SIST EN 14997:2015
(Main)Characterisation of waste - Leaching behaviour test - Influence of pH on leaching with continuous pH control
Characterisation of waste - Leaching behaviour test - Influence of pH on leaching with continuous pH control
This European Standard is applicable for determining the influence of pH on the leachability of inorganic constituents from a waste material. Approaching equilibrium as defined in this document is established by continuous adjustment of the pH by addition of acid or base to reach desired pH values. This test method produces eluates, which are subsequently characterized physically and chemically.
This document is a parameter specific test as specified in EN 12920. The application of this test method alone is not sufficient for the determination of the detailed leaching behaviour of a waste under specified conditions.
NOTE This generally requires the application of several test methods, behavioural modelling and model validation as specified in EN 12920.
Charakterisierung von Abfällen - Untersuchung des Auslaugungsverhaltens - Einfluss des pH-Wertes auf die Auslaugung bei kontinuierlicher pH-Wert-Kontrolle
Diese Europäische Norm legt ein Verfahren für die Bestimmung des Einflusses des pH Wertes auf die Eluierbarkeit von anorganischen Bestandteilen aus Abfall fest. Die Annäherung an das Gleichgewicht, wie es in dieser Europäischen Norm definiert ist, wird durch kontinuierliche Einstellung des pH-Wertes durch Zugabe von Säure oder Base hergestellt, um die gewünschten endgültigen pH Werte zu erreichen. Dieses Prüfverfahren führt zu Eluaten, die anschließend physikalisch und chemisch charakterisiert werden.
Diese Europäische Norm ist eine parameterspezifische Prüfung, wie in EN 12920 festgelegt. Die Anwendung nur dieses Prüfverfahrens ist für die Bestimmung des genauen Elutionsverhaltens eines Abfalls unter festgelegten Bedingungen nicht ausreichend.
Caractérisation des déchets - Essais de comportement à la lixiviation - Influence du pH sur la lixiviation avec contrôle continu du pH
La présente Norme européenne définit une méthode de détermination de l’influence du pH sur la lixiviabilité des constituants inorganiques d’un déchet. L’approche de l'état d’équilibre tel que défini dans la présente Norme européenne s’obtient par un ajustement permanent du pH en ajoutant un acide ou une base pour atteindre les valeurs de pH souhaitées. Cette méthode d’essai produit des éluats qui sont ensuite caractérisés du point de vue physicochimique.
La présente Norme européenne est un essai paramétrique, tel que spécifié dans l'EN 12920. Cette méthode d’essai n’est pas suffisante, à elle seule, pour déterminer en détail le comportement à la lixiviation d’un déchet dans des conditions spécifiées.
Karakterizacija odpadkov - Izluževalni preskus - Vpliv pH na izluževanje z uravnavanjem pH
General Information
Relations
Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Karakterizacija odpadkov - Izluževalni preskus - Vpliv pH na izluževanje z uravnavanjem pHCharakterisierung von Abfällen - Untersuchung des Auslaugungsverhaltens - Einfluss des pH-Wertes auf die Auslaugung bei kontinuierlicher pH-Wert-KontrolleCaractérisation des déchets - Essais de comportement à la lixiviation - Influence du pH sur la lixiviation avec contrôle continu du pHCharacterisation of waste - Leaching behaviour test - Influence of pH on leaching with continuous pH control13.030.01Odpadki na splošnoWastes in generalICS:Ta slovenski standard je istoveten z:EN 14997:2015SIST EN 14997:2015en,fr,de01-junij-2015SIST EN 14997:2015SLOVENSKI
STANDARDSIST-TS CEN/TS 14997:20071DGRPHãþD
SIST EN 14997:2015
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 14997
March 2015 ICS 13.030.01 Supersedes CEN/TS 14997:2006English Version
Characterization of waste - Leaching behaviour test - Influence of pH on leaching with continuous pH control
Caractérisation des déchets - Essais de comportement à la lixiviation - Influence du pH sur la lixiviation avec contrôle continu du pH
Charakterisierung von Abfällen - Untersuchung des Elutionsverhaltens - Einfluss des pH-Wertes auf die Elution bei kontinuierlicher pH-Wert-Kontrolle This European Standard was approved by CEN on 26 December 2014.
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the 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, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre:
Avenue Marnix 17,
B-1000 Brussels © 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 14997:2015 ESIST EN 14997:2015
EN 14997:2015 (E) 2 Contents Page Foreword .4 Introduction .5 1 Scope .7 2 Normative references .7 3 Terms and definitions .7 4 Symbols and abbreviations .8 5 Principle .9 6 Reagents .9 7 Equipment . 10 7.1 General . 10 7.2 Laboratory equipment . 10 8 Sample preparation . 11 8.1 Laboratory sample . 11 8.2 Preparation of the test sample . 11 8.3 Determination of dry residue . 11 8.4 Preparation of the test portion . 12 9 Procedure . 12 9.1 Contact time . 12 9.2 pH range . 12 9.3 Leaching test . 12 9.3.1 General . 12 9.3.2 Preparation of leachant . 13 9.3.3 Leaching procedure . 15 9.4 Natural pH . 16 10 Eluate treatment, storage and analysis . 16 11 Blank test . 16 12 Performance characteristics . 17 13 Test report . 17 Annex A (informative)
Example of a data sheet . 19 Annex B (informative)
Operation and uses of the test — Influence of pH on the leaching behaviour . 20 B.1 Clarification of the two modes of operation of the test: influence of pH on the leaching behaviour . 20 B.2 Expression of results . 22 B.3 Scope and limits of the application field of the test . 22 B.3.1 Remarks on the use of pH dependence test results to assess the effects of ageing . 22 B.3.2 Examples of test result use and considerations on scope . 23 B.4 Example: Identification of the sensitivity of leaching to pH over the environmentally relevant pH range. 24 Annex C (informative)
Preliminary determination of the acid/base consumption . 25 C.1 General . 25 C.2 Titration procedure to estimate the ANC and the BNC . 25 SIST EN 14997:2015
EN 14997:2015 (E) 3 C.2.1 Reagents and laboratory devices . 25 C.2.2 Test portion . 25 C.2.3 Procedure . 25 C.2.4 Expression of results . 26 C.3 Arbitrary division of the maximum acid/base consumption for the extreme pH values . 27 C.3.1 General . 27 C.3.2 Reagents and laboratory devices . 27 C.3.3 Test portion . 27 C.3.4 Procedure . 27 C.3.5 Expression of results . 28 Annex D (informative)
Examples of acid and base neutralization capacities for waste, soil, sediment and construction materials . 29 D.1 Examples of acid and base neutralization capacities . 29 D.2 Use of acid and base neutralization capacity data . 31 Annex E (informative)
Repeatability and reproducibility data . 32 E.1 Materials used in the interlaboratory comparison study . 32 E.2 Interlaboratory comparison results . 32 Bibliography . 50
SIST EN 14997:2015
EN 14997:2015 (E) 4 Foreword This document (EN 14997:2015) has been prepared by Technical Committee CEN/TC 292 “Characterization of waste”, the secretariat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by September 2015, and conflicting national standards shall be withdrawn at the latest by September 2015. 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. This document supersedes CEN/TS 14997:2006. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. The following significant technical changes have been implemented in this new edition of the text: —
the status of the document has been changed from a CEN/TS into an European Standard; —
performance data has been added (see Annex E). According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. SIST EN 14997:2015
EN 14997:2015 (E) 5 Introduction This document has been developed primarily to support the requirements for leaching behaviour testing within EU and EFTA countries. This document specifies a test method for the determination of the influence of pH on the leachability of inorganic constituents from waste materials. For the complete characterization of the leaching behaviour of waste under specified conditions the application of other test methods is required (see EN 12920). Anyone dealing with waste and sludge analysis should be aware of the typical risks of that kind of material irrespective of the parameter to be determined. Waste and sludge samples can contain hazardous (e.g. toxic, reactive, flammable, infectious) substances, which can be liable to biological and/or chemical reaction. Consequently these samples should be handled with special care. Gases which can be produced by microbiological or chemical activity are potentially flammable and will pressurize sealed bottles. Bursting bottles are likely to result in hazardous shrapnel, dust and/or aerosol. National regulations will be followed with respect to all hazards associated with this method. In the different European countries, tests have been developed to characterize and assess the constituents which can be leached from waste materials. The release of soluble constituents upon contact with water is regarded as one of the main mechanism of release which results in a potential risk to the environment during life-cycle of waste materials (disposal or re-use scenario). The intent of these tests is to identify the leaching properties of waste materials. The complexity of the leaching process makes simplifications necessary. Not all of the relevant aspects of leaching behaviour can be addressed in one single standard. Procedures to characterize the behaviour of waste materials can generally be divided into three steps, using different tests in relation to the objective. The following test hierarchy is taken from the Landfill Directive 1) and the Decision on Annex II of this Directive 2) for disposal of waste. a) Basic characterization constitutes a full characterization of the waste by gathering all the necessary information for a safe management of the waste in the short and long term. Basic characterization may provide information on the waste (type and origin, composition, consistency, leachability, etc.), information for understanding the behaviour of waste in the considered management scenario, comparison of waste properties against limit values, and detection of key variables (critical parameters as liquid/solid (L/S) ratios, leachant composition, factors controlling leachability such as pH, redox potential, complexing capacity and physical parameters) for compliance testing and options for simplification of compliance testing. Characterization may deliver ratios between test results from basic characterization and results from simplified test procedures as well as information on a suitable frequency for compliance testing. In addition to the leaching behaviour, the composition of the waste should be known or determined by testing. The tests used for basic characterization should always include those to be used for compliance testing. b) Compliance testing is used to demonstrate that the sample of today fits the population of samples tested before by basic characterization and through that, is used to carry out compliance with regulatory limit values. The compliance test should therefore always be part of the basic characterization program. The compliance test focuses on key variables and leaching behaviour identified by basic characterization tests. Parts of basic characterization tests can also be used for compliance purposes.
1) Council Directive 1999/31/EC of 26 April 1999 on the landfill of waste. 2) Council Decision 2003/33/EC of 19 December 2002. SIST EN 14997:2015
EN 14997:2015 (E) 6 c) On-site verification tests are used as a rapid check to confirm that the waste is the same as that which has been subjected to characterization or compliance tests. On-site verification tests are not necessarily leaching tests. The test procedure described in this document is a basic characterization test and falls in category a). According to EN 12920 the evaluation of the release of constituents from waste materials in a certain scenario involves the performance of various tests. The test described in this European Standard is carried out by continuous automated adjustment of pH. Size reduction is performed to facilitate approaching of equilibrium. This test is different from the "Influence of pH on leaching with initial acid/base addition" (see EN 14429) in which the pH is controlled by addition of pre-determined amounts of acid or base to reach desired end pH values. The test is aiming at approaching equilibrium at the end of the procedure. NOTE In Annex B specific uses of both the pH dependence test with initial acid/ base addition and the pH dependence test with continuous pH control are indicated. SIST EN 14997:2015
EN 14997:2015 (E) 7 1 Scope This European Standard specifies a method for the determination of the influence of pH on the leachability of inorganic constituents from a waste material. Approaching equilibrium as defined in this European Standard is established by continuous adjustment of the pH by addition of acid or base to reach desired pH values. This test method produces eluates, which are subsequently characterized physically and chemically. This European Standard is a parameter specific test as specified in EN 12920. The application of this test method alone is not sufficient for the determination of the detailed leaching behaviour of a waste under specified conditions. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 14346:2006, Characterization of waste — Calculation of dry matter by determination of dry residue or water content EN 14899, Characterization of waste — Sampling of waste materials — Framework for the preparation and application of a Sampling Plan EN 15002, Characterization of waste — Preparation of test portions from the laboratory sample EN 16192, Characterization of waste — Analysis of eluates EN ISO 3696, Water for analytical laboratory use — Specification and test methods (ISO 3696) EN ISO 5667-3, Water quality — Sampling — Part 3: Preservation and handling of water samples (ISO 5667-3) 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 dry residue wdr remaining mass fraction of a sample after a drying process at 105 °C [SOURCE: EN 14346:2006] 3.2 eluate solution obtained by a leaching test 3.3 equilibrium condition achieved when the acid or base consumption during a checking period at the last 4 h of the test is less than 2 % of the total acid or base consumption during the entire test SIST EN 14997:2015
EN 14997:2015 (E) 8 3.4 laboratory sample sample or subsample(s) sent to or received by the laboratory [SOURCE: IUPAC, 1990] Note 1 to entry: When the laboratory sample is further prepared (reduced) by subdividing, cutting, crushing, sawing, coring, or by combinations of these operations, the result is the test sample. When no preparation of the laboratory sample is required, the laboratory sample is the test sample. A test portion is removed from the test sample for the performance of the test or for analysis. The laboratory sample is the final sample from the point of view of sampling but it is the initial sample from the point of view of the laboratory. Note 2 to entry: Several laboratory samples may be prepared and sent to different laboratories or to the same laboratory for different purposes. When sent to the same laboratory, the set is generally considered as a single laboratory sample and is documented as a single sample. 3.5 leachant liquid that is brought into contact with the test portion in the leaching procedure 3.6 liquid to solid-ratio L/S ratio between the amount of liquid (L) and of solid (S) in the test Note 1 to entry: L/S is expressed in l/kg dry matter. 3.7 suspension mixture of leachant and test portion 3.8 test portion amount or volume of the test sample taken for analysis, usually of known weight or volume [SOURCE: IUPAC, 1990] 3.9 test sample sample, prepared from the laboratory sample, from which test portions are removed for testing or for analysis [SOURCE: IUPAC, 1990] 4 Symbols and abbreviations For the purposes of this document, the following symbols and abbreviations apply. ANC acid neutralization capacity BNC base neutralization capacity DM dry matter DOC dissolved organic carbon L/S liquid to solid-ratio Md dried mass of the test portion md mass after drying SIST EN 14997:2015
EN 14997:2015 (E) 9 Mw un-dried mass of the test portion mr mass before drying t0 time at the start of the leaching test VA/B volume of acid or base used in leachant Vdemin volume of demineralized water used in leachant VL volume of added leachant wdr dry residue of the sample 5 Principle This European Standard describes a method to determine the influence of pH on the leachability of inorganic constituents from a waste material. Separate test portions are leached at a fixed L/S ratio with leachants where the pH is adjusted and controlled at pre-set pH values (pH static titration procedure). At least 8 final pH values are required, covering at the minimum the range pH 2 - pH 12 (both included i.e. the lowest value ≤ 2 and the highest value ≥ 12). The amounts of acid or base needed to cover the pH range can be derived from the results of a preliminary titration, from available experimental data on the material to be tested or from an arbitrary division of the predetermined maximum consumption of acid and base. The tests are carried out at a fixed contact time at the end of which equilibrium can be assumed to be approached for most constituents in most waste materials to be characterized. The approaching of equilibrium as defined in the standard is verified at the end of the leaching procedure. The results are expressed in mg/l of constituents for each final pH value. For each final pH value also the quantity of acid that is added is expressed in mol H+/kg dry matter and the quantity of base that is added is expressed as mol OH-/kg DM (for graphical presentation mol OH-/kg DM is expressed as - mol H+/kg DM). NOTE Other expression of results is possible (including mg leached /kg dry matter). Since this test is aiming at approaching equilibrium i.e. solubility controlled, the results alone cannot be used to quantify the soluble mass fraction. The ANC or BNC of the waste is also determined. The ANC or BNC is defined as the amount of acid or base (+/- mol H+/kg dry matter) needed to reach a given user-defined end-pH. It is graphically [6] or numerically derived from a curve representing each end-pH obtained as a function of the amounts of acid or base added. The pH range covered by the test may be restricted to a pH range relevant for the specific material and the considered problem (see 9.2). 6 Reagents Use only reagents of recognized analytical grade, unless otherwise specified. 6.1 Distilled water, demineralized water, de-ionized water or water of equivalent purity (5 < pH < 7,5) with a conductivity < 0,1 mS/m according to grade 2 specified in EN ISO 3696. 6.2 Nitric acid, c(HNO3) = 0,1 mol/l to 5 mol/l. 6.3 Sodium hydroxide, c(NaOH) = 0,1 mol/l to 5 mol/l. Sodium hydroxide is unstable due to possible uptake of CO2. Therefore it is recommended to prepare a fresh solution. SIST EN 14997:2015
EN 14997:2015 (E) 10 7 Equipment 7.1 General Check the materials and equipment specified in 7.2.3, 7.2.4, 7.2.7, 7.2.8 and 7.2.10 before use for proper operation and absence of interfering elements that may affect the result of the test. Calibrate the equipment specified in 7.2.1, 7.2.6, 7.2.11 and 7.2.12. 7.2 Laboratory equipment Usual laboratory apparatus, and in particular the following: 7.2.1 Analytical balance, with an accuracy of at least 0,1 g. 7.2.2 Bottles or vessels equipped with a lid. Use bottles or vessels (250 ml for the test portions of 15 g of dry mass, 500 ml for test portions of 30 g dry mass and 1 l for test portions of 60 g dry mass) made of polypropylene (PP), polyethylene (PE) or PTFE. In the bottles or the lid of the vessels an opening shall be present for the pH electrodes and for input of acid and/or base and a small outlet for gas. The bottles shall be as close as possible to prevent CO2 uptake. At high pH values it is recommended to perform the test under nitrogen to prevent CO2 intake. 7.2.3 Crushing equipment, e.g. a jaw crusher. NOTE Crushing is prescribed to avoid unnecessary grinding to very fine particle sizes, such as takes place in a rotary swing mill, ball mill or similar device. 7.2.4 Stirring device The parts in contact with sample and eluate shall be made of materials not affecting the outcome of the test like glass, PTFE. 7.2.5 Membrane filters, with a pore size of 0,45 µm. Membrane filters for the filtration device, fabricated from inert material, which is compatible with the waste. Filter shall be pre-rinsed with demineralized water or similarly clean in order to remove DOC. 7.2.6 pH meter, with an accuracy of at least ± 0,05 pH units. 7.2.7 Sample splitters, for sub-sampling of laboratory samples of a minimum test portion size equivalent of 15 g of dry mass. 7.2.8 Sieving equipment, with sieve of 1 mm nominal screen sizes. Due to crushing and sieving, contamination of the sample may occur to an extent, which may affect the leached amounts of some constituents of concern, e.g. Co and W from tungsten carbide crushing equipment or Cr, Ni, Mo and V from stainless steel equipment. 7.2.9 Device for continuous pH control, with a precision of 0,2 pH units through acid/base addition. NOTE The pH control is achieved by continuously measuring the pH of the suspension and in case of a deviation from the desired pH a continuously dosing of acid or base is required to maintain the desired pH. SIST EN 14997:2015
EN 14997:2015 (E) 11 7.2.10 Vacuum filtration device or pressure filtration device. 7.2.11 Conductivity meter, with an accuracy of at least 0,1 mS/m. 7.2.12 Redox potential meter (optional). 8 Sample preparation 8.1 Laboratory sample The laboratory sample shall consist of a mass equivalent of at least 1 kg of dry mass. In case less material is available, a justification shall be provided in the test report. Perform sampling in accordance with EN 14899 or a standard derived from EN 14899 in order to obtain a representative laboratory sample. 8.2 Preparation of the test sample The tests shall be made on material with a grain size of 95 % less than 1 mm. In order to ensure that the test sample consists in 95 % mass of particles less than 1 mm in diameter, it shall be sieved, using the sieving equipment, to separate the oversized particles. If oversized material exceeds 5 % (mass) the entire oversized fraction shall be crushed. Any non-crushable material (e.g. metallic parts such as nuts, bolts, scrap) shall be separated from the oversized fraction and the weight and nature of the non-crushable material shall be recorded. Crushed and uncrushed material shall be mixed to constitute the test sample. Moist material that is not possible to sieve needs to be dried prior to sieving and/or crushing. The drying temperature shall not exceed 40 °C. Perform size reduction, drying, if needed, and sub-sampling according to specifications provided in EN 15002. The crushed material can change upon storage due to ageing of fresh surfaces. It is therefore recommended to test the material as soon as possible after crushing. It is recommended that materials with a high natural pH should be crushed under nitrogen in order to avoid contact with air leading to carbonation. 8.3 Determination of dry residue The whole test sample, complying with the size criteria in 8.2 shall not be further dried. The dry residue (wdr) of the test sample shall be determined on a separate test portion. The dry residue of the sample shall be determined at 105 oC ± 3 oC according to EN 14346. The dry residue expressed as a percentage of the mass fraction is calculated as follows: 100ddrrmwm×= (1) where wdr is the dry residue of the sample, expressed as percentage (%); md is the mass after drying , in grams (g); mr is the mass before drying, in grams (g). SIST EN 14997:2015
EN 14997:2015 (E) 12 8.4 Preparation of the test portion Prepare at least 8 test portions by the use of a sample splitter or
...
SLOVENSKI STANDARD
oSIST prEN 14997:2013
01-oktober-2013
Karakterizacija odpadkov - Izluževalni preskus - Vpliv pH na izluževanje z
uravnavanjem pH
Characterisation of waste - Leaching behaviour test - Influence of pH on leaching with
continuous pH control
Charakterisierung von Abfällen - Untersuchung des Auslaugungsverhaltens - Einfluss
des pH-Wertes auf die Auslaugung bei kontinuierlicher pH-Wert-Kontrolle
Caractérisation des déchets - Essais de comportement à la lixiviation - Influence du pH
sur la lixiviation avec contrôle continu du pH
Ta slovenski standard je istoveten z: prEN 14997
ICS:
13.030.01 Odpadki na splošno Wastes in general
oSIST prEN 14997:2013 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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oSIST prEN 14997:2013
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oSIST prEN 14997:2013
EUROPEAN STANDARD
DRAFT
prEN 14997
NORME EUROPÉENNE
EUROPÄISCHE NORM
September 2013
ICS 13.030.01 Will supersede CEN/TS 14997:2006
English Version
Characterisation of waste - Leaching behaviour test - Influence
of pH on leaching with continuous pH control
Caractérisation des déchets - Essais de comportement à la Charakterisierung von Abfällen - Untersuchung des
lixiviation - Influence du pH sur la lixiviation avec contrôle Auslaugungsverhaltens - Einfluss des pH-Wertes auf die
continu du pH Auslaugung bei kontinuierlicher pH-Wert-Kontrolle
This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee CEN/TC 292.
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, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, 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
Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2013 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 14997:2013: E
worldwide for CEN national Members.
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oSIST prEN 14997:2013
prEN 14997:2013 (E)
Contents Page
Foreword .4
Introduction .5
1 Scope .6
2 Normative references .6
3 Terms and definitions .6
4 Symbols and abbreviations .7
5 Principle .8
6 Reagents .8
7 Equipment .9
7.1 General .9
7.2 Laboratory equipment .9
8 Sample preparation . 10
8.1 Laboratory sample . 10
8.2 Preparation of test sample . 10
8.3 Determination of dry residue . 10
8.4 Preparation of the test portion . 11
9 Procedure . 11
9.1 Contact time . 11
9.2 pH range . 11
9.3 Leaching test . 11
9.3.1 General . 11
9.3.2 Preparation of leachant . 12
9.3.3 Leaching procedure . 13
9.4 Natural pH . 15
10 Eluate treatment, storage and analysis . 15
11 Blank test . 15
12 Performance characteristics . 16
13 Test report . 16
Annex A (informative) Example of a data sheet . 18
Annex B (informative) Operation and uses of the test — Influence of pH on the leaching
behaviour . 19
B.1 Clarification of the two modes of operation of the test: influence of pH on the leaching
behaviour . 19
B.2 Expression of results . 21
B.3 Scope and limits of the application field of the test . 21
B.4 Example: Identification of the sensitivity of leaching to pH over the environmentally
relevant pH range. 22
Annex C (informative) Preliminary determination of the acid/base consumption . 24
C.1 General . 24
C.2 Titration procedure to estimate the ANC and the BNC . 24
C.2.1 Reagents and laboratory devices . 24
C.2.2 Test portion . 24
C.2.3 Procedure . 24
2
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prEN 14997:2013 (E)
C.2.4 Expression of results . 26
C.3 Arbitrary division of the maximum acid/base consumption for the extreme pH values . 26
C.3.1 General . 26
C.3.2 Reagents and laboratory devices . 26
C.3.3 Test portion . 26
C.3.4 Procedure . 26
C.3.5 Expression of results . 27
Annex D (informative) Examples of acid and base neutralisation capacities for waste, soil,
sediment and construction materials . 28
D.1 Examples of acid and base neutralisation capacities . 28
D.2 Use of acid and base neutralisation capacity data . 30
Annex E (informative) Repeatability and reproducibility data . 31
E.1 Materials used in the interlaboratory comparison study . 31
E.2 Interlaboratory comparison results . 31
Bibliography . 42
3
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oSIST prEN 14997:2013
prEN 14997:2013 (E)
Foreword
This document (prEN 14997:2013) 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 CEN Enquiry.
This document will supersede CEN/TS 14997:2006.
This document has been prepared under a mandate given to CEN by the European Commission and the
European Free Trade Association.
This document has been developed primarily to support the requirements for leaching behaviour testing within
EU and EFTA countries.
This document specifies a test method for the determination of the influence of pH on the leachability of
inorganic constituents from waste materials.
For the complete characterization of the leaching behaviour of waste under specified conditions the
application of other test methods is required, (see EN 12920).
Anyone dealing with waste and sludge analysis should be aware of the typical risks of that kind of material
irrespective of the parameter to be determined. Waste and sludge samples can contain hazardous (e.g. toxic,
reactive, flammable, infectious) substances, which can be liable to biological and/or chemical reaction.
Consequently these samples should be handled with special care. Gases which can be produced by
microbiological or chemical activity are potentially flammable and will pressurise sealed bottles. Bursting
bottles are likely to result in hazardous shrapnel, dust and/or aerosol. National regulations should be followed
with respect to all hazards associated with this method.
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Introduction
In the different European countries, tests have been developed to characterize and assess the constituents
which can be leached from waste materials. The release of soluble constituents upon contact with water is
regarded as one of the main mechanism of release which results in a potential risk to the environment during
life-cycle of waste materials (disposal or re-use scenario). The intent of these tests is to identify the leaching
properties of waste materials. The complexity of the leaching process makes simplifications necessary. Not all
of the relevant aspects of leaching behaviour can be addressed in one single standard.
Procedures to characterize the behaviour of waste materials can generally be divided into three steps, using
1)
different tests in relation to the objective. The following test hierarchy is taken from the Landfill Directive and
2)
the Decision on Annex II of this Directive for disposal of waste.
a) Basic characterization constitutes a full characterization of the waste by gathering all the necessary
information for a safe management of the waste in the short and long term. Basic characterization may
provide information on the waste (type and origin, composition, consistency, leachability, etc.),
information for understanding the behaviour of waste in the considered management scenario,
comparison of waste properties against limit values, and detection of key variables (critical parameters as
liquid/solid (L/S) ratios, leachant composition, factors controlling leachability such as pH, redox potential,
complexing capacity and physical parameters) for compliance testing and options for simplification of
compliance testing. Characterization may deliver ratios between test results from basic characterization
and results from simplified test procedures as well as information on a suitable frequency for compliance
testing. In addition to the leaching behaviour, the composition of the waste should be known or
determined by testing. The tests used for basic characterization should always include those to be used
for compliance testing.
b) Compliance testing is used to demonstrate that the sample of today fits the population of samples tested
before by basic characterization and through that, is used to carry out compliance with regulatory limit
values. The compliance test should therefore always be part of the basic characterization program. The
compliance test focuses on key variables and leaching behaviour identified by basic characterization
tests. Parts of basic characterization tests can also be used for compliance purposes.
c) On-site verification tests are used as a rapid check to confirm that the waste is the same as that which
has been subjected to characterization or compliance tests. On-site verification tests are not necessarily
leaching tests.
The test procedure described in this document is a basic characterization test and falls in category a).
According to EN 12920 the evaluation of the release of constituents from waste materials in a certain scenario
involves the performance of various tests. The test described in this European Standard is carried out by
continuous automated adjustment of pH. Size reduction is performed to facilitate approaching of equilibrium.
This test is different from the "Influence of pH on leaching with initial acid/base addition" (see EN 14429) in
which the pH is controlled by addition of pre-determined amounts of acid or base to reach desired end pH
values. The test is aiming at approaching equilibrium at the end of the procedure.
NOTE In Annex B specific uses of both the pH dependence test with initial acid/ base addition and the pH
dependence test with continuous pH control are indicated.
1) Council Directive 1999/31/EC of 26 April 1999 on the landfill of waste.
2) Council Decision 2003/33/EC of 19 December 2002.
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1 Scope
This European Standard is applicable for determining the influence of pH on the leachability of inorganic
constituents from a waste material. Approaching equilibrium as defined in this document is established by
continuous adjustment of the pH by addition of acid or base to reach desired pH values. This test method
produces eluates, which are subsequently characterized physically and chemically.
This document is a parameter specific test as specified in EN 12920. The application of this test method alone
is not sufficient for the determination of the detailed leaching behaviour of a waste under specified conditions.
NOTE This generally requires the application of several test methods, behavioural modelling and model validation as
specified in EN 12920.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated references,
the latest edition of the referenced document (including any amendments) applies.
EN 14346, Characterization of waste – Calculation of dry matter by determination of dry residue or water
content
EN 14899, Characterisation of waste – Sampling of waste materials – Framework for the preparation and
application of a sampling plan
EN 15002, Characterization of waste – Preparation of test portions from the laboratory sample
EN 16192, Characterisation of waste – Analysis of eluates
EN ISO 3696, Water for analytical laboratory use – Specification and test methods
EN ISO 5667-3, Water quality – Sampling – Part 3: Preservation and handling of water samples
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
dry residue
w
dr
o
remaining mass fraction of a sample after a drying process at 105 C
[SOURCE: EN 14346:2007]
3.2
eluate
solution obtained by a laboratory leaching test
[SOURCE: EN 12457-1:2002]
3.3
equilibrium
condition achieved when the acid or base consumption during a checking period at the last 4 h of the test is
less than 2 % of the total acid or base consumption during the entire test
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3.4
laboratory sample
sample or subsample(s) sent to or received by the laboratory
[SOURCE: IUPAC, 1997]
Note 1 to entry: When the laboratory sample is further prepared (reduced) by subdividing, cutting, sawing, coring, or
by combinations of these operations, the result is the test sample. When no preparation of the laboratory sample is
required, the laboratory sample is the test sample. A test portion is removed from the test sample for the performance of
the test or for analysis. The laboratory sample is the final sample from the point of view of sampling but it is the initial
sample from the point of view of the laboratory.
Note 2 to entry: Several laboratory samples may be prepared and sent to different laboratories or to the same
laboratory for different purposes. When sent to the same laboratory, the set is generally considered as a single laboratory
sample and is documented as a single sample.
3.5
leachant
liquid to be mixed with the test portion in the leaching procedure
3.6
liquid to solid-ratio
L/S
ratio between the amount of liquid (L) and of solid (S) in the test
Note 1 to entry: L/S is expressed in l/kg dry matter.
3.7
suspension
mixture of leachant and test portion
3.8
test portion
amount or volume of the test sample taken for analysis, usually of known weight or volume
[SOURCE: IUPAC, 1997]
3.9
test sample
sample, prepared from the laboratory sample, from which test portions are removed for testing or for analysis
[SOURCE: IUPAC, 1997]
4 Symbols and abbreviations
For the purposes of this document, the following symbols and abbreviations apply.
ANC acid neutralization capacity
BNC base neutralization capacity
DM dry matter
DOC dissolved organic carbon
L/S liquid to solid-ratio
M dried mass of the test portion
d
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m mass after drying
d
M un-dried mass of the test portion
w
m mass before drying
r
t time at the start of the leaching test
0
V volume of acid or base used in leachant
A/B
V volume of demineralised water used in leachant
demin
w dry residue of the sample
dr
5 Principle
This European Standard describes a method to determine the influence of pH on the leachability of inorganic
constituents from a waste material.
Separate test portions are leached at a fixed L/S ratio with leachants where the pH is adjusted and controlled
at pre-set pH-values. At least 8 final pH values are required, covering at the minimum the range pH 4 - pH 12
(both included i.e. the lowest value ≤ 4 and the highest value ≥ 12). The amounts of acid or base needed to
cover the pH range can be derived from the results of a preliminary titration, from available experimental data
on the material to be tested or from an arbitrary division of the predetermined maximum consumption of acid
and base. The tests are carried out at a fixed contact time at the end of which equilibrium can be assumed to
be approached for most constituents in most waste materials to be characterized. The approaching of
equilibrium as defined in the standard is verified at the end of the leaching procedure.
The results are expressed in mg/l of constituents for each final pH value. For each final pH value also the
+
quantity of acid that is added is expressed in mol H /kg dry matter and the quantity of base that is added is
- +
expressed as mol OH /kg dry matter (-mol H /kg dry matter).
NOTE 1 Other expression of results is possible (including mg leached /kg dry matter). Since this test is aiming at
approaching equilibrium i.e. solubility controlled, the results alone cannot be used to quantify the soluble mass fraction.
The ANC or BNC of the waste is also determined. The ANC or BNC is defined as the amount of acid or base
+
/kg dry matter) needed to reach a given user-defined end-pH. It is graphically [2] or numerically
(+/- mol H
derived from a curve representing each end-pH obtained as a function of the amounts of acid or base added.
NOTE 2 The pH range covered by the test may be restricted to a pH range relevant for the specific material and the
considered problem (see 9.2).
6 Reagents
Use only reagents of recognized analytical grade, unless otherwise specified.
6.1 Distilled water, demineralised water, de-ionised water or water of equivalent purity (5 < pH < 7,5) with
a conductivity < 0,1 mS/m according to grade 2 specified in EN ISO 3696
6.2 Nitric acid, c(HNO ) = 0,1 mol/l to 5 mol/l
3
6.3 Sodium hydroxide, c(NaOH) = 0,1 mol/l to 5 mol/l
NOTE Sodium hydroxide is unstable due to possible uptake of CO . Therefore it is recommended to prepare a fresh
2
solution.
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7 Equipment
7.1 General
Check the materials and equipment specified in 7.2.3, 7.2.4, 7.2.7, 7.2.8 and 7.2.10 before use for proper
operation and absence of interfering elements that may affect the result of the test.
Calibrate the equipment specified in 7.2.1, 7.2.6, 7.2.11 and 7.2.12.
7.2 Laboratory equipment
Usual laboratory apparatus, and in particular the following:
7.2.1 Analytical balance, with an accuracy of at least 0,1 g
7.2.2 Bottles or vessels equipped with a lid
Use bottles or vessels (250 ml for the test portions of 15 g of dry mass, 500 ml for test portions of 30 g dry
mass and 1 l for test portions of 60 g dry mass) made of polypropylene (PP), polyethylene (PE) or PTFE. In
the bottles or the lid of the vessels an opening must be present for the pH-electrodes and for input of acid
and/or base and a small outlet for gas. The bottles have to be as close as possible to prevent CO uptake.
2
NOTE At high pH values it is recommended to perform the test under nitrogen to prevent CO intake.
2
7.2.3 Crushing equipment, e.g. a jaw crusher
NOTE Crushing is prescribed to avoid unnecessary grinding to very fine particle sizes, such as takes place in a rotary
swing mill, ball mill or similar device.
7.2.4 Stirring device
The parts in contact with sample and eluate shall be made of materials not affecting the outcome of the test
like glass, PTFE.
7.2.5 Membrane filters, with a pore size of 0,45 µm
Membrane filters for the filtration device, fabricated from inert material, which is compatible with the waste.
Filter shall be pre-rinsed with demineralised water or similarly clean in order to remove DOC.
7.2.6 pH meter, with an accuracy of at least ± 0,05 pH units
7.2.7 Sample splitters, for sub-sampling of laboratory samples of a minimum test portion size equivalent of
15 g of dry mass
7.2.8 Sieving equipment, with sieve of 1 mm nominal screen sizes
NOTE Due to crushing and sieving, contamination of the sample may occur to an extent, which may affect the
leached amounts of some constituents of concern, e.g. Co and W from tungsten carbide crushing equipment or Cr, Ni, Mo
and V from stainless steel equipment.
7.2.9 Device for continuous pH control, with a precision of 0,2 pH units through acid/base addition
NOTE The pH-control of the suspension is achieved by continuous addition of acid/base by measuring the pH of the
solution in case of a deviation from the desired pH a continuous dosing of acid or base is required.
7.2.10 Vacuum filtration device or pressure filtration device
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7.2.11 Conductivity meter, with an accuracy of at least 0,1 mS/m
7.2.12 Redox potential meter (optional).
8 Sample preparation
8.1 Laboratory sample
The laboratory sample shall consist of a mass equivalent of at least 1 kg of dry mass. In case less material is
available, a justification shall be provided in the test report.
Perform sampling in accordance with EN 14899 or a standard derived from EN 14899 in order to obtain a
representative laboratory sample.
8.2 Preparation of test sample
The tests shall be made on material with a grain size of 95 % less than 1 mm. In order to ensure that the test
sample consists in 95 % mass of particles less than 1 mm in diameter, it shall be sieved, using the sieving
equipment, to separate the oversized particles. If oversized material exceeds 5 % (mass) the entire oversized
fraction shall be crushed. Any non-crushable material (e.g. metallic parts such as nuts, bolts, scrap) shall be
separated from the oversized fraction and the weight and nature of the non-crushable material shall be
recorded. Crushed and uncrushed material shall be mixed to constitute the test sample.
Moist material that is not possible to sieve needs to be dried prior to sieving and/or crushing. The drying
o
temperature shall not exceed 40 C.
Perform size reduction, drying, if needed, and sub-sampling according to specifications provided in EN 15002.
NOTE 1 The crushed material can change upon storage due to ageing of fresh surfaces. It is therefore recommended
to test the material as soon as possible after crushing.
NOTE 2 It is recommended that materials with a high natural pH should be crushed under nitrogen in order to avoid
contact with air leading to carbonation.
8.3 Determination of dry residue
The whole test sample, complying with the size criteria in 7.2 shall not be further dried. The dry residue (w )
dr
of the test sample shall be determined on a separate test portion.
o o
The dry residue of the sample shall be determined at 105 C ± 5 C according to EN 14346. The dry residue
expressed as a percentage of the mass fraction is calculated as follows:
m ×100
d
(1)
w =
dr
m
r
where
w is the dry residue of the sample, expressed as percentage (%);
dr
m is the mass after drying , in grams (g);
d
m is the mass before drying, in grams (g).
r
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