES
3020.00
3031.00
3070.00
3080.00
3090.00
3058.20
30.92
06 ICPMS
3052.70
3121.20
3089.90
3045.90
3040.40
3070.02
34.55
09 1CPMS
3010.00
2914.00
2902.00
3142.00
3088.00
3011.20
105-33
3004.00
3091.00
3127.00
3097.00
2983.00
3126.00
3071.33
62.40
04 INAA
2872.60
2906.20
2880.60
2818.00
2813.70
2858.22
40.65
10 EDXRF
3097.25
3144.57
3229.18
3092.02
3077.85
3128.17
61.78
13 IDMS
Figure 18
2750.0
2850.0
2950.0
3050.0
03 FAAS
11 FAAS
12 FAAS
02 ICPAES
05 ICPAES
06 ICPMS
09 ICPMS
13 IDMS
04 INAA
10 EDXRF
MEANS;
80
3150.0
...+
+.
3250.0
... +
European Commission
EUR 16892
The certification of the total contents (mass fractions) of Cd, Co, Cr, Cu, Hg, Mn, Pb
and Zn and the aqua regia soluble contents (mass tractions) of Cd, Co, Cr, Cu, Hg, Mn,
Ni, Pb and Zn in a sewage sludge from industrial origin - CRM 146 R
Ph. Quevauviller, H. Muntau, U. Fortunati and K. Vercoutere

Luxembourg: Office for Official Publications of the European Communities
1996 87 pp, num. tab., fig. - 21.0x29.7 cm
BCR information series
ISBN 92-827-7415-5
This report describes the preparation as well as the homogeneity and stability studies, of a sewage sludge
reference material intended to replace the exhausted BCR CRM 146 sewage sludge from industrial origin. It
also summarises the analytical work for the certification of the total contents and the aqua regia soluble contents
(expressed as mg/kg on a dry mass basis) of some elements. The report contains all the results and a
description of the methods used to certify the total contents of Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, and Zn, as
well as the aqua regia soluble contents of Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, and Zn.
PLEASE CONSULT T H E INSTRUCTIONS FOR USERS PRIOR TO OPENING A
BOTTLE OF REFERENCE MATERIAL
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ISSN 1018-5593

THE CERTIFICATION OF THE TOTAL CONTENTS

THE CERTIFICATION OF THE TOTAL CONTENTS

Cataloguing data can be found at the end of this publication

Luxembourg: Office for Official Publications of the European Communities, 1995

Aqua regia soluble fraction

Cold vapour atomic absorption spectrometry

Differential pulse anodic stripping voltammetry

Differential pulse cathodic stripping voltammetry

Energy dispersive X-ray fluorescence spectrometry

Electrothermal atomic absorption spectrometry

Flame atomic absorption spectrometry

Inductively coupled plasma atomic emission spectrometry

Inductively coupled plasma atomic mass spectrometry

Isotope dilution inductively coupled plasma mass spectrometry

Isotope dilution mass spectrometry

Instrumental neutron activation analysis

Radiochemical neutron activation analysis

Preparation of the material

Aqua regia soluble contents

Technical and statistical discussion

Instructions for users

Tables of individual results and graphical presentations

Agriculture & Food Development Authority, Wexford

Service Central d'Analyse, CNRS, Vernaison

ECN Energieonderzoekcentrum Nederland, Petten

Ecole Europenne des Hautes Etudes des Industries Chimiques,

GSF Forschungszentrum fr Umwelt und Gesundheit, Oberschleiheim

INTRA, Station d'Agronomie, Villenave d'Ornon

Institute for Soil Fertility, Haren

Institut fr Analytische Chemie, Technische Universitt Wien

Laboratorium voor Analytische Scheikunde, INW, Universiteit Gent

Ris National Laboratory, Roskilde

Universidad de Barcelona, Dept. de Qumica Analtica

Universit di Pavia, Centro de Chimica Nuclearia

PREPARATION OF THE MATERIAL

A comparison of the composition of the 2 sludges is given in table 3.1; the

determinations of major components were performed by X-ray fluorescence spectrometry.

Comparison of the composition (expressed as mass fraction (g/kg) of the original

Results for the within-and between-bottle homogeneity of BCR CRM 146 R at 50

Results for the within-and between-bottle homogeneity of BCR CRM 146 R at

single determination on the content of each of 10 bottles

They are separated by chromatography

(Poropax column) and are determined through thermal conductivity.

In reality however there are some random

AQUA REGIA SOLUBLE CONTENTS

Wherever possible, the performance of the method, as carried out by the

Some possible sources of error and their elimination

dilutions etc carried out with calibrated

correction to dry mass according to

contamination from lab

participants used H F treatment with

different calibration methods were

Non destructive methods

flux monitors were added in the irradiation process

peak overlap intrinsic

deconvolution; selection of proper

calibrants and unknowns were both in

the same remarks as for destructive

Pressurised digestion using HNO3 (1 ml) for 10 h at

High pressure ashing in quartz vessels with H N 0 3 (2

Pressurised microwave digestion with H F (4 ml),

Open digestion with H N 0 3 / H C 1 0 , / H F for 16 h at 20

Digestion with aqua regia (1 ml) and H F (10 ml) for