SIST-TP CEN/TR 16184:2012

Characterization of waste - State-of-the-art document - Analysis of eluates

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, NO2, Pb, total S, SO4, 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?

Charakterisierung von Abfällen - Stand der Technik - Analyse der Eluate

Caractérisation des déchets - Document de l’état de l’art et analyse des éluats

Karakterizacija odpadkov - Dokument stanja tehnike - Analiza izlužkov

V Odločbi Sveta z dne 19. decembra 2002 o določitvi meril in postopkov za sprejemanje odpadkov na odlagališčih na podlagi člena 16 in Priloge II k Direktivi 1999/31/ES so opisane preskusne metode za določanje sprejemljivosti odpadkov na odlagališčih. V oddelku 3 Priloge k tej odločbi so navedeni krovni evropski standardi za analizo izlužkov: ENV 12506 Analiza izlužkov – določanje pH, As, Ba, Cd, Cl, Co, Cr, Cr(VI), Cu, Mo, Ni, NO2, Pb, skupnega S, SO4, V in Zn (analiza anorganskih sestavin trdnih odpadkov in/ali njihovih izlužkov; glavni, stranski elementi in elementi v sledeh); Analiza izlužkov – določanje amonija, AOX, prevodnosti, Hg, fenolnega indeksa, TOC, nestabilni CN, F (analiza anorganskih sestavin trdnih odpadkov in/ali njihovih izlužkov (anioni)). Oba evropska standarda sta bila odobrena leta 2003 in tako postala končna standarda, tj. EN 12506 in EN 13370. Trenutno sta ta standarda v reviziji, zato se pripravlja dokument stanja tehnike za potrditev naslednjih točk: Ali so vsi parametri iz odločbe vključeni v ta dva evropska standarda? Ali bi bilo treba vključiti nove ustrezne standarde (npr. serijo EN ISO 17294)? Ali je s sedanjimi tehnikami analize mogoče dovolj zanesljivo potrditi predpisane mejne vrednosti?

General Information

• Status: Published
• Public Enquiry End Date: 19-Jan-2011
• Publication Date: 15-Jan-2012
• ICS: 13.030.20 - Liquid wastes. Sludge
• Technical Committee: KAT - Soil quality
• Current Stage: 6060 - National Implementation/Publication (Adopted Project)
• Start Date: 27-Dec-2011
• Due Date: 02-Mar-2012
• Completion Date: 16-Jan-2012
• Ref Project: CEN/TR 16184:2011 - Characterization of Waste - State-of-the-art document - Analysis of eluates

Standards Content (Sample)

SLOVENSKI STANDARD
SIST-TP CEN/TR 16184:2012
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
SIST-TP CEN/TR 16184:2012 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST-TP CEN/TR 16184:2012

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SIST-TP CEN/TR 16184:2012


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.

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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

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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.
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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
4
(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);
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-
 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.
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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 ,
2
Pb, total S, SO , V and Zn (analysis of inorganic constituents of solid waste and/or its eluate; major, minor
4
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.
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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 =
0
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).
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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
2
EN ISO 10304-2
EN ISO 13395
ISO 8288
Pb
EN ISO 11885
Total S EN ISO 11885
EN ISO 10304-1
2-
SO
4
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.
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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 ,
2
total S, V), but are currently included in EN 12506:2003 are indicated in bold.
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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
2003
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
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Parameter Test methods – Test methods – Validated by ISO Validated by
b d
2003 version Proposal revision on waste water EN 12506 in
a
2003
EN 26777 (1993) EN 26777:1993 X X
EN ISO 10304-1 (1995) EN ISO 10304-1:2009 X 1 matrix
-
NO
2
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
4
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.
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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
4
(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.
12

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SIST-TP CEN/TR 16184:2012
CEN/TR 16184:2011 (E)
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.
13

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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
...

SLOVENSKI STANDARD
kSIST-TP FprCEN/TR 16184:2010
01-december-2010
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: FprCEN/TR 16184
ICS:
13.030.20 7HNRþLRGSDGNL%ODWR Liquid wastes. Sludge
kSIST-TP FprCEN/TR 16184:2010 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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kSIST-TP FprCEN/TR 16184:2010

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kSIST-TP FprCEN/TR 16184:2010


TECHNICAL REPORT
FINAL DRAFT
FprCEN/TR 16184
RAPPORT TECHNIQUE

TECHNISCHER BERICHT

October 2010
ICS
English Version
Characterization of Waste - State-of-the-art document - Analysis
of eluates
Caractérisation des déchets - Document de l'état de l'art et Charakterisierung von Abfällen - Stand der Technik -
analyse des éluats Analyse der Eluate


This draft Technical Report is submitted to CEN members for Technical Committee Approval. 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.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are aware and to
provide supporting documentation.

Warning : This document is not a Technical Report. It is distributed for review and comments. It is subject to change without notice and
shall not be referred to as a Technical Report.


EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2010 CEN All rights of exploitation in any form and by any means reserved Ref. No. FprCEN/TR 16184:2010: E
worldwide for CEN national Members.

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FprCEN/TR 16184:2010 (E)
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

2

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Foreword
This document (FprCEN/TR 16184:2010) has been prepared by Technical Committee CEN/TC 292
“Characterization of waste”, the secretariat of which is held by NEN.
This document is currently submitted to the Technical Committee Approval.
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.
3

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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,
CrVI, Cu, Mo, Ni, NO , Pb, total S, SO , V and Zn (analysis of inorganic constituents of solid waste and/or
2 4
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 4 a proposal is worked out 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
4
(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);
4

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-
 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, 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.
5

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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 ,
2
Pb, total S, SO , V and Zn (analysis of inorganic constituents of solid waste and/or its eluate; major, minor
4
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.
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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 =
0
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).
7

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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
2
EN ISO 10304-2
EN ISO 13395
ISO 8288
Pb
EN ISO 11885
Total S EN ISO 11885
EN ISO 10304-1
2-
SO
4
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 moment the
EN 12506:2003 standard was approved.
8

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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 ,
2
total S, V), but are currently included in EN 12506:2003 are indicated in bold.
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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
2003
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
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Parameter Test methods – Test methods – Validated by ISO Validated by
b d
2003 version Proposal revision on waste water EN 12506 in
a
2003
EN 26777 (1993) EN 26777:1993 X X
EN ISO 10304-1 (1995) EN ISO 10304-1:2009 X 1 matrix
-
NO
2
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
4
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.
11

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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
4
(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.
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kSIST-TP FprCEN/TR 16184:2010
FprCEN/TR 16184:2010 (E)
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 the EN 1483:2007 standard 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.
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kSIST-TP FprCEN/TR 16184:2010
FprCEN/TR 16184:2010 (E)
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
pl
...