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BS en 13657-2002
BS en 13657-2002
13657:2002
Characterization of
waste — Digestion for
subsequent
determination of aqua
regia soluble portion of
elements
ICS 13.030.40
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BS EN 13657:2002
National foreword
This British Standard is the official English language version of
EN 13657:2002.
The UK participation in its preparation was entrusted by Technical Committee
B/508, Waste management, to Subcommittee B/508/3, Characterization of
waste, which has the responsibility to:
ICS 13.030.40
English version
Caractérisation des déchets - Digestion en vue de la Charakterisierung von Abfällen - Aufschluss zur
détermination ultérieure de la part des éléments solubles anschließenden Bestimmung des in Königswasser
dans l'eau régale contenus dans les déchets löslichen Anteils an Elementen in Abfällen
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national
standards may be obtained on application to the Management Centre or to any CEN member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CEN member into its own language and notified to the Management Centre has the same status as the official
versions.
CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece,
Iceland, Ireland, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom.
© 2002 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 13657:2002 E
worldwide for CEN national Members.
EN 13657:2002 (E)
Contents
page
Foreword......................................................................................................................................................................3
Introduction .................................................................................................................................................................4
1 Scope ......................................................................................................................................................................5
2 Normative references............................................................................................................................................5
3 Terms and definitions ...........................................................................................................................................5
4 Safety remarks.......................................................................................................................................................6
5 Sample ....................................................................................................................................................................6
5.1 Sample pre-treatment .......................................................................................................................................6
5.2 Mass of test portion ...........................................................................................................................................7
6 Equipment ..............................................................................................................................................................7
6.1 Closed vessel system .......................................................................................................................................7
6.1.1 Microwave unit ............................................................................................................................................7
6.1.2 Digestion vessels ........................................................................................................................................7
6.2 Semi-open vessel system .................................................................................................................................8
6.2.1 Microwave unit ............................................................................................................................................8
6.2.2 Digestion vessels ........................................................................................................................................8
6.3 Apparatus for thermal heating digestion ...........................................................................................................8
6.3.1 Reaction vessels.........................................................................................................................................8
6.3.2 Reflux condenser ........................................................................................................................................8
6.3.3 Absorption vessel........................................................................................................................................8
6.3.4 Roughened glass beards............................................................................................................................8
6.3.5 Temperature-controlled heating apparatus ................................................................................................8
6.4 General equipment............................................................................................................................................8
7 Reagents.................................................................................................................................................................9
8 Interferences and sources of error......................................................................................................................9
8.1 General informations .........................................................................................................................................9
8.2 Closed vessel system .......................................................................................................................................9
8.3 Semi-open vessel system for microwave or thermal heating digestion ..........................................................10
9 Procedure .............................................................................................................................................................10
9.1 Blank test.........................................................................................................................................................10
9.2 Procedure for microwave assisted digestion in closed vessels ......................................................................10
9.3 Procedure for microwave assisted digestion in semi-open vessels................................................................11
9.3.1 Amount of samples ...................................................................................................................................11
9.3.2 Digestion ...................................................................................................................................................11
9.3.3 Preparation of the solution for analysis ....................................................................................................11
9.4 Procedure for thermal heating digestion in reflux systems .............................................................................11
9.4.1 Amount of samples ...................................................................................................................................11
9.4.2 Digestion ...................................................................................................................................................12
9.4.3 Preparation of the solution for analysis ....................................................................................................12
10 Test report ..........................................................................................................................................................12
Annex A (normative) Calibration of the power adjustment .................................................................................14
Annex B (informative) Validation ............................................................................................................................15
B.1 Inter-laboratory study......................................................................................................................................15
B.2 Robustness study ...........................................................................................................................................23
Bibliography ..............................................................................................................................................................26
2
EN 13657:2002 (E)
Foreword
This document EN 13657:2002 has been prepared by Technical Committee CEN/TC 292 "Characterization of
waste", the secretariat of which is held by NEN.
This European Standard shall be given the status of a national standard, either by publication of an identical text
or by endorsement, at the latest by April 2003, and conflicting national standards shall be withdrawn at the latest
by April 2003.
In this European Standard the annex A is normative and the annexe B is informative.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark,
Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal,
Spain, Sweden, Switzerland and the United Kingdom.
3
EN 13657:2002 (E)
Introduction
The aim of this European Standard is to describe suitable methods for the extraction of elements in waste,
soluble by digestion with aqua regia, i. e. aqua regia soluble elements.
For those types of waste, where the sample material by the described digestion with aqua regia are not brought
totally in solution, the obtained results will not be the total amount of the elements in the waste.
The obtained results of aqua regia soluble elements cannot be regarded as available for leaching, as the
digestion with aqua regia is too vigorous to represent natural processes.
4
EN 13657:2002 (E)
1 Scope
This European Standard specifies methods of digestion with aqua regia. Solutions produced by the methods are
suitable for analysis e.g. by atomic absorption spectrometry (FLAAS, HGAAS, CVAAS, GFAAS), inductively
coupled plasma emission spectrometry (ICP-OES) and inductive coupled plasma mass spectrometry (ICP-MS).
The digestion with aqua regia will not necessarily release all elements completely. However for most
environmental application and waste characterization the results fit for the purpose.
The method is applicable to the digestion of waste for example for the following elements: Al, Sb, As, B, Ba, Be,
Ca, Cd, Cr, Co, Cu, Fe, Pb, Mg, Mn, Hg, Mo, Ni, P, K, Se, Ag, S, Na, Sr, Sn, Te, Ti, Tl, V, Zn.
2 Normative references
This European Standard incorporates by dated or undated reference, provisions from other publications. These
normative references are cited at the appropriate places in the text, and the publications are listed hereafter. For
dated references, subsequent amendments to or revisions of any of these publications apply to this European
Standard only when incorporated in it by amendment or revision. For undated references the latest edition of the
publication referred to applies (including amendments).
EN ISO 3696:1995, Water for analytical laboratory use - Specification and test methods (ISO 3696:1987).
For the purposes of this European Standard, the following terms and definitions apply.
3.1
aqua regia
digestion solution obtained by mixing 1 volume of nitric acid (65 % m/m to 70 % m/m) and 3 volumes of
hydrochloric acid (35 % m/m to 37 % m/m)
3.2
digestion
mineralization of the organic matter of a sample and dissolution of its mineral part, more or less completely,
when reacted with a reagent mixture
3.3
sample
portion of material selected from a larger quantity of material
[ENV 12506:2001]
3.4
laboratory sample
sample or subsample(s) sent to or received by the laboratory
[ENV 12506:2001]
3.5
test sample; analytical sample
sample, prepared from the laboratory sample, from which test portions are removed for testing or analysis
[ENV 12506:2001]
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EN 13657:2002 (E)
3.6
test portion; analytical portion
quantity of material of proper size for measurement of the concentration or other properties of interest, removed
from the test sample
[ENV 12506:2001]
NOTE 1 The test portion may be taken from the laboratory sample directly if no preparation of sample is required (e. g. with
liquids), but usually it is taken from the prepared test sample.
NOTE 2 A unit or increment of proper homogeneity, size and fineness, needing no further preparation, may be a test portion.
3.7
dry residue
dry matter expressed as a percentage by mass after drying at 105 °C ± 5 °C to the constancy of weight
3.8
digestion vessel
special flask where the test portion and the acid mixture are filled in and the digestion is performed
3.9
microwave unit
whole microwave digestion system (oven and associated equipment)
3.10
microwave unit cavity
the inner part of the microwave unit in which the digestion vessel is located and the microwave digestion is
performed
3.11
focused microwave unit
microwave unit in which a precise control of the electric field is made by using a wave guide
NOTE Microwaves are focused at the bottom part of the digestion vessel.
4 Safety remarks
The reagents used within this EN are strongly corrosive and partly very toxic. Safety precautions are absolutely
necessary due to strong corrosive reagents, high temperature and high pressure.
All procedures have to be performed in a hood or in closed force-ventilated equipment. By the use of strong
oxidising reagents the formation of explosive organic intermediates is possible especially when dealing with
samples with a high organic content. Do not open pressurised vessels before they have cooled down. Avoid
contact with the chemicals and the gaseous reaction products. Samples and solutions have to be disposed of
according to regulations.
5 Sample
The test portion should be transferred into the vessel as it is without any pre-treatment if possible.This is
applicable only if the test portion is representative for the laboratory sample and the effectiveness of the
digestion is proven.
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EN 13657:2002 (E)
If these conditions are not met a pre-treatment of the laboratory sample is necessary. This procedure shall not
change the concentration of the elements of interest.
Pre-treatment should include drying or grain size reduction below a particle size of 250 µm for solid waste or
homogenizing by use of a high speed mixer or sonification for liquid samples.
The mass of laboratory samples shall be sufficient for the multiple digestion procedures and determination of
the dry residue.
The mass of test portion for a single digestion has to be selected in a way, that:
NOTE If the representative test portion exceeds the manufacturers specifications the test portion should be devided into
smaller quantities and digested seperately. The individual digests should be combined prior to analysis.
For representativity reason mass above 200 mg is to be preferred. Unless recommended by the manufacturer
the amount of organic carbon shall not exceed 100 mg because of safety reasons in the case of closed
digestion vessel.
6 Equipment
The microwave unit shall provide programmable power which can be programmed to within ± 10 W of the
required power. Typical units provide a nominal 600 W to 1 200 W of power. If necessary (referring to
manufactures specifications) calibration of the microwave unit has to be performed (see annex A).
The microwave unit has to comply to European and national regulations relevant to microwave radiation.
The microwave unit cavity has to be well ventilated. It has to have an exhaust air tube which is connected to a
corrosion resistant laboratory air outlet system or the instrument is provided for use in a laboratory hood.
All electronics are sufficiently protected against corrosion for safe operation. All parts which could have contact
with acids or their vapours have to be corrosion resistant.
The microwave unit shall be designed in a way that guarantees homogeneous heating of the samples.
The microwave unit cavity has to be built in a way that even in case of leakage or explosion of the vessels the
safety of the operators can be guaranteed. Household instruments are not suitable for laboratory use.
NOTE The microwave unit should include a temperature and/or pressure control system.
The vessels used in the microwave unit shall be equiped with a pressure relieve valve or another technical
equipment which avoids the bursting of the vessels at suddenly occuring excess pressure. The material of the
vessels has to be inert to the acids used for digestion. The digestion vessel shall withstand the pressure of at
least 8 bar. If the amount of organic carbon exceeds 100 mg it has to be ensured that the digestion vessel is
capable of withstanding higher pressures.
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EN 13657:2002 (E)
The microwave unit shall be equiped with power control. Typical unit provides a nominal 200 W or 300 W of
released power. If necessary, calibration of the microwave unit has to be performed by the manufacturer.
The microwave unit shall comply with European and national regulations relevant to microwave radiation.
Fume extraction equipment, used to extract acid vapours from the reaction vessels during the digestion
program, shall have sufficient flow rate to prevent the release of dangerous vapours into the laboratory.
All electronics shall be sufficiently protected against corrosion for safe operation. All parts which can be in
contact with acids or their vapours shall be corrosion resistant.
The vessel is working at atmospheric pressure and has to be connected with a reflux system to avoid losses of
analytes. The vessel shall comply with the manufactures specifications and should have a minimum volume of
50 ml.
The material of the vessels has to be inert to the reagents used for digestion.
The reaction vessel shall have a volume of at least 5 times of the volume of the aqua regia used.
Water-cooled reflux condenser, minimum assembled length 340 mm with conical ground joints.
Non-return type.
The following equipment is used by the systems described in 6.1, 6.2 and 6.3:
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EN 13657:2002 (E)
For the preparation of standards and the treatment and storage of samples for determination of boron the use of
borosilicate glass shall be avoided.
7 Reagents
Use reagents of analytical grade quality or better and water of grade 1 according to EN ISO 3696:1995.
Due to the volatility of some compounds it is of great importance to take care, that the sample is not heated
before the digestion and that the volatile reaction products which might be formed during the digestion are not
allowed to escape.
The container in which the sample is delivered and stored can be a source of errors. Its material shall be chosen
according to the elements to be determined (e.g. elemental Hg can penetrate polyethylene walls very fast in
both directions. Glass can contaminate samples with elements contained: e.g. B, Na, K, Al).
Grinding or milling samples includes a risk of contamination of the sample by the environment (air, dust, wear of
milling equipment). Due to elevate temperature losses of volatile compounds are possible.
For the determination of elements forming volatile compounds (e.g. Hg, As, Pb) special care has to be taken at
sample pre-treatment.
The use of the described digestion procedures may leave large parts of the sample undissolved. This includes
the risk of bad repeatability.
High acid and solute concentrations in the digest may cause interferences at determination.
Depending on the concentration of the element of interest and the wanted precision, a particular caution to the
cleaning of the vessels shall be taken. It is recommended to clean the vessels with 10 % nitric acid.
Care shall be taken to ensure that all of the test portion is brought into contact with the acid mixture in the
reaction vessel.
Some elements of interest can be lost because of precipitation with some ions of the solution. It is the case for
insoluble chlorides, fluorides and sulphates for example. In this case the precipitate can be analysed separately.
In the case of filtration of the digested solution it is necessary to take care that the filtration procedure does not
introduce contaminants.
The upper limits of mass of the test portion referring to the manufacturers specifications have to be taken into
account.
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EN 13657:2002 (E)
Very reactive or volatile materials that may create high pressures when heated may cause a venting of the
vessels with potential loss of sample and analytes. The complete decomposition of either carbonates, or carbon
based samples, may cause enough pressure to vent the vessel.
After digestion, the vessel shall be cooled to room temperature before opening. If not, losses of certain
elements, particulary volatile elements as mercury or arsenic can occur.
Depending on the volatility of some elements of interest, the reflux system can be inefficient to condense the
vapours and losses of some elements of interest can happen.
9 Procedure
To detect possible contaminations from vessels and/or reagents, blank tests shall be carried out in parallel by
the same digestion procedure and filtration if appropriate, using the same quantities of all reagents but omitting
the test portion.
Weigh between 0,2 g to 0,5 g of the sample, to the nearest 0,1 mg, prepared according to clause 5 and transfer
it into the vessel. If necessary the sample may be moistened with a minimum amount of water. Then add
seperately 6 ml of HCl and 2 ml of HNO3.
It is necessary to use only one specific reaction mixture as well as the same kind of matrix in the same quantity
of test portion in a single batch in the microwave unit cavity to ensure consistent reaction conditions.
If a vigorous reaction occurs, allow the reaction to lie down before capping the vessel. Transfer the digestion
vessels into the microwave unit cavity according to the manufactures instructions and start the following
digestion procedure.
Time Power
min W
2 250
2 0
5 250
5 400
5 500
The power programme (see Table 1) is intended to be used for batches of 6 samples. Commercial available
microwave units may contain more or less sample positions. In order to ensure consistant reaction conditions in
these cases the power programme has to be adjusted according to the manufactures instructions. For batches
where all positions are not occupied either the empty positions shall be filled up with e.g. blanks or duplicates or
the power programme shall be adjusted in accordance with the number of samples.
At the end of the programme let the vessels cool down to room temperature. Confirm that no losses of digestion
solution occured during the procedure (e.g. by control of burstmembran referring to the manufactures
specifications or controll of mass). Otherwise the samples have to be discarded. Carefully uncap and vent each
vessel in a fume hood, then transfer quantitatively the content of the vessels into a suitable sized volumetric
flask and fill to the mark.
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EN 13657:2002 (E)
If the digested sample contains particles which might clog the nebulizers of the measurement apparatus or
which might interfere with the injection of the sample into the instrument, the sample solution may be
centrifuged, allowed to settle or be filtered. In the case of filtration, dilute the content of the vessel before
filtering, rinse and then fill to the mark of the volumetric flask. The method used has to be reported in the test
report.
Weigh between 0,2 g to 1,0 g of the sample, to the nearest 0,1 mg, prepared according to clause 5 and transfer
it into the vessel. If necessary the sample may be moistened with a minimum amount of water.
9.3.2 Digestion
Transfer the digestion vessels into the microwave unit cavity according to the manufactures instructions and
start the following digestion procedure.
NOTE Introduction of the digestion vessel into the microwave cavity, reagent injection into the digestion vessel,
temperature and/or power control can be done automatically or manually depending on the apparatus used.
24 ml of aqua regia is sufficient only for the oxidation of about 0,4 g organic carbon. If there is any doubt of the amount of
carbon present, carry out a determination. If there is more than 0,4 g of organic carbon in the test portion, proceed as
follows.
Allow first reaction with the aqua regia to subside. Then add an extra 1 ml of nitric acid only to every 0,1 g of organic carbon
above 0,4 g. Do not add more than 10 ml of nitric acid at any time, and allow any reaction to subside before preceeding
further.
At the end of the programme let the vessels cool down to room temperature.
Transfer quantitatively the solution content of each vessel into a suitable sized volumetric flask and dilute to the
mark.
If the digested mixture contains particles which might clog the nebulizers of the measurement apparatus or
which might interfere with the injection of the sample into the instrument, the sample may be centrifuged,
allowed to settle or be filtered. In the case of filtration, dilute the content of the vessel before filtering, rinse and
then dilute to the mark of the volumetric flask. The method used has to be reported in the test report.
Weigh 1 g to 10 g, to the nearest 0,1 mg of the prepared sample and transfer to the reaction vessel.
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EN 13657:2002 (E)
9.4.2 Digestion
Add, while mixing, the appropriate amount of hydrochloric acid followed by nitric acid, dropwise if necessary to
reduce foaming. The mass: volume ratio between sample and acid mixture shall be 1:10. Connect the
condenser to the reaction vessel, fill the absorption vessel with aqua regia. Connect the absorption vessel to the
condenser and allow to stand at room temperature until effervescence lies down to allow for slow oxidation of
the organic matter in the test portion.
30 ml of aqua regia is sufficient only for the oxidation of about 0,5 g organic carbon. If there is any doubt of the
amount of carbon present, carry out a determination. If there is more than 0,5 g of organic carbon in the test
portion, proceed as follows.
Allow first reaction with the aqua regia to subside. Then add an extra 1 ml of nitric acid only to every 0,1 g of
organic carbon above 0,5 g. Do not add more than 10 ml of nitric acid at any time, and allow any reaction to
subside before preceeding further.
Raise the temperature of the reaction mixture slowly to reflux conditions and maintain for 2 h ensuring that the
condensation zone is lower than 1/3 of the height of the condenser, then allow to cool. Add the content of the
adsorption vessel to the reaction vessel via the condenser, rinsing both the absorption vessel and condenser
with further 10 ml of diluted nitric acid.
If the digested mixture contains particles which might clog the nebulizers of the measurement apparatus or
which might interfere with the injection of the sample into the instrument, the sample may be centrifuged,
allowed to settle or be filtered. In the case of filtration, dilute the content of the vessel before filtering, rinse and
then dilute to the mark of the volumetric flask. The method used has to be reported in the test report.
10 Test report
The work carried out by the testing laboratory shall be covered by a report which accurately, clearly and
unambiguously presents the test results and all other relevant informations.
b) name and address of the testing laboratory and location where the test was carried out when different from
the address of the testing laboratory;
c) unique identification of report (such as serial number) and of each page, and total number of pages of the
report;
e) quantity and date of receipt of the laboratory sample(s) and date(s) of performance of the test;
— reference to the actual digestion method (e.g. digestion system, reagents, microwave programme);
— technique used for the separation of the solid residue, if any (e.g. centrifugation, filtering);
— description and reasons for any deviation from the standard procedures;
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EN 13657:2002 (E)
g) a signature and title or an equivalent marking of person(s) accepting technical responsibility for the test
report and date of issue;
h) a statement, that the information contained in the report relate exclusively to the laboratory
sample(s) tested;
i) a statement that the report shall not be reproduced except in full without the written approval of the testing
laboratory.
2) results of the analytical determinations carried out with other methods on the same samples, if any.
The traceability of the work carried out by the testing laboratory (e.g. instruments, worksheets, printouts, forms
with samples weight) shall be recorded and stored. This information shall be available on customers request.
A test report shall not include any advice or recommendation arising from the test results.
NOTE The final report should include all results and relevant information on the sampling, the digestion
method and the analysis methods used.
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EN 13657:2002 (E)
Annex A
(normative)
Calibration is carried out by heating a known amount of water during a fixed time period (e.g. 2 min) at different
microwave power rates. Each raise of temperature has to be measured accuratly to ± 0,1 °C after each heating
cycle. The absorbed power is calculated from the raise of temperature (see formula at the end of this annex).
Put e.g. 1 kg of water in a plastic beaker (or a beaker made of other material that does not absorb or reflect
microwave energy, glass beaker must be avoided), stir and measure the temperature. Place the beaker in the
microwave oven. Do always select the same position. Set the microwave during 2 min at full power. Remove the
beaker, stir and measure the final temperature. Repeat this procedure also at lower power rates.
Cp × m × ∆ T
P=
t
where
m is the mass of the water that is used for the calibration in kg;
If in the described procedure 2 min and 1 kg water are used, the formula can be simplified to:
P = ∆ T × 34,87
14
EN 13657:2002 (E)
Annex B
(informative)
Validation
During 1998 to1999 a project for validation of this standard has been organised and carried out. The validation
included an inter-laboratory study for evaluation of performance characteristics of methods included in the
standard (reproducibility, repeatability, accuracy where applicable), and a robustness study (i.e. the evaluation
of the influence of some defined operational parameters on the methods).
A questionnaire has been circulated by all CEN/TC292/WG3 members to collect a list of interested European
laboratories. About seventy laboratories gave their availability to participate to the inter-laboratory trial. All of
them were asked to declare that they fulfill the minimum requirements to carry out digestion and analyses
according to this standard. According to ISO 5725 series no selection has been made in advance on the basis
of the supposed "ability" of laboratories, their certifications, etc: it's therefore possible to assume that
participating laboratories are a rather good "sample" of "normal" European laboratories.
The materials to be used in the inter-laboratory study had to satisfy all the following requisites:
— available in a homogeneous form or, alternatively, not too difficult to grind, sieve and homogenise;
— city waste incineration fly ash ("oxidised" matrix) (CEN6/99 FLY ASH CW6 POWDER);
— city waste incineration bottom ash ("silicate" matrix) (CEN7/99 "ASH CW4 POWDER");
— ink waste sludge (organic matrix) (CEN8/99 "INK WASTE CW12 POWDER");
— electronic industry sludge ("metallic" matrix) (CEN9/99 "SEWAGE SLUDGE SL11 POWDER");
For the evaluation of performances of digestion procedures, independently from the subsequent analyses
performed on digested samples, all laboratories have been asked to analyse some already-prepared aqueous
solutions with different degrees of difficulty (clean synthetic solutions, acid digested solutions of the above four
materials). This has been used as a tool for discarding from the evaluation laboratories that did not prove their
analytical ability for some matrices/elements.
For accuracy evaluation, two certified reference material (CRM) have been also included:
All samples, including the two CRMs, have been delivered to laboratories in anonymous form.
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EN 13657:2002 (E)
B.1.3 Experimental
Preparation and homogenisation of samples, packaging, delivering, collection and evaluation of results have
been carried out by Environmental Monitoring Sector of European Commission Joint Research Centre in Ispra
(Italy).
B.1.4 Results
About fifty laboratories have actually returned results for the inter-laboratory study. The evaluation of results has
been performed by following these steps:
— removing of "obviously erroneous data", both means and single data according to ISO 5725, part 2, 7.2.6;
— results from laboratories failing to correctly measure some elements in "clean metals" solution were removed
from the whole data set (for the failed elements only);
— results from laboratories failing to correctly measure some elements in digested aqueous solutions were
removed from the whole data set (for the failed elements only);
— the remaining data sets were evaluated according to ISO 5725 series, with calculation of repeatability,
reproducibility and, where a "conventional true value" was available, accuracy (recovery); results of this
evaluation are reported in the tables below.
The inter-laboratory study involved a large number of laboratories, performing analyses in four replicates on
several samples (five aqueous, six powders), for the determination of a large number of elements (up to 31), by
using one to three digestion methods: this led to a very large data set. For some digestion methods and for
some elements determination, only few data were available (a minimum of 24 outlyer-free results is generally
required); anyway, even for these methods and elements, useful information on performance have been
obtained.
B.1.5 Conclusions
The performances of the three methods should be compared on an element-by-element, matrix-by-matrix basis,
in the tables below. In general words, performances are actually well comparable, especially for most
environmentally-sensitive elements.
Recovery rates for CRM: sewage sludge (BCR 146 R, non-refractory matrix) are in generally high, for CRM: city
waste incineration ash (BCR 176, refractory matrix) in many cases low. Digestion with aqua regia will not
necessarily release elements completely.
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EN 13657:2002 (E)
Table B.1 – Sample CEN 6/99 “Fly ash cw 6 powder”
N = Number of results, L = Number of laboratories, NA = Number of outliers, XREF = Conventional true value (where applicable)
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EN 13657:2002 (E)
N = Number of results, L = Number of laboratories, NA = Number of outliers, XREF = Conventional true value (where applicable)
18
EN 13657:2002 (E)
N = Number of results, L = Number of laboratories, NA = Number of outliers, XREF = Conventional true value (where applicable)
19
EN 13657:2002 (E)
N = Number of results, L = Number of laboratories, NA = Number of outliers, XREF = Conventional true value (where applicable)
20
EN 13657:2002 (E)
N = Number of results, L = Number of laboratories, NA = Number of outliers, XREF = Conventional true value (where applicable)
21
EN 13657:2002 (E)
N = Number of results, L = Number of laboratories, NA = Number of outliers, XREF = Conventional true value (where applicable)
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EN 13657:2002 (E)
B.2.1 General
Two key variables have been taken into account: particle size and mass of test portions; their influence on
microwave-assisted digestion method in closed vessels (see 9.2) has been independently evaluated; each variable
has been varied on different levels and each digestion has been performed at least in four replicates on a portion of
the same original sample (coal bottom ash); all digested solutions and blanks have been analyzed for the
determination of Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Se, Sn, Ti, V, Zn. A sequential
inductively coupled plasma optical emission spectrometer (ICP-OES) with pneumatic nebulizer was used for
determination of most elements; As, Cd, and Se were determined with both ICP-OES and a graphite furnace
atomic absorption spectrometer (GFAAS) with Zeeman background correction system; Hg was determined by
using a cold vapour atomic absorption spectrometer (CVAAS). Evaluation has not been possible for As, Cd, Hg and
Se because of their very low concentration (below limits of detection).
Levels of variables:
— sample particle size (digestions performed by weighing a test portion of 300 mg):
23
EN 13657:2002 (E)
B.2.3 Results
Influence of mass of test portion and sample particle size has been evaluated both visually and statistically.
Statistical evaluation has been carried out by using a "data pair comparison" criterion: for each digestion method
and element, recovery values in mg/kg have been paired for each level variation and the following parameters have
been calculated:
— the differences from recovery value at level A and level B: di = xA,i - xB,I ;
md ⋅ n
— the distribution-t, with the formula tˆ = ;
s
All distribution-t values, calculated as above, have been matched against tabled values tν shown in Table B.9;
when tˆ > tν , we assume that the differences between the two series of values (recovery at level 1 and recovery at
level 2) are significant, otherwise we assume that the difference is only casual (see Table B.8).
A qualitative evaluation of the overall robustness of the method with respect to a variable might be performed by
simply counting the number of elements that are not significantly affected by that variable.
24
EN 13657:2002 (E)
Table B.9 — Tabled values used for "data pair comparison" tests
ν tˆ
(n - 1)
1 12,706
2 4,303
3 3,182
4 2,776
5 2,571
6 2,447
7 2,365
B.2.4 Conclusion
Most elements behave in a very consistent way, showing small but significant effect of both variables: recovery rate
decreases slightly with the mass of test portion in almost all cases, and decreases slightly with increasing particle
size in most cases. Within the range specified by the standard (200 mg to 500 mg, < 250
a very small influence. It is important to stress that the study has been carried out on a sample with refractory
matrix. Most other kinds of samples are much less affected by both mass of test portion and particle size.
25
EN 13657:2002 (E)
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26
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BS EN
13657:2002
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