SIST-TP CEN/TR 16184:2012

SLOVENSKI STANDARD
01-februar-2012
Karakterizacija odpadkov - Dokument stanja tehnike - Analiza izlužkov
Characterization of waste - State-of-the-art document - Analysis of eluates
Charakterisierung von Abfällen - Stand der Technik - Analyse der Eluate
Caractérisation des déchets - Document de l’état de l’art et analyse des éluats
Ta slovenski standard je istoveten z: CEN/TR 16184:2011
ICS:
13.030.20 7HNRþLRGSDGNL%ODWR Liquid wastes. Sludge
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL REPORT
CEN/TR 16184
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
June 2011
ICS 13.030.99
English Version
Characterization of Waste - State-of-the-art document - Analysis
of eluates
Caractérisation des déchets - Document de l'état de l'art - Charakterisierung von Abfällen - Stand der Technik -
Analyse des éluats Analyse der Eluate

This Technical Report was approved by CEN on 1 March 2011. It has been drawn up by the Technical Committee CEN/TC 292.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland,
Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2011 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 16184:2011: E
worldwide for CEN national Members.

Contents Page
Foreword .3
Introduction .4
1 Scope .6
2 Normative references .6
3 Legislation .6
4 EN 12506:2003 and EN 13370:2003 - Current status .8
5 EN 12506 and EN 13370 – Proposal revision .9
6 Evaluation of the revised and new standards towards the available validation data . 13
6.1 Revised standards . 13
6.2 New standards . 14
7 Round robin test for the determination of Ba, Cd, Cr, Mo, Sb and Se in eluates . 17
7.1 General . 17
7.2 Round robin samples . 17
7.3 Results of the round robin test . 17
8 Determination of fluoride using ion selective electrode. 20
9 Results of round robin tests in the framework of acceptability of waste at landfills . 24
10 Conclusion . 26
Bibliography . 28

Foreword
This document (CEN/TR 16184:2011) has been prepared by Technical Committee CEN/TC 292
“Characterization of waste”, the secretariat of which is held by NEN.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
Introduction
For determining the acceptability of waste at landfills, test methods are described in two umbrella European
Standards:
 EN 12506, Characterization of waste – Analysis of eluates – Determination of pH, As, Ba, Cd, Cl-, Co, Cr,
Cr Vl, Cu, Mo, Ni, NO2-, Pb, total S, SO42-, V and Zn (analysis of inorganic constituents of solid waste
and/or its eluate; major, minor and trace elements);
 EN 13370, Characterization of waste – Analysis of eluates – Determination of Ammonium, AOX,
conductivity, Hg, phenol index, TOC, easily liberatable CN-, F (analysis of inorganic constituents of solid
waste and/or its eluate (anions)).
At the moment these standards are under revision and therefore this state-of-the-art document is prepared in
order to verify the following items:
 Are all parameters mentioned in the Council Decision of 19 December 2002 included in these two
European Standards?
 Should new relevant standards (e.g. EN ISO 17294 series) be included?
 Are the current analytical techniques capable of verifying the prescribed limit values with an acceptable
confidence level?
In Clause 5, a proposal is given for the revision of the EN 12506 and EN 13370 umbrella standards.
The major changes between the umbrella standard EN 12506:2003 and the proposal for revision are:
 Addition of the parameters Sb and Se together with the related analytical methods;
 Revision of the standards ISO 11885 (ICP-AES) and ISO 10304-1 (IC) (the versions of ISO 10304-1:1992
and ISO 10304-2:1995 have been combined in one standard ISO 10304-1:2007);
 Addition of the ICP-MS method (EN ISO 17294-1:2006 and EN ISO 17294-2:2004);
 Addition of the AAS with graphite furnace technique (EN ISO 15586:2003);
- 2-
 Addition of the flow analysis techniques for Cl (ISO 15682:2000), Cr(VI) (ISO 23913:2006) and SO
(ISO 22743:2006).
The major changes between the umbrella standard EN 13370:2003 and the proposal for revision are:
 Addition of the parameter TDS (total dissolved solids) together with the related analytical method;
 Replacement of the parameter TOC (total organic carbon) by DOC (dissolved organic carbon);
 Revision of the standards EN ISO 11732 (ammonium by flow analyser) and ISO 10304-1 (IC);
 Replacement of EN 1485 (AOX) by EN ISO 9562:2004;
 Revision and addition of new standards for Hg determination – EN 1483, EN ISO 17852 (and EN 12338);
-
 For the determination of F using the ion selective electrode it is recommended to use the buffer as
described in DIN 38405-4 instead of the buffer as described in ISO 10359-1, considering the higher
efficiency as decomplexing agent for Al, Fe, Mg and Ca-fluoride compounds.
With regard to the revised standards, there is no need for an additional validation round robin test when
implementing the revised standards into the umbrella standards EN 12506 and EN 13370.
Regarding the additional standards, all of these have waste water and/or leachates included in their scope,
meaning there are strong indications that the method is suitable for the analysis of eluates. Nevertheless, an
additional validation of these standards for eluate matrices is required when implementing them into the
umbrella standard, with the exception of:
 EN 12338:1998 (Hg – enrichment methods by amalgamation): There is no need to incorporate this
standard into the umbrella standard EN 13370 because a measurement in this low concentration range is
not required;
 EN 15126:2007 (TDS): As this parameter was validated for eluates in the EN 15126:2007, no additional
validation is required when implementing this standard into the umbrella standard EN 13370.
For the determination of the elements Mo, Ba, Cr, Cd, Sb and Se in eluates validation data are available from
a round robin test between 19 recognized laboratories (from Flanders – Belgium and the Netherlands)
organized by VITO (see Clause 6). Based on these results it can be concluded that for the various elements
using the ICP-AES technique according to ISO 11885 and the ICP-MS technique according to ISO 17294,
there are enough validation data available to implement in the umbrella standard. No additional validation of
the standard according to EN ISO/IEC 17025 is required. On the other hand, for the determination of Sb and
Se using the hydride generation procedure or the graphite furnace technique, additional validation data
according to the prescribed standards are required.
For all other parameters determined according to the new standards, additional validation data need to be
gathered. Once a year (in March) VITO organizes a round robin test for the analysis of eluates in the
framework of the acceptability of waste at landfills (see results of 2005, 2007 and 2008 in Clause 8). For this
purpose, round robin samples are yearly prepared. Having these samples available, it may be interesting to
distribute the same samples also to other European laboratories in order to validate the various parameters
according to the new European Standards.
Additionally, from the laboratories there is an increasing interest to implement the discrete analyser technique
in their laboratory to measure parameters such as ammonium, nitrite, chloride and sulfate in water samples.
At the moment, no International (ISO) or European (EN) Standard method is available. Moreover, the
Netherlands Standardization Institute (NEN) has developed and validated a standard method NEN 6604:2007
(Water – Determination of ammonium, nitrate, nitrite, chloride, ortho-phosphate, sulfate and silicate using a
discrete analyzer and spectrophotometric detection). This method should also be taken into consideration
when revising the standard.
The elements Hg and S are not included in the scope of the ICP-MS standard, however it is advisable to
investigate the determination of Hg and S with ICP-MS. Therefore, additional validation is required.
1 Scope
In the Council Decision of 19 December 2002 establishing criteria and procedures for the acceptance of waste
at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC, the test methods are described for
determining the acceptability of waste at landfills. In section 3 of the annex of this decision the following
umbrella European Standards are included for the analysis of eluates:
 ENV 12506 Analysis of eluates – Determination of pH, As, Ba, Cd, Cl, Co, Cr, Cr(VI), Cu, Mo, Ni, NO ,
Pb, total S, SO , V and Zn (analysis of inorganic constituents of solid waste and/or its eluate; major, minor
and trace elements);
 ENV 13370 Analysis of eluates – Determination of ammonium, AOX, conductivity, Hg, phenol index,
TOC, easily liberatable CN, F (analysis of inorganic constituents of solid waste and/or its eluate (anions)).
In 2003 both European Standards were approved and became final standards i.e. EN 12506 and EN 13370.
At the moment these standards are under revision and therefore a state-of-the-art document is prepared in
order to verify the following items:
 Are all parameters mentioned in the decision included in these two European Standards?
 Should new relevant standards (e.g. EN ISO 17294 series) be included?
 Are the current analytical techniques capable of verifying the prescribed limit values with an acceptable
confidence level?
2 Normative references
Not applicable.
3 Legislation
In the Council Decision of 19 December 2002 limit values for waste acceptable at the landfills are defined. The
limit values differ depending on the type of waste i.e.
 inert waste;
 non-hazardous waste;
 non-hazardous waste (stable, non-reactive);
 hazardous waste.
The limit values taken over from the Council Decision of 19 December 2002 are presented in Table 1.
Table 1 — Leaching limit values for L/S = 10 l/kg
Component Non- Non-hazardous
Hazardous
Inert waste hazardous waste (stable,
waste
waste non-reactive)
L/S = 10 l/kg L/S = 10 l/kg L/S = 10 l/kg L/S = 10 l/kg
mg/kg dm mg/kg dm mg/kg dm mg/kg dm
As 0,5 2 2 25
Ba 20 100 100 300
Cd 0,04 1 1 5
Cr total 0,5 10 10 70
Cu 2 50 50 100
Hg 0,01 0,2 0,2 2
Mo 0,5 10 10 30
Ni 0,4 10 10 40
Pb 0,5 10 10 50
Sb 0,06 0,7 0,7 5
Se 0,1 0,5 0,5 7
Zn 4 50 50 200
Chloride 800 15 000 15 000 25 000
Fluoride 10 150 150 500
a
Sulphate 1 000 20 000 20 000 50 000
Phenol index 1 - - -
b d d e
DOC 500 800 800 1000
c
TDS 4 000 60 000 50 000 100 000
a
If the waste does not meet these values for sulphate, it may still be considered as complying with the acceptance criteria
if the leaching does not exceed either of the following values: 1500 mg/l as C at L/S = 0,1 l/kg and 6 000 mg/kg at L/S =
10 l/kg. It will be necessary to use a percolation test to determine the limit value at L/S = 0,1 l/kg under initial equilibrium
conditions, whereas the value at L/S = 10 l/g may be determined either by a batch leaching test or by a percolation test
under conditions approaching local equilibrium.
b
If the waste does not meet these values for DOC at its own pH value, it may alternatively be tested at L/S = 10 l/kg and a
pH between 7,5 and 8,0. The waste may be considered as complying with the acceptance criteria for DOC, if the results of
this determination does not exceed 500 mg/kg. (A draft method based on EN 14429 is available).
c
The values for total dissolved solids (TDS) can be used alternatively to the values for sulphate and chloride.
d
If the waste does not meet these values for DOC at its own pH value, it may alternatively be tested at L/S = 10 l/kg and a
pH between 7,5 and 8,0. The waste may be considered as complying with the acceptance criteria for DOC, if the results of
this determination does not exceed 800 mg/kg. (A draft method based on EN 14429 is available).
e
If the waste does not meet these values for DOC at its own pH value, it may alternatively be tested at L/S = 10 l/kg and a
pH between 7,5 and 8,0. The waste may be considered as complying with the acceptance criteria for DOC, if the results of
this determination does not exceed 1 000 mg/kg. (A draft method based on EN 14429 is available).
4 EN 12506:2003 and EN 13370:2003 - Current status
The reference methods included in the current version of the umbrella standard EN 12506:2003 are described
in Table 2. The following text is included in the EN standard:
“It is pointed out that the standardized test methods listed in Table 2 have primarily been developed for the
analysis of water samples. They were validated in a new interlaboratory trial for a limited number of waste
eluate matrices performed by CEN/TC 292. Their suitability for other waste eluates has to be checked in the
laboratory performing the analysis.
If the test methods referred to in Table 2 are found to be inappropriate by reason of, for example, detection
limits, repeatability or interference, other methods validated for water analysis such as GF-AAS, ICP-MS can
be used. Their suitability for waste eluates has to be checked in the laboratory performing the analysis. The
reason for the deviation shall be stated in the test report.”
Table 2 — Parameters and test methods EN 12506:2003
Parameter Test method
a
pH ISO 10523
EN ISO 11885
As
EN ISO 11969
Ba EN ISO 11885
ISO 8288
Cd
EN ISO 11885
ISO 9297
-
Cl EN ISO 10304-1
EN ISO 10304-2
Co EN ISO 11885
Cr EN ISO 11885
Cr VI ISO 11083
ISO 8288
Cu
EN ISO 11885
Mo EN ISO 11885
ISO 8288
Ni
EN ISO 11885
EN 26777
EN ISO 10304-1
-
NO
EN ISO 10304-2
EN ISO 13395
ISO 8288
Pb
EN ISO 11885
Total S EN ISO 11885
EN ISO 10304-1
2-
SO
EN ISO 10304-2
V EN ISO 11885
ISO 8288
Zn
EN ISO 11885
a
at pH < 3 or pH > 10 use the same method but be aware that inaccuracy can increase.
NOTE The references towards the European or International Standards are those published at the time of the
approval of EN 12506:2003.
The reference methods included in the current version of the umbrella standard EN 13370:2003 are described
in Table 3. The following text is included in the EN standard:
“It is pointed out that the standardized test methods listed in Table 3 have primarily been developed for
the analysis of water samples. They were validated in a new interlaboratory trial for a limited number of
waste eluate matrices performed by CEN/TC 292. Their suitability for other waste eluates has to be
checked in the laboratory performing the analysis.
If the test methods referred to in Table 3 are found to be inappropriate by reason of, for example,
detection limits, repeatability or interference, other methods validated for water analysis such as AFS,
ICP-MS can be used. Their suitability for waste eluates has to be checked in the laboratory performing
the analysis. The reason for the deviation shall be stated in the test report.”
Table 3 — Parameters and test methods EN 13370:2003
Parameter Test method – current status
EN ISO 11732
Ammonium
ISO 7150-1
AOX EN 1485
Conductivity EN 27888
Hg EN 1483
ISO 6439
Phenol index
a
EN ISO 14402
TOC EN 1484
ISO 6703-2
-
CN easily liberatable
b
EN ISO 14403
c
EN ISO 10304-1
-
F
ISO 10359-1
a
after distillation.
b
free cyanide is equivalent to easily liberatable cyanide.
c
for eluates with low organic contamination.
5 EN 12506 and EN 13370 – Proposal revision
After the final approval in 2003 of both umbrella EN standards some of the cited standards were revised or
new standards were developed within CEN/TC 230 'Water analysis' or ISO/TC 147 'Water Quality'. Additional,
some parameters which are included in the Council Decision of 19 December 2002 are not included in the
current umbrella standards.
In Table 4, a proposal is worked out for the new EN 12506 umbrella standard, including all the cited
parameters in the Directive, related test methods and also the indication whether these standards are
validated for waste water by ISO/TC 147 or within the development of the EN 12506:2003 standard.
-
Parameters to be added (Sb and Se) and parameters which are not cited in the Directive (Co, Cr(VI), NO ,
total S, V), but are currently included in EN 12506:2003 are indicated in bold.
Table 4 — Parameters and test methods EN 12506 – proposal revision
Parameter Test methods – Test methods – Validated by ISO Validated by
b d
2003 version Proposal revision on waste water EN 12506 in
a
c
pH ISO 10523 (1994) ISO 10523:1994 X
EN ISO 11885 (1997) EN ISO 11885:2009 X X
EN ISO 11969 (1996) EN ISO 11969:1996
EN ISO 17294-1:2006  1 matrix
As
EN ISO 17294-2:2004
EN ISO 15586:2003 X
X
EN ISO 11885 (1997) EN ISO 11885:2009 X X
EN ISO 17294-1:2006
Ba
EN ISO 17294-2:2004
X
ISO 8288 (1986) ISO 8288:1996 X
EN ISO 11885 (1997) EN ISO 11885:2009 X X
EN ISO 17294-1:2006
Cd
EN ISO 17294-2:2004 .
EN ISO 15586:2003 X
X
ISO 9297 (1989) ISO 9297:1989 X X
-
Cl EN ISO 10304-1 (1995) ISO 15682:2000 X
EN ISO 10304-2 (1996) EN ISO 10304-1:2009 X X
EN ISO 11885 (1997) EN ISO 11885:2009 X X
EN ISO 17294-1:2006
Co EN ISO 17294-2:2004
EN ISO 15586:2003 X
X
EN ISO 11885 (1997) EN ISO 11885:2009 X X
EN ISO 17294-1:2006
Cr EN ISO 17294-2:2004
EN ISO 15586:2003 X
X
ISO 11083 (1994) ISO 11083:1994 X X
Cr(VI) EN ISO 10304-3:1997
EN ISO 23913:2009 X
ISO 8288 (1986) ISO 8288:1986 X
EN ISO 11885 (1997) EN ISO 11885:2009 X X
EN ISO 17294-1:2006
Cu
EN ISO 17294-2:2004
EN ISO 15586:2003 X
X
EN ISO 11885 (1997) EN ISO 11885:2009 X
EN ISO 17294-1:2006
Mo EN ISO 17294-2:2004
EN ISO 15586:2003 X
X
X
ISO 8288 (1986) ISO 8288:1986
EN ISO 11885 (1997) EN ISO 11885:2009 X X
EN ISO 17294-1:2006
Ni
EN ISO 17294-2:2004
EN ISO 15586:2003 X
X
Parameter Test methods – Test methods – Validated by ISO Validated by
b d
2003 version Proposal revision on waste water EN 12506 in
a
EN 26777 (1993) EN 26777:1993 X X
EN ISO 10304-1 (1995) EN ISO 10304-1:2009 X 1 matrix
-
NO
EN ISO 10304-2 (1996) EN ISO 13395:1996
EN ISO 13395 (1996) X 1 matrix
ISO 8288 (1986) ISO 8288:1986 X
EN ISO 11885 (1997) EN ISO 11885:2009 X X
EN ISO 17294-1:2006
Pb
EN ISO 17294-2:2004
EN ISO 15586:2003 X
X
Total S EN ISO 11885 (1997) EN ISO 11885:2009 X X
EN ISO 10304-1 (1995) EN ISO 10304-1:2009 X X
2-
SO EN ISO 10304-2 (1996) ISO 22743:2006
X
EN ISO 11885 (1997) EN ISO 11885:2009 1 matrix
EN ISO 17294-1:2006
V EN ISO 17294-2:2004
EN ISO 15586:2003 X
X
ISO 8288 (1986) ISO 8288:1986 X
EN ISO 11885 (1997) EN ISO 11885:2009 X X
EN ISO 17294-1:2006
Zn
EN ISO 17294-2:2004
EN ISO 15586:2003 X
X
EN ISO 11885:2009
EN ISO 17294-1:2006
Sb
EN ISO 17294-2:2004
EN ISO 15586:2003 X
EN ISO 11885:2009
EN ISO 17294-1:2006
EN ISO 17294-2:2004
Se
ISO 9965
EN ISO 15586:2003 X
X
a
Validated on minimum 2 eluate matrices.
b
Date between brackets indicates the version at the time the EN 12506 standard was approved.
c
at pH < 3 or pH > 10 use the same method but be aware that inaccuracy can increase.
d
For the determination of the elements the validation by ISO on waste water is always performed on a digested sample.
The major changes between the umbrella standard EN 12506:2003 and the proposal for revision are:
 Addition of the parameters Sb and Se together with the related analytical methods;
 Revision of the standards EN ISO 11885 and EN ISO 10304-1 (the old versions of EN ISO 10304-1:1995
and EN ISO 10304-2:1996 are now combined in 1 standard EN ISO 10304-1:2009);
 Addition of the ICP-MS method (EN ISO 17294-1:2006 and EN ISO 17294-2:2004);
 Addition of the AAS with graphite furnace method (EN ISO 15586:2003);
- 2-
 Addition of the flow analysis methods for Cl (EN ISO 15682:2001), Cr(VI) (ISO 23913:2006) and SO
(ISO 22743:2006).
In Table 5 a proposal is worked out for the new EN 13370 umbrella standard, including all the cited
parameters in the Directive, related test methods and also the indication whether these standards are
validated for waste water. Parameters to be added/changed (DOC and TDS) and parameters which are not
-
cited in the Directive (ammonium, AOX, CN easily liberatable), but are currently included in the EN
13370:2003 are indicated in bold.
Table 5 — Parameters and test methods EN 13370 – proposal revision
Parameter Test methods – Test methods – Validated Validated by EN
g a
current status Proposal revision by ISO/EN 13370 in 2003
on waste
water
Ammonium EN ISO 11732 (1997) EN ISO 11732:2005 X X
ISO 7150-1 (1984) ISO 7150-1:1984 X
EN ISO 14911:1999 X
b,
AOX EN 1485 (1986) EN ISO 9562:2004 X X
Conductivity EN 27888 (1993) EN 27888:1993 X X
Hg EN 1483 (1997) EN 1483:2007 X 1 matrix
EN ISO 17852:2008 X (effluent)
EN 12338:1998 X
Phenol index ISO 6439 (1990) ISO 6439:1990 1 matrix
d
EN ISO 14402 (1999) EN ISO 14402:1999 X 1 matrix
c
DOC EN 1484 (1997) EN 1484:1997 X X
-
CN easily ISO 6703-2 (1984) ISO 6703-2:1984 1 matrix
e
liberatable EN ISO 14403 (2002) EN ISO 14403:2002 X 1 matrix
- f f
F EN ISO 10304-1(1995) EN ISO 10304-1:2009 X
ISO 10359-1 (1992) ISO 10359-1:1992
X X
TDS - EN 15216:2007 X
a
Validated on minimum 2 eluate matrices.
b
EN 1485 is replaced by EN ISO 9562:2004.
c
TOC should be replaced by DOC.
d
After distillation.
e
Free cyanide is equivalent to easily liberatable cyanide.
f
For eluates with low organic contamination.
g
Date between brackets indicates the version at the time the EN 13370 standard was approved.
The major changes between the umbrella standard EN 13370:2003 and the proposal for revision are:
 Addition of the parameter TDS (total dissolved solids) together with the related analytical method;
 Replacement of the parameter TOC (total organic carbon) by DOC (dissolved organic carbon);
 Revision of the standards EN ISO 11732 and EN ISO 10304-1;
 Replacement of EN 1485 by EN ISO 9562:2004;
 Revision and addition of new standards for Hg determination – EN 1483, EN ISO 17852 (and EN 12338).
6 Evaluation of the revised and new standards towards the available validation data
6.1 Revised standards
6.1.1 EN 1483 (Hg using CV-AAS) – revised standard
The standard specifies two methods using AAS as detection technique; the first uses tin(II)chloride as
reducing agent, while the second uses sodium borohydride as reducing agent. Both methods are suitable for
the determination of Hg in water, for example drinking, ground, surface and waste waters, in a concentration
range from 0,1 µg/l to 10 µg/l.
In the normative part of EN 1483:2007 no significant technical changes were made compared to the previous
version. The major change is the addition of the potassium bromate – potassium bromide digestion in Annex
A. Therefore, no new validation round robin test was organized to implement in the 2007 standard, and the
validation data of the previous standard were taken over.
6.1.2 EN ISO 9562:2004 (AOX) – revised standard
The standard specifies a method for the direct determination of an amount of usually 10 µg/l in water of
organically bound chlorine, bromine and iodine (expressed as chloride) adsorbable on activated carbon). The
standard contains validation data determined on industrial waters, a leachate, sea water, technical HCl and a
blank.
6.1.3 EN ISO 10304-1:2009 (ion chromatography) – revised standard
The versions of EN ISO 10304-1:1995 (low contaminated water) and EN ISO 10304-2:1996 (waste water) are
now combined in one standard EN ISO 10304-1:2009. The latter specifies a method for the determination of
dissolved bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate in water, e.g. drinking water,
ground water, surface water, waste water and marine water by liquid chromatography of ions.
In EN ISO 10304-1:2009 no significant technical changes were made compared to the previous versions.
Therefore, no new validation round robin test was organized to implement in the 2009 standard, and the
-
validation data of the previous standards were taken over. For the parameter F the validation is only
- - 2-
performed on drinking water and a synthetic sample, while for the other parameters (Cl, NO , SO ) the
2 4
validation is performed on a broad range of matrices including waste water. During the validation of
- - - 2-
EN 12506:2003 and EN 13370:2003 for eluate analysis all the parameters F , Cl , NO (1 matrix) and SO
2 4
were included.
6.1.4 EN ISO 11732:2005 (ammonium with flow analysis) – revised standard
The standard specifies methods suitable for the determination of ammonium nitrogen in various types of
waters (such as ground, drinking, surface and waste water), applying either FIA or CFA.
In EN ISO 11732:2005 no significant technical changes were made compared to the previous version. The
validation data of the previous standard are incorporated in the revised standard without any changes.
Validation data are available for the matrices drinking water, river water, effluent of a domestic water treatment
plant and effluent from an industrial water treatment plant.
6.1.5 EN ISO 11885:2009 (ICP-AES) – revised standard
EN ISO 11885:2009 specifies a method for the determination of dissolved elements, elements bounds to
particles and total content of elements in different types of water (e.g. ground, surface, raw, potable and waste
water).
In the scope of this standard the following is mentioned:
“Taking into account the specific and additionally occurring interferences, these elements can also be
determined in digests of water, sludges and sediments (for example, digests of water as specified in
EN ISO 15587-1 or EN ISO 15587-2). The method is suitable for mass concentrations of particulate matter in
waste water below 2g/l. The scope of this method may be extended to other matrices or to higher amounts of
particulate matter if it can be shown that additionally occurring interferences are considered and corrected for
carefully. It is up to the user to demonstrate the fitness for purpose.”
The major technical adaptation of the 2009 version of the standard compared to the 1996 version involves the
addition of the measurement using the axial viewing mode, complementary to the radial viewing mode which
was previously described. For most trace elements this results in a lowering of the limits of detection. An
interlaboratory trial was performed in February 2006. A range of elements including As, Ba, Cd, Co, Cr, Cu,
Ni, Pb, S, Zn (not Mo, V) were analysed in drinking water, surface water (after filtration) and waste water (after
digestion according to EN ISO 15587-1 or EN ISO 15587-2).
6.1.6 Conclusion – revised standards
Based on the available information there is no need for an additional validation round robin test when
implementing the revised standards into the umbrella standards EN 12506 and EN 13370.
6.2 New standards
6.2.1 EN ISO 10304-3 (chromate with ion chromatography) – new standard
The standard specifies a method for the determination of dissolved anions such as chromate in aqueous
solutions using liquid chromatography of ions. The standard contains validation data for the matrices drinking
water, sewage industrial and sewage domestic.
6.2.2 EN 12338:1998 (Hg – enrichment methods by amalgamation) – new standard
The standard specifies two methods using AAS as detection technique after amalgamation; the first uses
tin(II)chloride as reducing agent, while the second uses sodium borohydride as reducing agent. Both methods
are suitable for the determination of Hg in water, for example drinking, ground, surface and waste waters, in a
concentration range from 0,01 µg/l to 1 µg/l.
Besides the enrichment by amalgamation, this method is comparable with EN 1483. As for landfills the lowest
limit value for Hg is 0,01 mg/kg dm (inert waste), meaning 1 µg/l using a L/S = 10 l/kg, this limit value can be
controlled with an acceptable confidence level without enrichment. Note that within EN 1483 the concentration
range is from 0,1 µg/l up to 10 µg/l.
There is no need to incorporate the standard into the umbrella standard EN 13370 because a measurement in
this low concentration range is not required.
6.2.3 EN ISO 14911:1999 (ammonium with ion chromatography) – new standard
+
This standard specifies a method for the determination of dissolved cations of which NH in water (e.g.
drinking water, surface water, waste water) using ion chromatography. The standard includes validation data
for the matrices water (synthetic), drinking water, river water and domestic sewage water.
6.2.4 EN 15216:2007 (TDS) – new standard
The standard describes a method for the determination of total dissolved solids in water and eluates.
Validation data are included for the matrices surface water, waste water and eluates.
As this parameter was validated for eluates in EN 15126:2007, no additional validation is required when
implementing ISO 15126:2007 in the revised EN 13370.
6.2.5 EN ISO 15586:2003 (GF-AAS) – new standard
The standard includes principles and procedures for the determination of trace levels of: Ag, Al, As, Cd, Co,
Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, Tl, V and Zn in surface water, ground water, drinking water, wastewater
and sediments, using atomic absorption spectrometry with electrothermal atomization in a graphite furnace.
An interlaboratory trial was performed in 2002 that included synthetic water samples, natural water, waste
water (analysed after digestion), sediment digest, and dried homogenized lake sediment. Antimony in waste
water was not evaluated because it was determined by fewer than three laboratories.
6.2.6 EN ISO 15682:2001 (chloride using flow analysis) – new standard
The standard specifies two methods for the determination of chloride by flow analysis using a photometric
detection or using a potentiometric detection. Both methods are applicable to the analysis of water and waste
water (including leachates).
Validation data are available for a synthetic water standard, a surface water and an industrial waste water.
6.2.7 EN ISO 17294-2:2004 (ICP-MS) – new standard
EN ISO 17294-2 specifies a method for the determination of 62 elements in water (for example drinking water,
surface water, ground water, waste water and eluates). For eluates, the standard described the determination
of the total mass concentration after digestion (nitric acid digestion according to EN ISO 15587-2 is preferred
instead of the aqua regia digestion according to EN ISO 15587-1). Nevertheless the standard states that if
experience has shown that the elements will be recovered quantitatively without decomposition, the digestion
may be omitted.
As the eluates are filtered after leaching, the dissolved elements may be measured directly into the solution
without digestion.
Validation results for the elements As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, V and Zn were obtained from analyses
performed on a surface water, an aqua regia digest (also Sb) and a synthetic standard (also Sb). No validation
data for Se in the water matrix are included.
NOTE The elements Hg and S are not included in the scope of the ICP-MS standard, however it is advisable to
investigate the determination of Hg and S with ICP-MS. Therefore, additional validation is required.
6.2.8 EN ISO 17852:2008 (Hg using AFS) – new standard
The standard specifies a method for the determination of mercury in drinking, surface, ground and rain water
using atomic fluorescence spectrometry. The standard may be applied to industrial and municipal waste water
after an additional digestion step under appropriate conditions. The standard contains validation data
determined on a spiked blank, two standard solutions, a spiked river water and a spiked trade effluent.
6.2.9 ISO 22743:2006 (sulfate using flow analysis) – new standard
The standard specifies a continuous flow analysis (CFA) method for the determination of sulfate in various
types of water (such as ground water, drinking water and waste water).
Validation data are available for drinking water, surface water and domestic waste water.
6.2.10 EN ISO 23913:2009 (Cr(VI) using flow analysis) – new standard
The standard specifies flow injection analysis (FIA) and continuous flow analysis (CFA) methods for the
determination of Cr(VI) in various types of water. The FIA technique is applicable for surface water, leachates
and waste water. The CFA technique can be applied for drinking water, ground water, surface water,
leachates and waste water.
Validation data are available for drinking water, surface water and domestic waste water.
6.2.11 Conclusions – new standards
All of the new standards have waste water and/or leachates included in their scope, meaning strong
indications that the method is suitable for the analysis of eluates. Nevertheless an additional validation of
these standards for eluate matrices is required when implementing them into the umbrella standard, with the
exception of:
 EN 12338:1998 (Hg – enrichment methods by amalgamation): There is no need to incorporate this
standard into the umbrella standard EN 13370 because a measurement in this low concentration range is
not required;
 EN 15126:2007 (TDS): As this parameter was validated for eluates in the EN 15126:2007, no additional
validation is required when implementing this standard into the umbrella standard EN 13370.
For the determination of the elements Mo, Ba, Cr, Cd, Sb and Se in eluates validation data are available from
a round robin test between 19 recognized laboratories (from Flanders – Belgium and the Netherlands)
organized by VITO (see Clause 7). The obtained results show that for the determination of the elements Sb
and Se the ICP-MS technique is the method of choice, especially to control the lowest limit values. Using the
ICP-AES technique, the limit of detection for Sb and Se is too high to verify the lowest limit values with an
acceptable confidence level. In addition, Cr interfere on the spectral line of Sb (206,836 nm), therefore an
interelement correction has to be performed or an alternative line for Sb has to be taken. The hydride
generation ICP-AES technique and the graphite furnace can also be used to measure Sb and Se, provided
that the hydride generation procedure is capable of obtaining maximum yields for these elements. For the
other elements evaluated (Mo, Ba, Cr, Cd) it can be concluded that accurate and reproducible data can be
obtained, independent of the applied technique (ICP-MS or ICP-AES).
Based on these results it can be concluded that for the various elements using the ICP-AES technique
according to EN ISO 11885 and the ICP-MS technique according to EN ISO 17294 series, there are enough
validation data available to implement in the umbrella standard. No additional validation is required. On the
other hand, for the determination of Sb and Se using the hydride generation procedure or the graphite furnace
technique, additional validation data according to the prescribed standards are required.
For all other parameters determined according to the new standards, additional validation data need to be
gathered. Once a year (in March) VITO organizes a round robin test for the analysis of eluates in the
framework of the acceptability of waste at landfills (see results of 2005, 2007 and 2008 in Clause 9). For this
purpose, round robin samples are yearly prepared. Having these samples available, it may be interesting to
distribute the same samples also to other European laboratories in order to validate the various parameters
according to the new European Standards.
Additionally, from the laboratories there is an increasing interest to implement the discrete analyser technique
in their laboratory to measure parameters such as ammonium, nitrite, chloride, sulfate in water samples. At
the moment no International (ISO) or European (EN) Standard method is available. Moreover, the
Netherlands Standardization Institute (NEN) has developed and validated a standard method NEN 6604:2007
(Water – Determination of ammonium, nitrate, nitrite, chloride, ortho-phosphate, sulfate and silicate using a
discrete analyzer and spectrophotometric detection). This method should also be taken into consideration
when revising the standard.
The elements Hg and S are not included in the scope of the ICP-MS standard, however it is advisable to
investigate the determination of Hg and S with ICP-MS. Therefore, additional validation is required.
7 Round robin test for the determination of Ba, Cd, Cr, Mo, Sb and Se in eluates
7.1 General
In 2004-2005 a round robin test was organized by VITO in commission of the Public Waste Agency of
Flanders (OVAM) to evaluate the analytical performance of the laboratories for the determination of Ba, Cd,
Cr, Mo, Sb and Se in eluates. Nineteen laboratories (from Flanders – Belgium and the Netherlands)
participated to this round robin test and analysed four samples spiked with the elements at relevant
concentration levels.
7.2 Round robin samples
Eluate samples were prepared from 2 waste samples i.e. a blasting grit (eluate 1) and a contaminated soil
(eluate 2). To these eluate matrices the elements Ba, Cd, Cr, Mo, Sb and Se were added at 4 concentration
levels (low and high region). The reference values for these spiked eluates are presented in Table 6.
Table 6 — Reference values of round robin samples
Element Eluate 1-1 Eluate 1-2 Eluate 2-1 Eluate 2-2
µg/l µg/l µg/l µg/l
Mo 54,8 1 175 43 494
Sb 7,5 79 101 12,4
Se 12 59 15,5 79
Ba 1 275 2 937 996 1 977
Cr 39 1 174 3 921 26
Cd 2,95 117 4,96 147
7.3 Results of the round robin test
7.3.1 General
The results of the round robin test were subjected to a Grubbs outlier test (95 % confidence level,
2-sided). The outliers were removed and from the remaining values the average, the relative standard
deviation (% RSD) and the bias towards the reference value, were calculated.
7.3.2 Results for the elements Mo, Ba, Cr and Cd
For the elements Mo, Ba, Cr and Cd an overview of the obtained results is presented in Table 7. Combining
the results of both ICP-MS and ICP-AES, results in a relative standard deviation for all elements and type of
eluates of less than 7 %. The bias of the average is within acceptable limits. Only for the element Cd in eluate
2-1 an increased negative bias of -12 % is observed.
Evaluation of the dataset as a function of the applied analytical technique (i.e. ICP-MS and ICP-AES) results
in comparable measurement errors.
Table 7 — Overview of the round robin results for Mo, Ba, Cr and Cd
All results ICP-MS ICP-AES
Refer
Eluate value Average % %
µg/l n / o µg/l % RSD % Bias n / o RSD n / o RSD
Mo 54,8 19/2 54 4,0 -0,8 4/0 5,0 15/2 3,6
Ba 1 275 21/0 1 258 3,2 -1,3 4/0 3,0 17/0 3,2
1-1
Cr 39 21/0 39 6,5 0,1 4/0 5,2 17/0 6,9
Cd 2,95 18/3 2,9 5,2 -3,1 5/1 7,7 13/2 4,3
Mo 1 175 20/1 1 178 5,4 0,2 4/0 6,0 16/1 5,2
Ba 2 937 21/0 2 988 4,6 1,7 4/0 6,7 17/0 3,9
1-2
Cr 1 174 20/1 1 191 4,3 1,5 4/0 5,1 16/1 4,0
Cd 117 20/1 115 3,4 -1,4 6/0 3,7 14/1 2,9
Mo 43 19/2 46 6,3 6,9 4/0 7,1 15/2 6,3
Ba 996 21/0 961 5,3 -3,5 4/0 6,5 17/0 5,2
2-1
Cr 3 921 21/0 4 048 3,5 3,3 4/0 4,2 17/0 3,5
Cd 4,96 19/2 4.3 7,2 -12 6/0 4,8 13/2 7,9
Mo 494 20/1 472 6,3 -4,5 4/0 6,9 16/1 6,0
Ba 1 977 21/0 1 948 4,6 -1,4 4/0 5,8 17/0 5,4
2-2
Cr 26 20/1 26 6,1 0,8 4/0 7,3 16/1 6,0
Cd 147 20/1 143 4,5 -3,0 6/0 4,3 14/1 4,2
n: validated results; o: amount of outliers
Based on these results it can be concluded that for the elements Mo, Ba, Cr and Cd accurate and
reproducible data can be obtained, independent of the applied technique (ICP-MS or ICP-AES).
7.3.3 Results for the elements Sb and Se
For the elements Sb and Se an overview of all the results is given in Table 8. These results show that for low
levels of Sb and Se (7 to 15 µg/l) relative high measurement errors up to ± 16 % are obtained. And although
the concentration level of Sb in eluate 2-1 is higher, a relative standard deviation of 25 % is observed.
Table 8 — Overview round robin results for Sb and Se
...