1、BRITISH STANDARD Water quality - Gas BS EN 12673:1999 BS 6068-2.65 : chromatographic determination of some selected chlorophenols in water The European Standard EN 126731998 has the status of a British Siandard ICs 13.060.50 U- NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW S
2、TD-BSI BS EN 12b73-ENGL 1999 m 1b29bb 07BL751 3T5 BS EN 12673:1999 Environment Sector Committee, Amd. No. D - present to the responsible internatio - 2,6dibromophenol, C - 2,3,6trichlorophenol (see 6.24), C - 2,4,Mbromophenol, CgH3OBr3. For mass selective detection similar labelled compounds can be
3、used NOTE The two internai standards are used as a control for the analytical procedure. The choice of the two intenial standards should reflect the anticipated occurrence of the chlorophenols in the sample (e.g. if dichiorophenols are expected 2,rl-dibromophenol and 2,6dibromophenol should be used)
4、. Prepare a mixed standard of two component solutions in such a concentration that if a smal volume is added to a sample, the amount of the internai standards gives peak heights on the chromahgram in the upper part of the linear workmg range. for electron capture detection at least two with stationa
5、ry phases of Werent polariw, for mass spectsometsic detection one column sunices. dace water Is0 5667-6; sea water IS0 5667-9; rainwater IS0 5667-8; waste water IS0 5667-10; groundwater IS0 5667-11. The bottles sha be filled to the brim with the water sample and stoppered. On sample collection, take
6、 care that no interfering substances enter the water sample, and no losses of the determinands occur. This is especially important in the use of any plastic tubing used within the sampling apparatus. If necessary, it shall be proved by control tests that no losses by adsorption occur. Glass and stai
7、nless steel devices are preferable. Some chlorophenois may degrade in an aqueous environment. Therefore, unless experimental stability triais indicate otherwise, extract samples wih two days of sampling. If extraction is extended beyond two days this shall be noted in the test report. If the interva
8、l between sampling and extraction exceeds one day, keep the samples at 4 OC in the dark. If free halogens are suspected, add, at the time of sampling, some crystals of Na2S203-5H20 or 0,l ml of a 10 % (dm) NazS203 solution (6.12) per 125 ml of sample. Otherwise, do not add any preservation agent. 9
9、Procedure 9.1 Sample pretreatment In this section two procedures are given: - a method including acid-base partition which may be applied for dugr samples or when enrichment of the sample is required (9.1.1); - a procedure employing direct acetylation suitable for relatively clean samples (9.1.2). I
10、t is permissible for sample volumes to be increased if required The volumes of d other reagents (except the internai standard) shail be usted accordingly. Moreover, as the calibration is based on the totai procedure, the volumes used for the prepamtion of calibration solutions shall also be austed a
11、ccordingly. Apply one of the following procedures. salts. Shake the collected toluene extract with a 3 X 20 mi 0,l mom potassium carbonate solution (6.6), for 3 minutes each time, in a 250 ml separaijng funnel. Collect the water layers and proceed with 9.2.2. 9.1.2 Pretreatment if no clean ufienrich
12、ment procedure is followed Take a sample of 50 mi or an aiquot diluted with distilled water to a volume of 50 mi. Neutraiize acidic samples with sodium hydroxide (6.11) to a pH value of about 7 and alkaJine samples with phosphoric acid (6.9) to a pH of about 10. Add 200 pJ of internai standard (6.32
13、.1). 9.2 Acetylation procedure 9.2.1 Acetulatwn of the working standards That each of the working standards (6.32.4) as follows. Zt-ancfer with a pipette into a 100 ml open flask (7.3): - 50 mi of med water, - 2,00 ml of the working standard (6.32.4); - 200 1 of the internal standard (6.32.1). The f
14、ollowing steps shall be carried out in the exact times given and without interruption. Add 5 ml of the 1 moM potassium carbonate solution (6.6) and subsequently 1 rd of the acetic anhydride (6.7) and stir vigorously for 5 min to allow the release of carbon dioxide. NOTE 1 This procedure can also be
15、canied out using a separating funnel or a microseparator (see annex C). Allow to stand for 10 min and then add 5,O ml of n-hexane (6.4). Close the flask with the stopper and stir for 5 min Allow the two phases to separate. Transfer as large a portion as possible of the hexane phase to a vial. Dry th
16、e hexane phase with anhydrous sodium sulfate (6.10) or by freezing. Store at 4 OC. These acetylated solutionc are the calibration solutions. Calculate the content of each substance (p.g/ml) in each of the calibration solutions. NOTE 2 The efficiency of the derivatization step may be checked with a s
17、election of chiorophenolacetates. Generally these compounds are not suitable for calibration purposes because sufficiently pure chiorophenolacetates are not always available. O BSI 06-1999 STD-BSI BS EN 32b73-ENGL 1779 E Lb2qbb7 0783757 AL3 Page 6 EN 12673:1998 i e 9.2.2 Acetylation of the sample li
18、.ansfer the collected aqueous phases or an aliquot of 9.1.1 or the (neutralized) sample of 9.1.2 int a 100 ml open flask (7.3) and add 5 ml of the 1 mou potassium carbonate solution (6.6). Cany out the following steps in the exact times given and without interruption. NOTE 1 This procedure can also
19、be canied out using a separating funnel or a microseparator (see annex C). Add 1 ml of acetic anhydride (6.7). Stir vigorously for 5 min to allow the release of carbon dioxide. Mow to stand at room temperature for 10 min and add 5,O mi of n-hexane (6.4). Close the flask with the stopper and stir for
20、 5 min. Allow the phases to separate. Remove the water iayer and dry the hexane phase with anhyrous sodium sulfate (6.10) or by fkezing. NOTE 2 If an emulsion forms during the extraction process, the emulsion can be broken by e.g. violent shaking, deep freezing, uitrasonification or separating out b
21、y means of the addition of salts. In case of emulsification recoveries should be checked. 9.3 Calibration 9.3.1 Gas chromatograph calibration Set up the gas chromatographic instrument, equipped with the columns (7.6), according to the manufacturers instructions. Optimize gas flows. Ensure it is in a
22、 stable condition Guidance on the initiai gas chromatographic conditions is given in annex D. Calibrate by direct injection of the acetylated working standards (9.2.1) and in addition run a blank. Measure the gas chromatographic signais for each substance against concentsation. This gives informatio
23、n on retention times and relative responses of the determinands and the linear working range of the gas chromatogmph and detector. NOTE 1 Chromatograms of standards should be checked for retention time and peak resolution changes, and losses caused by decomposition within the injection liner. NOTE 2
24、 Separation can be considered as satisfactory if the height measured from the base line of the trough between the two adjacent peaks is no more than 20 % of the height of the highest peak; the peaks in this instance need to be of comparable height. Separation between 2,3,4,5tetrachiorophenol acetate
25、 and 2,3,4, is the measured due of the internal standard s as e.g. peak height or peak area; is the mass concentration of the determinand i in the caiibdon solution in micrograms per litre; is the mass concentration of the internal standard s in the calibration solution in micrograms per litre; is t
26、he slope of the calibration function, also called the response factoq is the intercept of the caiibdon function with the ordinate as e.g. peak height or peak area 9.4 Measurement is the measured value of the internai standard in the sample as e.g. peak height or peak area; is the mass concentration
27、of the internai standard in the sample e.g. in micrograms per litre; is the mass concentration of substance i, e.g. in micrograms per litre; is the slope of the calibration functioq is the intercept of the caiibration function with the ordinate as e.g. peak height or peak ma; concentmion factoq 4 fo
28、r the procedure with clean-upenrichment (9.1.1); 1 for direct procedure (9.1.2). 1 0,Ol 10 o, 1 Using mass spectrometry take for or us respedvely the peak height or peak area of the most intensive (fragment-) mass (base peak) from the corresponding substance?s spectsum. 10.2 Results When using elect
29、ron capture detection employing two gas chromatographic methods the application of the caldation method (10.1) provides one individual result for each column used. Derive the finai quantitative result from these results as follows: - take the arithmetic mean, provided that the differences between th
30、e individual results are less than 10 % of the lowest result; - choose the smallest value in the event of iarger differences. The larger values can be the result of peak overlap. Such resuits shall be labelled as measured values obtained from a single separation only. For both the MS resuit obtained
31、 from a single column and the final quantitative ECD result report the mass concentrations of the substances to not more than two significant figures. Round off the resuits as in Table 2. Table 2 - Rounding of resuits 11 %st report The following information b) the data required for identification of
32、 the sample examined c) the interval between sampling and extraction; d) if stabilization by soium thiosulfate is applied; e) the types of columns and gas chromatography conditions employed; f) the concentration of each of the chlorophenois, in micrograms per litre; g) any special circumstances obse
33、rved during the determination, such as for instance other peaks observed in the chromatogram; h) ail operations (e.g. the sew or Mon of the sample) not prescribed in the standard which might have affected the result; i) detection with ECD or Ms, For detection with MS Identjfication through the regis
34、tmtion of complete mass-spectsa (SCAN mode) or individual registration of selected masses (SIM mode); number of registered or examined ion masses (given in annex F); possible occurrence of divergence of the experimental expected isotopehagment ion-ratio; quantification mass. o BSI 06-1999 nble 3 - P
35、erformance data for drinki Sample type kinking water AW Drinking water Kigh Phenol 2- 3- i- 2) 3 2, 4 3) 5 3, 6- 394 3, 5 3, 3) 4 3,3) 5 2, 3) 6- 2, 4,s 2, 4) 6- 3) 4) 5 2, 3) 4) 5 2, 3) 4) 6- 2, 3,5) 6- pentachioro 2- 3- 4- 2, 3- 2) 4- 2,s 296- 3,4 375 2,394- 2,375 2,396- 2,495 2,476- 3,475 2,3,4,5
36、 2,3,4,6- 2,3,5,6- pentachioro - n - 51 34 55 jo 16 M 27 43 37 25 44 55 33 56 - 55 54 16 49 47 58 47 46 58 - - P - 15 11 16 14 12 15 8 13 11 7 12 16 10 16 16 15 5 14 14 17 14 14 16 - - O % - 5,9 6,7 797 11,l 13,3 22,2 16,7 5,9 16,7 6,7 67 17,6 5,9 - n is the number of values is the number of data se
37、ts, i.e. number of laboratories is the percentage of outliers is the general mean, without outliers is the indicator value is the relative repeatability standard deviation is the repeatability standard deviation is the relative between-laboratory standard deviation is the between-laboratory standard
38、 deviation is the relative reproducibility standard deviation is the reproducibility standard deviation g water (h Pg/l Fg/i !4,89 16,50 5,77 3,18 1,60 1,60 X P 1,30 1,14 0,80 o, 1,24 1,28 0,15 0,15 0,21 0,18 0,23 0,20 0,08 OJO 0,11 0,13 22,76 27,50 10,lO 10,61 3,27 3,21 5,41 6,50 5,11 6,24 0,08 0,0
39、8 4,68 5,11 1,63 1,94 0,87 0,9C 0,90 0,93 2,47 2,91 0,98 1,2 Page 9 EN 126731998 :h and low concentration) sr % Pgll 15 2,185 11 2,354 14 0,231 20 0,257 19 0,154 31 0,264 15 0,022 12 0,026 30 0,047 9 0,008 20 0,022 22 5,045 8 0,788 8 0,27 10 0,516 18 0,913 9 0,008 5 0,229 10 0,158 17 0,145 7 0,059 8
40、 0,198 8 0,082 SL kLg/l 33 4,866 21 7,009 47 0,747 43 0,564 21 0,169 45 0,556 49 0,074 36 0,077 23 0,054 45 0,037 24 0,028 33 7,584 38 3,888 44 1,453 32 1,722 34 1,744 39 0,032 21 0,996 27 0,432 26 0,229 44 0,395 30 0,747 28 0,272 SR % Pgn 36 5,295 28 7,398 49 0,782 48 0,624 27 0,22 50 0,62 57 0,086
41、 41 0,088 31 0,072 47 0,039 45 0,051 41 9,229 40 4,034 45 1,478 36 1,974 40 0,033 22 1,048 29 0,467 32 0,277 38 1,966 45 0,406 33 0,818 35 0,345 I O BSI 06-1999 STD*BSI BS EN 12b?3-ENGL 1799 LbZqbbS 07817bl 244 = Page 10 EN 12673:1998 Table 4 - Performance data for surface water h Sample type Wace w
42、ater High Surface water A3W Phenol 2- 3- 4- 233- 2,4 2, 5 2,6- 3, 4 3, 5 2,3,4 1,3, 5 2, 3, 6 2,4, 5- 1,4,6 3,475 2,3,4, 5 2, 3,4, 6- 2,3,5, 6- )entachlor0 - n - 50 48 56 58 50 50 15 52 56 51 44 60 50 - 32 56 58 48 33 27 37 44 32 $6 - - P - 14 14 16 16 14 14 7 15 16 15 13 17 14 - 10 16 16 13 15 9 16
43、 12 9 13 - - O % 12,5 12,5 - 5,9 12,5 697 12,5 6,s 579 11,8 791 12,5 971 599 - 13,3 10,o 14,3 10,o 771 - X P PLPjl P 91,31 110,02 78,B 97,64 21,51 %,O6 11,M 10,69 44,57 57,17 8,04 490 OJO 0,09 14,99 19,45 8,83 9,04 2,81 2,78 8,29 9,71 5,44 6,31 25,16 33,Ol 4,40 6,37 3,29 3,21 2,lO 2,B 1,51 1,78 2,29
44、 2,55 0,32 0,29 0,39 0,36 0,40 0,40 0,25 0,19 0.20 0.25 !h and low concentratia 12 10,67 8 6,065 9 1,969 13 1,468 8 3,362 7 0,544 1 9E-04 7 1,027 5 0,437 15 0,416 5 0,419 9 0,468 il 2,712 13 0,561 7 0,239 13 0,269 LO 0,156 14 0,313 8 0,027 12 0,047 12 0,049 9 0,023 -7 0,034 29 26,13 28 21,82 33 7,18
45、 43 4,763 36 16,O6 21 1,689 74 0,074 34 5,083 26 2,29 39 1,092 27 2,25 29 1,586 32 7,939 40 1,744 45 1,494 36 0,765 21 0,318 45 1,021 65 0,207 25 0,099 14 0,055 63 0,16 21 0,042 30 27,13 29 22,73 34 7,392 45 4,941 37 16,59 24 1,914 74 0,074 35 5,181 27 2,364 42 1,168 28 2,338 31 1,7 33 8,401 12 1,85
46、2 16 1,522 i4 0,917 25 0,379 17 1,069 i5 0,209 !9 0,113 !4 0,096 I9 0,226 17 0,073 or the explanation of symbols see Table 3. O BSI W1999 STD.BSI BS EN LZb73-ENGL 1999 LbZqbbS I178L7b2 LBO m Table 6 - Performance data for waste water (hi4 Sample type Vaste water w Naste water rOW For the emlanation
47、( Phenol n la 52 56 jo 52 50 14 16 36 47 41 50 46 19 52 54 50 23 50 52 56 47 46 54 3. - P - .3 .5 .6 .4 .4 14 5 13 16 14 12 14 13 7 15 15 14 7 14 15 16 14 13 15 - O % 13,3 - 6,3 12,5 677 16,7 13,3 12,5 777 12,5 X P Pgll Pg/i 7,58 110,02 2,62 97,64 1,78 28,06 1,Ol 10,69 5,48 57,17 7,77 8,90 0,09 0,09
48、 9,19 9,04 4,15 19,45 2,69 2,78 8,18 9,71 4,98 6,31 .8,47 27,50 6,06 10,61 3,19 3,21 4,37 6,50 4,61 6,24 0,11 0,08 4,48 5,11 1,60 1,94 0,95 0,90 0,83 0,93 2,43 2,91 0,92 1,26 Page 11 EN 126731998 and low concentration sr %J Pg/l 5 4,568 5 3,437 ,O 2,194 9 0,944 il 5,087 9 0,674 2 0,001 5 0,65 8 0,77
49、6 36 0,97 6 0,504 9 0,465 10 1,789 4 0,24 12 0,37 17 0,725 14 0,65 6 0,007 7 0,297 13 0,212 20 0,191 12 0,097 25 0,599 19 0,171 Pl 29,84 a 19,89 I5 7,723 19 5,423 u) 18,37 20 1,553 54 0,047 31 2,825 il 5,746 12 1,121 35 2,893 24 1,172 30 5,549 81 53 35 33 47 29 35 37 34 28 15 4,931 1,685 1,531 1,537 0105 1,32 0,564 0,35 0,282 0168 O, 14 SR % (L 15 30,75 13 20,81 17 8,018 i0 5,525 L3 19,44 !2 1,706 54 0,047 i1 5,852 32 2,947 56 1,492 36 2,936 36 1,307 36 6,604 32 4,943 M 1,723 39 1,709 37 1,713 48 0,051 30 1,353 38 0,606 40 0,383 36 0,3 34 0,311 38 0,918 O BSI 61999 STD
