CEN/TR 16184:2011

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
...