FprEN 16166

Soil, treated biowaste and sludge - Determination of adsorbed organically bound halogens (AOX)

This document specifies an operationally defined method for the direct determination of organically bound halogens (chlorine, bromine and iodine) adsorbed and occluded to the sample matrix. AOX being a methodologically defined parameter, it is essential that the procedure is applied without any modification.
This document is intended for analysis of sludge, treated biowaste or soil in concentrations ranging from 5 mg/kg dry matter. The upper limit and exact concentration range covered depend on the instrumentation used for determination.
NOTE   This method can also be applied to other environmental solid matrices, provided the user has verified the applicability.

Boden, behandelter Bioabfall und Schlamm - Bestimmung von adsorbierten organisch gebundenen Halogenen (AOX)

Dieses Dokument legt ein operativ definiertes Verfahren zur direkten Bestimmung von organisch gebundenen Halogenen (Chlor, Brom und Iod) adsorbiert und von der Probenmatix umschlossen fest. Da es sich bei AOX um einen methodisch definierten Parameter handelt, ist es wichtig, dass das Verfahren unverändert angewendet wird.
Dieses Dokument ist für die Untersuchung von Schlamm, behandeltem Bioabfall oder Boden in Konzentrationen im Bereich von 5 mg/kg Trockenmasse vorgesehen. Der obere Grenzwert und der tatsächlich erfasste Konzentrationsbereich hängen von dem zur Bestimmung verwendeten Gerät ab.
Anmerkung      Dieses Verfahren kann auch auf weitere feste Umweltmatrizes angewendet werden, sofern der Anwender die Anwendbarkeit bestätigt hat.

Boues, biodéchets traités, sols et sédiments - Détermination des composés organiques halogénés adsorbables (AOX)

Le présent document spécifie une méthode opérationnelle définie pour la détermination directe des composés organiques halogénés (chlore, brome et iode) adsorbés et occlus dans la matrice d’échantillon. Comme les AOX constituent un paramètre défini sur le plan méthodologique, il est essentiel que le mode opératoire soit appliqué sans aucune modification.
Le présent document est destiné à l’analyse des boues, des biodéchets traités ou des sols de concentrations à partir de 5 mg/kg de matière sèche. La limite supérieure et la gamme exacte de concentrations dépendent de l’appareillage utilisé pour la détermination.
NOTE   Cette méthode peut également être appliquée à d’autres matrices solides environnementales, sous réserve que l’utilisateur ait vérifié son applicabilité.

Blato, obdelani biološki odpadki, tla in sedimenti - Določevanje adsorbiranih organsko vezanih halogenov (AOX)

General Information

• Status: Not Published
• ICS: 13.030.01 - Wastes in general
• ICS: 13.080.10 - Chemical characteristics of soils
• Technical Committee: CEN/TC 444 - Environmental characterization
• Drafting Committee: CEN/TC 444/WG 3 - Inorganic analysis
• Current Stage: 5060 - Closure of Vote - Formal Approval
• Due Date: 21-Oct-2021
• Completion Date: 21-Oct-2021
• Directive: 86/278/EEC - Protection of the environment, and in particular of the soil, when sewage sludge is used in agriculture
• Mandate: M/330 - Mandate given to CEN for the development of horizontal standards in the fields of sludge, biowaste and soil.
• Ref Project: kSIST FprEN 16166:2021 - Sludge, treated biowaste, soil and sediments - Determination of adsorbed organically bound halogens (AOX)

RELATIONS

• Revised: EN 16166:2012 - Sludge, treated biowaste and soil - Determination of adsorbable organically bound halogens (AOX)
• Effective Date: 07-Aug-2019

Standards Content (sample)

SLOVENSKI STANDARD
oSIST prEN 16166:2020
01-julij-2020

Blato, obdelani biološki odpadki in tla - Določevanje organsko vezanih halogenov,

sposobnih adsorpcije (AOX)

Sludge, treated biowaste and soil - Determination of adsorbable organically bound

halogens (AOX)

Schlamm, behandelter Bioabfall und Boden - Bestimmung von adsorbierbaren organisch

gebundenen Halogenen (AOX)

Boues, biodéchets traités et sols - Détermination des composés organiques halogénés

adsorbables (AOX)
Ta slovenski standard je istoveten z: prEN 16166
ICS:
13.030.20 Tekoči odpadki. Blato Liquid wastes. Sludge
13.080.10 Kemijske značilnosti tal Chemical characteristics of
soils
oSIST prEN 16166:2020 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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oSIST prEN 16166:2020
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oSIST prEN 16166:2020
DRAFT
EUROPEAN STANDARD
prEN 16166
NORME EUROPÉENNE
EUROPÄISCHE NORM
June 2020
ICS 13.030.01; 13.080.10 Will supersede EN 16166:2012
English Version
Sludge, treated biowaste, soil and sediments -
Determination of adsorbed organically bound halogens
(AOX)

Boues, biodéchets traités et sols - Détermination des Schlamm, behandelter Bioabfall und Boden -

composés organiques halogénés adsorbables (AOX) Bestimmung von adsorbierbaren organisch

gebundenen Halogenen (AOX)

This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee

CEN/TC 444.

If this draft becomes a European Standard, CEN members are bound to comply with the CEN/CENELEC Internal Regulations

which stipulate the conditions for giving this European Standard the status of a national standard without any alteration.

This draft European Standard was established by CEN in three official versions (English, French, German). A version in any other

language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC

Management Centre has the same status as the official versions.

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, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey 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 European Standard. It is distributed for review and comments. It is subject to change without

notice and shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels

© 2020 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 16166:2020 E

worldwide for CEN national Members.
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oSIST prEN 16166:2020
prEN 16166:2020 (E)
Contents Page

European foreword ............................................................................................................................................ 3

Introduction .......................................................................................................................................................... 4

1 Scope .......................................................................................................................................................... 5

2 Normative references .......................................................................................................................... 5

3 Terms and definitions ......................................................................................................................... 5

4 Principle ................................................................................................................................................... 5

5 Interferences .......................................................................................................................................... 5

6 Reagents ................................................................................................................................................... 6

7 Apparatus ................................................................................................................................................ 7

7.1 Apparatus for combustion and detection .................................................................................... 7

7.2 Equipment for adsorption ................................................................................................................. 7

7.3 Equipment for sample preparation ................................................................................................ 7

8 Sample storage and pretreatment .................................................................................................. 7

8.1 Sample storage ....................................................................................................................................... 7

8.2 Sample pretreatment .......................................................................................................................... 8

9 Procedure ................................................................................................................................................ 8

9.1 General...................................................................................................................................................... 8

9.2 Adsorption and inorganic halide removal ................................................................................... 8

9.3 Combustion ............................................................................................................................................. 9

9.4 Preliminary tests and daily checks................................................................................................. 9

9.5 Blank determination ......................................................................................................................... 10

10 Calculation ............................................................................................................................................. 10

10.1 Mass concentration of adsorbed organically bound halogens [ρ (AOX)] in dried

sample ..................................................................................................................................................... 10

10.2 Expression of results ......................................................................................................................... 11

11 Precision ................................................................................................................................................ 11

12 Test report ............................................................................................................................................. 11

Annex A (informative) Repeatability and reproducibility data ...................................................... 12

A.1 Materials used in the interlaboratory comparison study .................................................... 12

A.2 Interlaboratory comparison results ............................................................................................ 13

Annex B (informative) Storage of activated carbon ............................................................................ 14

Bibliography ....................................................................................................................................................... 15

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oSIST prEN 16166:2020
prEN 16166:2020 (E)
European foreword

This document (prEN 16166:2020) has been prepared by Technical Committee CEN/TC 444

“Environmental characterization of solid matrices”, the secretariat of which is held by NEN.

This document is currently submitted to the CEN Enquiry.

This document has been prepared under a mandate given to CEN by the European Commission and the

European Free Trade Association.
This document will supersede EN 16166:2012.

In comparison with the previous edition, the following technical modifications have been made:

• Calculation harmonized with EN ISO 9562;

• Initial check and daily check procedure harmonized with EN ISO 9562 and extended to include full

measuring process.
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oSIST prEN 16166:2020
prEN 16166:2020 (E)
Introduction

This document is the result of a desk study “Horizontal European standard for determination of AOX in

sewage sludge and comparable matrices” in the project “Horizontal” and aims at evaluating the latest

developments in assessing AOX in sludge, soil, treated biowaste and neighbouring fields. After an

evaluation study, in which the ruggedness of the method was studied, a Europe-wide validation of the

draft standard has taken place. The results of the desk studies as well as the evaluation and validation

studies have been subjected to discussions with all parties involved in the evaluation.

This document is applicable and validated for several types of matrices as indicated in Table 1 (see also

Annex A for the results of the validation).
Table 1 — Matrices for which this document is applicable and validated
Matrix Materials used for validation
Sludge Municipal sludge
Compost Fresh compost
Compost
Soil Sludge amended soil
Agricultural soil
Sediments Surface water sediments

WARNING — Persons using this document should be familiar with usual laboratory practice. This

document does not purport to address all of the safety problems, if any, associated with its use. It is the

responsibility of the user to establish appropriate safety and health practices and to ensure compliance

with any national regulatory conditions.

IMPORTANT — It is absolutely essential that tests conducted according to this document be carried out

by suitably trained staff.
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oSIST prEN 16166:2020
prEN 16166:2020 (E)
1 Scope

This document specifies an empirical method for the direct determination of organically bound halogens

adsorbable on activated carbon present in the aqueous phase of the sample prior to drying or adsorbed

to sample surface.

This document is intended for analysis of sludge, treated biowaste, soil or sediments in concentrations

ranging from 5 mg/kg dry matter. The upper limit and exact concentration range covered depend on the

instrumentation used for determination.
2 Normative references

The following documents are referred to in the text in such a way that some or all of their content

constitutes requirements of this document. For dated references, only the edition cited applies. For

undated references, the latest edition of the referenced document (including any amendments) applies.

EN 16179, Sludge, treated biowaste and soil — Guidance for sample pretreatment
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.

ISO and IEC maintain terminological databases for use in standardization at the following addresses:

• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at https://www.iso.org/obp/ui
3.1
adsorbed organically bound halogens, AOX

amount of chlorine, bromine, and iodine contained as organic compounds in the sample matrix, expressed

as chloride when determined according to this document

Note 1 to entry: This includes halogenated organic compounds adsorbed at the dry sample matrix as well as water

soluble halogenated compounds that can be adsorbed on to active carbon.
4 Principle

Activated carbon is added to a dried, homogenized solid sample. Inorganic halides are eluted and at the

same time water soluble organic compounds are adsorbed onto the activated carbon by shaking with

acidified nitrate solution.
The loaded carbon/sample mixture is combusted in an oxygen stream.

The hydrogen halides produced are absorbed followed by the determination of the halide ions, for

example, by microcoulometric titration. The result is expressed as the mass concentration of chloride.

5 Interferences

Sparingly soluble or occluded inorganic halides are included in the determination and can, if present, give

a significant positive bias. Adequate washing is essential to remove inorganic interference.

Iodide contained in the sample can be adsorbed to the active carbon and not be washed off, thus leading

to positive bias.
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oSIST prEN 16166:2020
prEN 16166:2020 (E)

Organic bromine and iodine compounds can, during combustion, lead to the formation of elemental

bromine or iodine respectively or to the formation of halogen oxides. The determination of these AOX

fractions can be incomplete, thus leading to negative bias.

Samples with significant amounts of volatile, purgeable organic halogen compounds can lead to negative

bias. In this case, the sample is to be suspended in water and purged with oxygen at 60 °C for 30 min. The

purged gases are analysed by the analytical instrument. The resulting portion of purgeable organic

halogens is added to the result of the regular determination.
6 Reagents

Use only reagents of recognized analytical grade. Water should be of high purity, for example, in

accordance with [3] grade 1.

The AOX contribution from water, reagents and gases should be significantly lower than the lowest AOX

content to be determined. The overall AOX content of water, chemicals, and gases shall be checked by

measuring the total blank (see 9.5).
6.1 Activated carbon, grain size approximately 10 µm to 50 µm.
For the storage of activated carbon, see Annex B.

The blank value of the activated carbon shall be less than 15 µg of chloride equivalent per gram of

activated carbon.
, ρ = 1,4 g/ml, 65 % (m/m) solution.
6.2 Nitric acid, HNO3
6.3 Hydrochloric acid, c(HCl) = 0,010 mol/l.
6.4 Sulfuric acid, H SO , ρ = 1,84 g/ml.
2 4

6.5 Gases for combustion, e.g. oxygen (O ), or a mixture of oxygen and an inert gas.

6.6 Sodium nitrate, NaNO , for the preparation of stock solution.
6.7 Nitrate stock solution, acidified, c(NaNO ) = 0,2 mol/l.

Dissolve 17 g of sodium nitrate (6.6) in water in a 1 000 ml volumetric flask, add 15 ml of nitric acid (6.2),

and make up to volume with water.
6.8 Nitrate washing solution, c(NaNO ) = 0,01 mol/l.

Pipette 50 ml of the nitrate stock solution (6.7) in a 1 000 ml volumetric flask, and make up to volume

with water.
6.9 4-chlorophenol, stock solution, ρ (AOX) = 200 mg/L.

Dissolve 72,5 mg of 4-chlorophenol (C H ClO) in water in a 100 ml volumetric flask and make up to

6 5
volume with water.
6.10 2-chlorobenzoic acid, stock solution ρ (AOX) = 250 mg/L.

Dissolve 110,4 mg 2-chlorobenzoic acid in a 100 ml volumetric flask in water and make up to volume

with water.
The dissol
...