1、BRITISH STANDARD BS EN 14345:2004 Characterization of waste Determination of hydrocarbon content by gravimetry The European Standard EN 14345:2004 has the status of a British Standard ICS 13.030.01 BS EN 14345:2004 This British Standard was published under the authority of the Standards Policy and S
2、trategy Committee on 1 November 2004 BSI 1 November 2004 ISBN 0 580 44701 4 National foreword This British Standard is the official English language version of EN 14345:2004. The UK participation in its preparation was entrusted by Technical Committee B/508, Waste management, to Subcommittee B/508/3
3、, Waste characterisation, which has the responsibility to: A list of organizations represented on this subcommittee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in
4、the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisions of a contract. Users are responsibl
5、e for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep the UK
6、 interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 16, an inside back cover and a back cover. The BSI copyright notice displayed in th
7、is document indicates when the document was last issued. Amendments issued since publication Amd. No. Date CommentsEUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM EN14345 September2004 ICS13.030.01 Englishversion CharacterizationofwasteDeterminationofhydrocarbon contentbygravimetry Caractrisationdesd
8、chetsDterminationdelateneur enhydrocarburespargravimtrie CharakterisierungvonAbfllenBestimmungdes KohlenwasserstoffgehaltsmittelsGravimetrie ThisEuropeanStandardwasapprovedbyCENon9July2004. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEurope
9、an Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandbibliographicalreferencesconcernings uchnational standardsmaybeobtainedonapplicationtotheCentralSecretariatortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguage
10、madebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheCentralSecretariathasthesamestatusast heofficial versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,Cyprus,CzechRepublic,Denmark,Estonia,Finland,France, Germany,Greece,Hungary,Iceland,Ireland,Italy
11、,Latvia,Lithuania,Luxembourg,Malta,Netherlands,Norway,Poland,Portugal, Slovakia, Slovenia,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2004CEN Allrightsofexploitati
12、oninanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.EN14345:2004:EEN 14345:2004 (E) 2 Contents page Foreword 3 Introduction4 1 Scope.5 2 Normative references.5 3 Terms and definitions.5 4 Principle.5 5 Hazards5 6 Interferences.6 7 Reagents6 8 Equipment.6 9 Sample conservation and
13、 pre-treatment.7 10 Procedure7 10.1 Blank7 10.2 Dry matter7 10.3 Extraction7 10.4 Clean-up.7 10.5 Gravimetric determination of the hydrocarbon content 8 10.6 Calculation and evaluation.8 10.7 Quality control.8 10.7.1 Suitability check of the clean-up procedure .8 10.7.2 Recovery of the hydrocarbon s
14、tandard solution8 11 Performance characteristics9 12 Test report.9 Annex A (informative) Inclusion of semi-volatile hydrocarbons .10 Annex B (informative) Aqueous liquid waste13 Annex C (informative) Flow diagram14 Annex D (informative) Summary of general requirements and recommendations 15 Bibliogr
15、aphy.16 EN 14345:2004 (E) 3 Foreword This document (EN 14345:2004) 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
16、text or by endorsement, at the latest by March 2005, and conflicting national standards shall be withdrawn at the latest by March 2005. 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 an
17、d sludge samples may 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 may be produced by microbiological or chemical activity are potenti
18、ally 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. According to the CEN/CENELEC Internal Regulations, the national standa
19、rds organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slo
20、vakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EN 14345:2004 (E) 4 Introduction Hydrocarbons have been determined up to now mainly by infrared spectroscopy after extraction with halogenated solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane or tetrachloromethane. The objective o
21、f the new standard is to provide an analytical method for the determination of hydrocarbon content by gravimetry avoiding the use of such solvents. The user of this standard should be aware that the results obtained with the new method might not be comparable with those obtained when using infrared
22、spectroscopy. This document is restricted to waste samples containing large amounts of relatively high boiling hydrocarbons (boiling point above 250 C) and may be used as a test that is easy to perform. EN 14345:2004 (E) 5 1 Scope This document specifies a gravimetric method for the determination of
23、 the hydrocarbon content in solid waste. It is applicable to hydrocarbon content greater than 0,5 % (m/m) on dry matter basis. This method does not permit to provide qualitative information on the nature and the source of the hydrocarbons. NOTE Aqueous liquid waste samples can be analysed in accorda
24、nce with prEN ISO 9377-1 or the procedure specified in Annex B. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced documen
25、t (including any amendments) applies. prEN 14346, Characterization of waste Calculation of dry matter by determination of dry residue and water content EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696:1987) 3 Terms and definitions For the purposes of this d
26、ocument, the following term and definition applies. 3.1 hydrocarbon content by gravimetry sum of compounds extractable with acetone/petroleum ether (2+1) which do not adsorb on Florisil and do not evaporate during the drying process. For practical reasons, the term “hydrocarbon content by gravimetry
27、“ is abbreviated “hydrocarbon content“ in the following text NOTE 1 Substances that comply with this definition are mainly non-polar long-chain or branched aliphatic, alicyclic, polycyclic or alkyl substituted aromatic hydrocarbons. NOTE 2 This definition differs from that given in EN 14039. 4 Princ
28、iple Depending on the type of waste, a known amount of the homogenised waste sample is extracted by mechanical shaking twice with acetone/petroleum ether (2+1). The combined extracts are washed twice with water. Polar compounds are removed by chromatography on Florisil. The final extract is evaporat
29、ed to dryness after which the mass of the residue is determined by weighing. 5 Hazards Acetone and petroleum ether are highly flammable solvents and shall therefore be handled with caution. Special care is required during centrifugation. During extraction substantial pressure can built-up in the ext
30、raction vessel. This pressure shall be released by occasional venting of the vessel in a fume hood. Due to its toxicity, the contact with the skin and eyes and the inhalation of petroleum ether vapours shall be avoided. EN 14345:2004 (E) 6 6 Interferences High concentrations of more polar compounds,
31、 e.g. animal and vegetable fats and oils, may exceed the adsorption capacity of the Florisil used. A mass fraction of up to 1,0 % of such compounds will not interfere with the determination of hydrocarbon content. 7 Reagents 7.1 In general, all reagents shall be at least of reagent grade and suitabl
32、e for their specific purposes Use water complying with at least EN ISO 3696, grade 3 7.2 Acetone, (CH 3 ) 2 CO; 7.3 Petroleum ether, (boiling range 40 C to 60 C); NOTE Other hydrocarbon solvents, boiling range 36 C to 69 C can be used providing extraction efficiencies are proven to be comparable. 7.
33、4 Florisil 1 , particle size 150 m to 250 m (mesh 100 to 60), heated for at least 16 h at 140 C and stored in a desiccator over a molecular sieve. Alternatively, commercially available Forisil cartridges containing 2 g of Florisil and 2 g of sodium sulfate are also applicable. 7.5 Anhydrous sodium s
34、ulfate, Na 2 SO 4, heated for at least 2 h at 550 C; 7.6 Test solution of n-octadecanoic acid octadecyl ester, C 36 H 72 O 2 . Dissolve about 2 g of n-octadecanoic acid octadecyl ester in 100 ml petroleum ether 7.3. 7.7 Hydrocarbon standard solution for recovery check Dissolve about 2 g of an heavy
35、mineral oil such as a lubricating oil, without any additives, in 100 ml of petroleum ether 7.3. 7.8 A plug of pre-washed glass wool or a PTFE frit is pushed down into the column 8.10. Then, successively 2 g of Florisil 7.4 and 2 g of sodium sulfate 7.5 are added. The column shall be prepared immedia
36、tely before use. 8 Equipment 8.1 Standard laboratory glassware, which shall be heated or rinsed with acetone 7.2 and dried before use; 8.2 Mechanical shaker, e g. horizontal or rotary shaker; 8.3 Evaporation device, e.g. a rotary evaporator; 8.4 Analytical balance (Accuracy equal or better than 0,1
37、mg); 8.5 Glass extraction vessel of at least 100 ml, with ground glass stopper or screw caps incorporating a septum coated with polytetrafluoroethylene (PTFE); 1Florisil is the trade name of a prepared diatomaceous substance, mainly consisting of anhydrous magnesium silicate. This information is giv
38、en for the convenience of users of this European Standard and does not constitute an endorsement by CEN of this product. Equivalent products may be used if it can be shown to lead to comparable results. EN 14345:2004 (E) 7 8.6 Conical flask, 100ml or 250 ml, with ground glass stopper; 8.7 Separating
39、 funnel of at least 500 ml, with ground glass stopper; 8.8 Glass evaporation vessel, e.g. 100 ml or 250 ml round bottom flask; 8.9 Glass beaker, 25 ml; 8.10 Chromatography column for clean-up, glass columns of about 10 mm internal diameter. shall be used. The upper part of the column should be widen
40、ed to use as solvent reservoir and the lower part to be narrowed to form a tip. 9 Sample conservation and pre-treatment The samples shall be kept sealed in darkness at a temperature of about 4 C and extracted within a period of one week. If this is not possible, the samples shall be stored at -18 C
41、or lower. Before analysis, the samples shall be homogenised. 10 Procedure 10.1 Blank With each series of samples, a blank determination has to be carried out in accordance with 10.3., using all reagents in identical amounts but without a sample. If blank values exceed 0,1 % (20 mg for a typical mass
42、 of the test portion of 20 g), every step in the procedure shall be checked to find the reason for these high blanks. 10.2 Dry matter Determine the dry matter on a separate sub-sample (or each of the phases when phase separation has taken place) in accordance with prEN 14346. . When stable emulsions
43、 exist, the sample shall be analysed without phase separation. 10.3 Extraction Weigh to the nearest 0,1 g about 20 g of the homogenised sample into a glass extraction vessel 8.5, add 40 ml 1 ml of acetone 7.2. After short shaking by hand add 20 ml 0,1 ml of petroleum ether 7.3. Extract the sample fo
44、r 10 min to 15 min on a mechanical shaker 8.2. After settling of the solid material transfer as much as possible of the supernatant into a separating funnel 8.7. Repeat extraction with the same volumes of fresh solvent. Combine the extracts and remove the acetone by washing with 100 ml of water twic
45、e. Collect the organic layer in an conical flask 8.6. Add sufficient amount of sodium sulfate 7.5 so that no lumps are formed anymore. NOTE 1 Alternative extraction procedures, e.g. ultrasonic or accelerated solvent extraction (ASE) can be used provided they give comparable extraction performances.
46、NOTE 2 To improve and accelerate phase separation centrifugation can be applied provided that the necessary safety precautions, especially with regard to inflammable solvents are taken into account. 10.4 Clean-up Fill the clean-up column with Florisil in accordance with 7.8. Transfer the extract qua
47、ntitatively to the top of the column. Rinse the conical flask containing the sodium sulfate twice with about 5 ml of petroleum ether and add this to the column. Collect the entire eluate in the evaporation vessel 8.8. Rinse the column twice with about 5 ml of petroleum ether and add that eluate to t
48、he evaporation vessel 8.8 EN 14345:2004 (E) 8 NOTE Alternatively, commercially available Forisil cartridges containing 2 g of Florisil and 2 g of sodium sulfate are also applicable. 10.5 Gravimetric determination of the hydrocarbon content Concentrate extract using an appropriate evaporation device 8.3 to a small volume, but do not evaporate to dryness. Transfer the concentrated extract into a previously weighed 25 ml beaker 8.9. Rinse the evaporation vessel with 3 small portions of the petroleum ether 6.3 and add the washi
