1、PUBLISHED DOCUMENTPD CEN/TR 15175:2006Characterization of sludges Protocol for organizing and conducting inter-laboratory tests of methods for chemical and microbiological analysis of sludgesICS 13.030.20g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g
2、3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58PD CEN/TR 15175:2006This Published Document was published under the authority of the Standards Policy and Strategy Committee on 30 April 2007 BSI 2007ISBN 978 0 580 50514 0National forewordThis Pu
3、blished Document was published by BSI. It is the UK implementation of CEN/TR 15175:2006.The UK participation in its preparation was entrusted to Technical Committee EH/5, Sludge characterization.A list of organizations represented on EH/5 can be obtained on request to its secretary.This publication
4、does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.Amendments issued since publicationAmd. No. Date CommentsTECHNICAL REPORTRAPPORT TECHNIQUETECHNISCHER BERICHTCEN/TR 15175March 2006ICS 13.030.20English VersionCharacterization of
5、 sludges - Protocol for organizing andconducting inter-laboratory tests of methods for chemical andmicrobiological analysis of sludgesCaractrisation des boues - Protocole dexcution dessaisinterlaboratoires portant sur des mthodes danalyseschimiques et microbiologiques des bouesCharakterisierung von
6、Schlmmen - Protokoll zurDurchfhrung von Ringversuchen fr Verfahren zurchemischen, mikrobiologischen und physikalischenAnalyse von SchlmmenThis Technical Report was approved by CEN on 30 September 2005. It has been drawn up by the Technical Committee CEN/TC 308.CEN members are the national standards
7、bodies of Austria, Belgium, 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 COM
8、MITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. CEN/TR 15175:2006: E2 Contents Page Forewo
9、rd3 Introduction .4 1 Scope 5 2 Planning protocol 5 3 Interlaboratory test protocol issues 5 4 Interlaboratory test procedure .6 5 Final report of the test.7 6 Other comments 8 Annex A (informative) Proposed protocol for sample preparation methods9 Annex B (informative) Agreement to participate in t
10、he . sludge method interlaboratory validation test 10 Bibliography 11 CEN/TR 15175:20063 Foreword This Technical Report (CEN/TR 15175:2006) has been prepared by Technical Committee CEN/TC 308 “Characterization of sludges”, the secretariat of which is held by AFNOR. Attention is drawn to the possibil
11、ity 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. CEN/TR 15175:20064 Introduction For international harmonization it is essential that a fit for purpose interlaboratory t
12、est using a range of typical sludges with relevant analyte concentrations be carried out prior to proposing for publication any method as a Technical Report. At least ten laboratories from three different countries should participate in this test. Only experienced laboratories routinely carrying out
13、 sludge analysis should participate. The organizer should aim for 12 to 15 laboratories to participate in each test in as many countries as possible. Efforts are needed to ensure that there is a minimum of intersample variation amongst the circulated samples. It is recommended that each test include
14、s a range of sludges that is representative of the proposed scope of the method, as a minimum this should include an untreated (raw) sludge, a treated (an aerobically digested) sludge, a presscake and samples of any other sludges relevant to the method being tested. In addition a spiking solution an
15、d a calibration check standard will generally be distributed. If possible, samples should be in the same form as would normally be submitted to a laboratory for analysis. For sample preparation methods without a final measurement stage (e.g. Aqua regia digestion for metal analysis), see Annex A. CEN
16、/TR 15175:20065 1 Scope This Technical Report specifies the requirements for interlaboratory tests to validate chemical and microbiological methods for sludges. 2 Planning protocol The main test variables to be agreed are: a) organising laboratory; b) documented method to be tested; c) number and na
17、ture of the samples; d) statistical calculations including rejection of outliers; e) deadlines for sending out samples, receipt of results from participants and final test report from the organizer; f) spiking protocol to calculate recovery; g) analysis of a calibration check standard. It will also
18、allow a check to be made on the comparative accuracy of the calibration standards used by all the participants. This can sometimes explain differences between laboratories). 3 Interlaboratory test protocol issues 3.1 Test organiser and dispatch of samples It is essential that the bulk material is ho
19、mogeneous. This should be checked using a suitable low cost parameter (e.g. Cu, Zn). The organizer will compile a test contact list with: a) contact name; b) contact full address; c) contact phone numbers (named contact and switchboard); d) contact fax number; e) contact E-mail address. The organize
20、r will obtain a written statement (see Annex B) from each laboratory agreeing to participate, agreeing to follow the provided method exactly and meet the deadlines for start and completion of analysis and for submission of the results on the appropriate form. An additional 20 % of samples shall be p
21、repared and held by the organizer at 18 C or less. These can be used if any problems are encountered during the test. For microbiology this may not be appropriate. CEN/TR 15175:20066 3.2 Participating laboratories Participating laboratories should be laboratories that routinely carry out sludge anal
22、ysis. 3.3 Statistical calculations An initial check should be made to confirm a normal distribution of results. If the distribution is not normal then appropriate robust statistics should be employed. Assuming a normal distribution, the statistical calculations should be carried out according to ISO
23、 5725 by a suitably experienced person for chemical parameters. Suitable rejection procedures should be used for microbiological parameters. Rejection of outliers should also follow ISO 5725. All Type B (reproducibility) outliers should be eliminated. All Type C outliers from the mean of one lab (re
24、peatability) should be included. In addition the elimination of obvious outliers by the statistical organizer (Type D) shall be allowed as long as they are fully documented with the reason for elimination. Each sample shall be analysed in replicate (x times) on y separate days (x and y to be agreed
25、for each individual test). 4 Interlaboratory test procedure 4.1 General The organizer should procure and prepare the samples. These should contain appropriate concentrations of the analyte. The minimum sample mass for wet sludges should be 1 kg. For presscakes a minimum mass of 500 g should be sent.
26、 For special purposes (e.g. methods that only require a few grams of sample) a smaller amount of sample will be circulated. All samples will be sent out in polyethylene, polypropylene, stainless steel or aluminium containers that will tolerate a slight increase in pressure. It is not thought necessa
27、ry, or advisable, to use glass bottles. Each bottle will be clearly labelled with the type of sample, the analysis required and the dates by which the analysis should commenced and completed. All sample containers will be packed in stout sealed polyethylene / polypropylene insulated containers. Samp
28、les will be sent out at a temperature below 4 C with suitable cooling boxes/bags/packs to ensure that the temperature remains below 4C for at least 48 h. 4.2 Courier arrangements The organizer will arrange a suitable courier with a guaranteed 24 h delivery that will accept sewage and other sludge sa
29、mples. The sample pick-up time will be agreed with the courier. The delivery time window for each participating laboratory by an authorized person will be agreed between the laboratory and the organising laboratory. Each participant will be informed of the expected delivery time window and should en
30、sure that suitable sample reception facilities are available. CEN/TR 15175:20067 The courier will be provided with full addresses (including the postcode) and contact details for each participating laboratory. A simple chain of custody protocol will be implemented for transport and receipt of the sa
31、mples. All participating laboratories will upon receipt immediately record the temperature of the samples. They should then store the received samples at a temperature of less than 4 C until commencement of analysis. This should be within two working days (they have had due warning) of receipt of th
32、e samples. The organizer should ensure that all appropriate sample transport of hazardous biological and chemical material regulations are complied with (e.g. pathogens, dioxin or PCB standard solutions etc.) This will cover within and between country deliveries of the samples. 4.3 Documentation Doc
33、umentation to be sent with the samples will be: a) another copy of the agreed method; b) spiking solution/material if relevant; c) instructions for the test; d) form for the submission of results; e) analysis start date (within four days after dispatch); f) analysis completion date (not more than tw
34、o weeks after the dispatch date); g) deadline for return of results (within three weeks of sample dispatch); h) full contact details of the organizer to allow for queries and for the return of results. 5 Final report of the test The organizer should provide a full report of the test to all participa
35、nts by the agreed deadline. This will include: a) a listing of all of the results; b) mean value for each tested parameter; c) calibration check solution result; d) reproducibility (absolute and relative); e) repeatability (absolute and relative); f) recovery (if relevant); g) names and countries of
36、 laboratories that returned valid results; h) total number of results returned; i) temperature of the samples upon receipt at the participating laboratories; j) number of outliers from non-rejected laboratories; CEN/TR 15175:20068 k) any exceptional circumstances/problems reported by any of the labo
37、ratories on an anonymous basis; l) summary of performance - i.e. interpretation of figures and data; m) a detailed description of the samples and of the interlaboratory test. 6 Other comments Ideally each test should include a range of analyte concentrations. However, with the range of sludge types
38、and the availability of contaminated sludge samples, this may not always be possible. A spiking solution of the analyte will normally be supplied, so a sample aliquot can be spiked with the analyte. This will allow a recovery to be calculated. It is accepted that the spike analyte will be more easil
39、y recovered than the endogenous analyte. However, the results should indicate whether there is any significant bias in the final analysis step. It will also allow a check to be made on the comparability of the calibration standards used by each of the participants. (For microbiological parameters, i
40、t should be possible to utilize suitable lenticules or pastiles for this purpose.) The spiking level ideally should be at least equal to the value of the analyte in the sample and should raise the concentration of the analyte to 75 % to 95 % of the calibration range of the method (without dilution o
41、f the sample). All published results should be anonymous with respect to originating laboratory. CEN/TR 15175:20069 Annex A (informative) Proposed protocol for sample preparation methods For methods which are only sample preparation methods without a final measurement stage (e.g. aqua regia digestio
42、n for metal analysis), the described protocol will not assess the errors of the preparation stage if all the participating laboratories analyse the final prepared digests. In this instance, the interlaboratory test would estimate the errors associated with both the digestion and the final measuremen
43、t stages. To attempt to minimise this problem, it is recommended that all the resulting prepared sample extracts are promptly returned to one specified experienced laboratory. This laboratory will then remove a known amount from each returned sample extract (e.g. 10 % of the volume received) and mak
44、e up a composite sample. This laboratory would then analyse all the received sample extracts, interposing composite extracts between each returned sample extract. By then assessing the results obtained against the preceding and subsequent composite sample, it should be possible to assess the results
45、 with respect to the sample preparation stage. The variation in the composite sample results is attributable to the measurement stage in the experienced laboratory. CEN/TR 15175:200610 Annex B (informative) Agreement to participate in the . sludge method interlaboratory validation test This signed f
46、orm to be returned to the test organizer We agree to participate in the above test and accept the following conditions: 1) we agree to follow the supplied method exactly. Results from any other method used by the laboratory are not acceptable; 2) our laboratory has previous experience of this type o
47、f analysis; 3) we agree to consult with the test organiser if any minor deviations from the supplied method are thought desirable and to report them in detail; 4) we agree to report any exceptional circumstances on the results submission form; 5) we agree to have a suitable laboratory representative
48、 to be available to receive the samples within the agreed receipt time window; 6) we will immediately, upon receipt store all samples at less than 4 C; 7) we undertake to commence the analysis within two day of receiving the samples. (The dispatch day will always be a Monday); 8) we undertake to com
49、plete the analysis within two weeks of the dispatch of the samples; 9) we undertake to supply the results by the agreed deadline of three weeks from the date of dispatch of the samples; 10) we undertake to return the sample cooling boxes, bags and packs if required; 11) if we encounter any problem with this interlaboratory test we undertake to inform the organizer immediately; 12) it is understood that all published results will be on an anonymous basis; 13) we accept that (in the event of participating in work for which there is fina
