1、December 2015 English price group 15No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 13.060.50!%Ir,“2387909www.din.d
2、eDIN EN 16694Water quality Determination of selected polybrominated diphenyl ether (PBDE) in wholewater samples Method using solid phase extraction (SPE) with SPE-disks combined with gas chromatography-mass spectrometry (GC-MS);English version EN 16694:2015,English translation of DIN EN 16694:2015-1
3、2Wasserbeschaffenheit Bestimmung von ausgewhlten polybromierten Diphenylethern (PBDE) in Gesamtwasserproben Verfahren mittels Festphasenextraktion (SPE) mit SPE-Disks in Verbindung mit Gaschromatographie-Massenspektrometrie (GC-MS);Englische Fassung EN 16694:2015,Englische bersetzung von DIN EN 1669
4、4:2015-12Qualit de leau Dosage dune slection dthers diphnyliques polybroms (PBDE) dans des chantillons deau totale Mthode par extraction en phase solide (SPE) avec disques SPE, avec couplage chromatographie en phase gazeuse-spectromtrie de masse (CG-SM);Version anglaise EN 16694:2015,Traduction angl
5、aise de DIN EN 16694:2015-12www.beuth.deDocument comprises 35 pagesDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.11.15 2 A comma is used as the decimal marker. National foreword This document (EN 16694:2015) has been prepared by T
6、echnical Committee CEN/TC 230 “Water analysis” (Secretariat: DIN, Germany). The responsible German body involved in its preparation was DIN-Normenausschuss Wasserwesen (DIN Standards Committee Water Practice), Working Committee NA 119-01-03-02 UA Organische Verbindungen of NA 119-01-03 AA Wasserunte
7、rsuchung. Designation of the method: Determination of selected polybrominated diphenyl ether (PBDE) in whole water samples Method using solid phase extraction (SPE) with SPE-disks combined with gas chromatography-mass spectrometry (GC-MS): Method DIN EN ISO 16694 F 48 This standard has been prepared
8、 under mandate M/424, which was given to CEN by the European Commission for the development and enhancement of standard methods in support of the Water Framework Directive (WFD) (Directive 2000/60/EC). The method specified in this standard supports the requirements given in Annex X of the Water Fram
9、ework Directive (WFD). The DIN Standard corresponding to the International Standard referred to in this document is as follows: ISO 5725-2 DIN ISO 5725-2 DIN EN 16694:2015-12 3 Expert assistance and specialized laboratories will be required to perform the analyses described in this standard. Existin
10、g safety requirements are to be observed. Depending on the objective of the analysis, a check shall be made on a case-by-case basis as to whether and to what extent additional conditions will have to be specified. This standard has been prepared by the DIN-Normenausschuss Wasserwesen (DIN Standards
11、Committee Water Practice) in collaboration with the Wasserchemische Gesellschaft - Fachgruppe in der Gesellschaft Deutscher Chemiker (Water Chemistry Society - Division of the German Chemical Society). It is part of the series Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung
12、 (German standard methods for the examination of water, waste water and sludge): Determination of selected polybrominated diphenyl ether (PBDE) in whole water samples Method using solid phase extraction (SPE) with SPE-disks combined with gas chromatography-mass spectrometry (GC-MS). Standard methods
13、 published as DIN Standards are obtainable from Beuth Verlag GmbH, either individually or grouped in volumes. The standard methods included in the loose-leaf publication entitled Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung will continue to be published by Beuth Verlag G
14、mbH and Wiley-VCH Verlag GmbH see 5.7.4.3), measured under identical conditions; two selected diagnostic ions (see Table 4) are present at the substance-specific retention time; relative intensities of all selected diagnostic ions measured in the sample do not deviate by more than (0,1 I + 10) % fro
15、m the relative intensities determined in the calibration standard solution, where I is the relative intensity of the diagnostic ion of the individual reference substance. DIN EN 16694:2015-12 EN 16694:2015 (E) 13 EXAMPLE Three selected diagnostic ions have the following relative intensities: 100 %,
16、50 % and 15 %. The maximum allowed deviation for I2and I3in the sample is (I1is by definition 100 % in both the sample and reference standard): I2: (0,1 50 + 10) % = 15 %; the relative intensity in the sample shall be between 35 % and 65 %; I3: (0,1 15 + 10) % = 11,5 %; the relative intensity in the
17、 sample shall be between 3,5 % and 26,5 %. NOTE 1 Further guidance on identification is given in EN ISO 22892 3 or in the guideline SANCO/12571/2013 10. NOTE 2 Deviating relative abundances are due to interferences. It is possible to remove interferences by applying a clean-up step (see e. g. Annex
18、D). DIN EN 16694:2015-12 EN 16694:2015 (E) 14 Table 4 Selected diagnostic ions for mass spectrometric detection and relative abundances Congener Ion 1 m/z Ion 2 m/z Diagnostic ions for GC-HRMS BDE-28 405,8026 (100) 407,8006 (97) BDE-47 483,7131 (68) 485,7111 (100) BDE-99 563,6215 (100) 565,6195 (98)
19、 BDE-100 563,6215 (100) 565,6195 (98) BDE-153 481,6975 (68) 483,6955 (100) BDE-154 481,6975 (68) 483,6955 (100) 13C-BDE-28 417,8428 (100) 419,8408 (97) 13C-BDE-47 495,7533 (68) 497,7513 (100) 13C-BDE-99 575,6619 (100) 577,6599 (98) 13C-BDE-153 493,7378 (68) 495,7357 (100) 13C-PCB-209 509,7229 (100)
20、511,7199 (86) Diagnostic ions for GC-NCI-MS all BDE 79 (100) 81 (98) all F-BDE 79 (100) 81 (98) Diagnostic ions for GC-MS/MS BDE-28 405,80 245,97 (100) 407,80 247,97 (97) BDE-47 483,71 325,88 (68) 485,71 325,88 (100) BDE-99 563,62 403,79 (100) 565,62 405,78 (98) BDE-100 563,62 403,79 (100) 565,62 40
21、5,78 (98) BDE-153 643,57 483,70 (100) 645,53 485,69 (73) BDE-154 643,57 483,70 (100) 645,53 485,69 (73) 13C-BDE-28 417,84 258,01 (100) 419,84 260,01 (97) 13C-BDE-47495,75 335,92 (68) 497,75 337,92 (100) 13C-BDE-99575,66 415,83 (100) 577,66 417,83 (98) 13C-BDE-153653,57 493,74 (100) 655,57 493,74 (73
22、) 13C-PCB-209509,72 439,80 (100) 511,72 439,80 (86) 8.6 Blank value measurements Use periodic blank value measurements (at least one measurement per sequence) to ensure the instruments and chemicals are free from contamination. Blank measurements shall comprise all steps of the analytical procedure.
23、 If blank values are unusually high (over 50 % of the lowest reporting level), review every step in the procedure and determine the cause by systematic checks so as to be able to eliminate the contamination source. Try to reduce the blank values as much as possible by applying various measures, such
24、 as avoiding contamination by ambient air and using suitable solvents (5.4) as well as checking the analytical instrumentation. DIN EN 16694:2015-12 EN 16694:2015 (E) 15 9 Calibration 9.1 Calibration with internal standards The use of an internal standard for the determination of the concentration m
25、inimizes possible errors made during injection and by sample losses during sample pretreatment, and corrects for differences in the final sample extract volumes and changes in recoveries caused by matrix effects. This calculation is usually available as an option in the quantification programs of mo
26、st manufacturers data analysis software. Additionally, it is possible to measure the recovery for the total procedure for each sample, if the values of the internal standard in the calibration solutions are compared to the values obtained for the extract. To achieve this, it is essential that the fi
27、nal volumes are identical. Alternatively, an injection standard can be used for the calculation of recoveries of internal standards (see 10.2). 9.2 Procedure 9.2.1 Evaluation of the range of linear relationship See Table 5 for typical concentrations of reference compounds and internal standards in s
28、olutions to evaluate the linear range. Adjust the concentrations according to the sensitivity of the used equipment and the required range of determinations. The linear relationship should be ensured with the concentration-response relationships as used in internal standardization. Plot for each sub
29、stance i the ratio values yi/yis,i(peak areas or peak heights of BDE compound i and corresponding internal standard is; use either the response of the diagnostic ion of highest intensity or the sum of the responses of both diagnostic ions) on the ordinate and the associated ratio of mass concentrati
30、ons i/is,ion the abscissa. Check the linear relationship by a graphical representation and statistical evaluation of the calibration data according to ISO 8466-1. 9.2.2 Two point calibration over the total linear range Carry out a two-point calibration, using calibration solutions with concentration
31、s corresponding to e.g. 20 % and 80 % of the linear range. Check the validity of this calibration function which is dependent on the stability of the GC-MS system at least with each batch of samples. Use the mean values of multi-injections e. g. yi(1)/yis,i(1), yi(2)/yis,i(2), yi(3)/yis,i(3)at two c
32、oncentration levels. DIN EN 16694:2015-12 EN 16694:2015 (E) 16 Establish the linear function of the two pairs of values yi/yis,iand i/is,iof the measured series using the following Formula (1): = +is, is,iiiiiiyaby(1) where yiis the measured response of substance i; the unit depends on the evaluatio
33、n, e.g. area value; iis the mass concentration of substance i, in the working standard solution, in picograms per millilitre, (pg/ml); aiis the slope of the calibration function of substance i, the unit depends on the evaluation; biis the ordinate intercept of the calibration curve, the unit depends
34、 on the evaluation; yis,iis the measured response of the corresponding internal standard for the substance i, the unit depends on the evaluation; is,iis the mass concentration of the corresponding internal standard for the substance i, in picograms per millilitre, (pg/ml). Estimate the accuracy of t
35、he calibration as described in 9.2.3. 9.2.3 Estimation of the accuracy of the calibration for the concentration of interest For example, analyze, as a minimum in triplicate, an independent standard solution (5.7.4.5) and calculate the results in accordance with the above calibration method. For each
36、 substance i the standard deviation between the single results ijand the known value qiof the concentration in the standard is then calculated according to Formula (1): ( )=211iNij ijqsN(2) where is is a measure of the accuracy of the calibration; ijis the measured mass concentration of substance i;
37、 qiis the known mass concentration of substance i; N is the number of measurements. DIN EN 16694:2015-12 EN 16694:2015 (E) 17 Table 5 Example concentrations in solutions for evaluating the linear range (GC-HRMS, 1 l injection) Congener Solution 1 pg/ml Solution 2 pg/ml Solution 3 pg/ml Solution4 pg/
38、ml Solution 5 pg/ml Solution 6 pg/ml Solution 7 pg/ml BDE-28 75 150 300 600 1 200 2 400 4 800 BDE-47 75 150 300 600 1 200 2 400 4 800 BDE-99 75 150 300 600 1 200 2 400 4 800 BDE-100 75 150 300 600 1 200 2 400 4 800 BDE-153 75 150 300 600 1 200 2 400 4 800 BDE-154 75 150 300 600 1 200 2 400 4 800 Int
39、ernal standards for EI 13C-BDE-28 600 600 600 600 600 600 600 13C-BDE-47 600 600 600 600 600 600 600 13C-BDE-99 600 600 600 600 600 600 600 13C-BDE-153 600 600 600 600 600 600 600 10 Quantification 10.1 Determination of the BDE concentrations in whole water samples The mass concentrations of the int
40、ernal standards isin the final volume of extract shall be the same for calibration and sample measurement. Use the same solvent composition for the working standard solutions and the extracts. Inject identical volumes of the sample extracts as injected as calibration solutions. Calculate the mass co
41、ncentration iof the substance using Formula (3). = =is, is, is,is,iiii iiiybym maV V(3) where iis the mass concentration of the substance i in the water sample in picograms per litre (pg/l); yiis the measured response, e.g. peak area, of the substance i in the sample extract; yis,iis the measured re
42、sponse, e.g. peak area, of the corresponding internal standard of substance i in the sample extract; is,iis the mass concentration of the corresponding internal standard of substance i in the sample extract, in picograms per millilitre, (pg/ml); mis,iis the mass of the added internal standard of sub
43、stance i in picograms (pg); V is the sample volume in litre (l); aisee Formula (1); bisee Formula (1). DIN EN 16694:2015-12 EN 16694:2015 (E) 18 10.2 Determination of the recoveries of the internal standards It is possible to measure the recoveries of the internal standards for single samples by com
44、paring the values of the internal and the injection standards obtained in the calibration with those obtained for sample extracts. Provided the relationship between the concentration and the response of the internal standard is linear and the intercept of this curve is negligible, the recovery of ea
45、ch internal standard is calculated according to Formula (4). = is,E inj,Cisis,C inj,E100yyAyy(4) where Ais is the recovery of the internal standard in percent (%); yis,E is the measured response, e.g. peak area, of the internal standard in the sample extract; yis,C is the measured response, e.g. pea
46、k area, of the internal standard in the calibration solution; yinj,E is the measured response, e.g. peak area, of the injection standard in the sample extract; yinj,C is the measured response, e.g. peak area, of the injection standard in the calibration solution. For a reliable quantification of the
47、 BDE congeners in the sample the recoveries of the internal standards should be between 70 % and 120 %. If this criterion is not met, it should be indicated in the test report. Re-analysis of the sample after dilution can help to improve the recoveries. 11 Expression of results Substract from the ca
48、lculated mass concentrations (see 10.1) the concentrations which were obtained for the blank determinations. The mass concentration, in nanograms per litre (ng/l), of the congeners listed in Table 1 shall be reported to two significant figures. EXAMPLES 2,4,4-Tribromodiphenyl ether, BDE-28 11 ng/l 2
49、,2,4,4-Tetrabromodiphenyl ether, BDE-47 1,2 ng/l 2,2,4,4,5-Pentabromodiphenyl ether, BDE-99 0,14 ng/l 2,2,4,4,6-Pentabromodiphenyl ether, BDE-100 0,021 ng/l DIN EN 16694:2015-12 EN 16694:2015 (E) 19 12 Test report The test report shall contain at least the following information: a) the applied test method, with a reference to this European Standard (EN 16694); b) all information necessary for the complete identificati
