1、:才中华人民共和国出入境检验检疫行业标准SN/T 0548. 1 2002 出口酱油中1，3-二氯-2-丙醇和2，3-二氯-1-丙醇的检验方法Determination of 1 ,3-dichloro-2-propanol and 2,3-dichloro-1-propanol in soy sauce for export 2002-08皿02发布2003-0个01实施中华人民共和国发布国家质量监督检验检菇总局前本标准中的测定方法是参考国内外有关文献，经研究，改进和验证后制定。本标准的附录A为资料性附录。本标准由国家认证认可监督管理委员会提出并归口。本标准负责起草单位z中华人民共和国广东出
2、入境检验检疫局。本标准主要起草人z容慧、王志元、张思群、梁伟大。本标准系首次发布的出入境检验检疫行业标准。SN/T 0548. 1-2002 1 范围出口酱油中1，3-二氯-2-丙醇和2，3-二氯-1-丙醇的检验方法SN/T 0548.1-2002 本标准规定了酱油中1，3-二氯-乙丙醇(简称1.3-氯丙醇、1，3-DCP)和2，3-二氯-1-丙醇(简称2，3-氯丙醇、2，3-DCP)的抽样，制样和气相色谱法测定方法。本标准适用于出口酱油中1，3-二氯乙丙醇及2，3-二氯-1丙醇的检验。2 抽样和制样2.1 抽样原则按检验批在不同部位抽取代表性样品。2.2 抽样方法2.2.1 100件以下抽取
3、6件，100件以上按式(1)计算抽样数量。n = .;万/2式中:n-一一抽样数量(取整数，小数部分向上修约hN一一全批总数量。. ( 1 ) 2.2.2 瓶装酱油每箱抽样一瓶至二瓶，每批抽样不得少于六瓶(每瓶以500mL计，下同)，其中四瓶用于检验，留样二瓶备套。2.2.3 散装酱油每批采集混合样不少于3000 mL(或3kg)，分装于三个磨口瓶中(微生物抽样容器及用具均需灭菌)。2.3标注抽样后必须立即在样品上标注品名、批号、生产日期、生产单位、抽样人员及抽样日期。3 检验方法3.1 方法提要试样中的1，3-二氯2丙醇和2，3-二氯-1-丙醇用硅藻土柱净化，被测物用正己烧-乙酶洗脱，收集洗
4、脱液，用配有电子捕获检测器的气相色谱仪测定，外标法定量。3. 2 试剂和材料除另有规定外，所有试剂均为分析纯，实验用水为蒸馆水。3.2.1 正己烧。3. 2. 2 正己皖乙酷体积比:9+1。3.2.3 无水硫酸铀:650CC灼烧4h，冷却后贮于密封容器中备用。3. 2. 4 硅藻土:600C灼烧6h，冷却后贮于密封容器中备用。3.2.51，3-二氯-2-丙醇和2，3-二氯-1-丙醇标准品z纯度二三99%。3. 2. 6 1，3-二氯2-丙醇和2，3-二氯-1-丙醇标准溶液:准确称取适量的1.3-二氯-2-丙醇和2，3-二氯L丙醇标准品，用少量的正己皖榕解，并以正己皖配成浓度为1000周/mL的
5、标准储备液。根据需要再用正己烧稀择成适用浓度的标准工作榕液。SN/T 0548.1-2002 3- 3 仪器3. 3. 1 层析柱:1. 5 cm X 20 cm.内装2cm高无水硫酸铀+5g硅藻土+2cm高无水硫酸铀。3.3.2 气相色谱仪:配有电子捕获检测器。3. 3- 3 微量注射器:10L。3.4 测定步骤3.4.1 提取与净化称取10.0g酱油于150mL烧杯中，加入约10g硅藻土(3.2.4).用玻璃棒搅匀至松散粉状，装入巳填好的层析柱(3.3.1).用玻璃棒挤实。上面再加2g无水硫酸铀。用100mL正己皖卢乙酷(9十1)氓合榕液淋洗，淋洗速度为2mL/min.收集前50mL淋洗液
6、于50mL比色管中，用氮气浓缩，定容至10.0 mL.供气相色谱分析。3.4.2 测定3.4.2.1 色谱条件a)色谱柱:HP-PAS-525 mXO. 32 mm(内径)X 0.32m(膜厚)，或相当者;b)色谱柱温度:60C保持3min，以每分钟10C升温至100C，再以每分钟20C升温至220C; c)进样口温度:250C; d)检测器温度:300C; e)载气:高纯氮，纯度二三99.999 % , 5. 0 mL/min; 0尾吹气:60mL/min; g)进样方式:无分流进样;h)进样量:2Lo3. 4. 2. 2 色谱测定根据样液中被测物含量情况，选定浓度相近的标准工作溶液。标准工
7、作溶液和待测样液中被测物的响应值均应在仪器检测的线性范围内。对标准工作溶液与样液等体积间插进样测定。在上述色谱条件下.1.3-二氯-乙丙醇的保留时间约为3min , 2，3-二氯-1-丙醇的保留时间约为4min。标准品的气相色谱图参见附录A。3.4.3 空白试验除不添加试样外，均按上述测定步骤进行。3. 5 结果计算和表述按式(2)计算试样中1，3-二氯-2-丙醇和2.二二氯-1-丙醇的含量。-A , X m 式中:x-一试样中的1.3-二氯-乙丙醇和2.3-二氯-1-丙醇的含量，单位毫克每千克(mg/kg); A-一样液中1，3-二氯-乙丙醇和2.3-二氯-1-丙醇的含量，单位为微克每毫升(
8、g/mU;. ( 2 ) A，-标准工作液中2.3-二氯-1丙醇和2，3-二氯1-丙醇的含量，单位为微克每毫升(p.g/mU;r一一标准工作液中1，3-二氯丙醇和2.3-二氯-1-丙醇的浓度，单位为微克每毫升(g/mL); v-一样液最终定容体积，单位为毫升(mU;m-一最终样液所代表的试样量，单位为克(g)。注:计算结果需将空白值扣除。4 测定限及回收率4. 1 测定限本方法1.3-二氯甲乙丙醇和2.3二氯-1-丙醇测定限均为0.050mg/峙。2 SN/T 0548.1 2002 4.2 回收率酱油中1.3-二氯-2-丙醇和2.3-二氯-1-丙醇的添加浓度及其回收率实验数据:1.3-二氯-
9、2-丙醇和2.3-二氯-1丙醇添加浓度为0.050mg/kg时，回收率分别为105.0%和100.0% ; 1.3-二氯-2-丙醇和2.3-二氯-1-丙醇添加浓度为0.50mg/同时，回收率分别为96.4%和95.3%; 1.3-二氯-2-丙醇和2.3-二氯-1-丙醇添加浓度为1.00mg/kg时，回收率分别为99.8%和91.5%。句。SN/T 0548.1一20025Hz 500 400 300 200 100 。1一-1.3-二氯-2-丙董事$2一一2.3-二氯-1-丙喜事。附录A(资料性附录)标准晶色晴圈2 3 4 mm 固A.11，3-二氯-2-丙醇和2，3-二氯-1-两醇标准晶气相
10、色晴圆4 SN/T 0548.1-2002 Foreword he method of determination of this standard was drafted by referring to relevant domestic and foreign literatures through research , modification and verification. Annex A of this standard is the informative annex. This standard was proposed administrated by National R
11、egulatory Commission for Certification and Accreditation. The main drafters of this standard are Rong Hui , Wuang Zhiyuan , Zhang siqun , Liang Weida. This standard is a professional standard of ent叩-exitinspection and quarantine promulgated for the first time. 5 SN/T 0548.1-2002 Determination of 1,
12、3-dichloro-2-propanol and 2，3国dichloro-1-propanolin soy sauce for expo同1 Scope 丁hisstandard specifies the methods of sampling , sample preparation and determination of 1, 3-dichloro-2-propanol (ab.1 , 3-DCP)and 2, 3-dichloro-1-propanol (ab.2, 3-DCP) by gas chromatog raphy in soy sauce for expo内.This
13、 standard is applicable to the determination of residue content of 1,3-dichloro-2-propanol and 2 ,3-dichloro-1-propanol in soy sauce. 2 sampling and sample preparation 2.1 Principle of sampling Take the representative sample from different part of each lot. 2.2 Method of sampling 2.2.1 Below 100 pac
14、kages ,take six packages;above 100 packages ,take the sample according to formula( 1) n = ;-市/2、zs. ，、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . where n一thenumber of sampling; N-the number of total samples. 2.2.2 For the bottled soy sauce , take 1-2 bottles from each package. Th
15、e samples taken back will not less than six bottles each lot (as 500 mL) , four of them are used for testing , two of them are used for storage. 2.2.3 For the bulk soy sauce , the combined primary sample is fully mixed and reduced to at least 3000 mL (3 kg) , then put it in three clean sample cans.
16、2.3 Mark Mark the sample name , lot, production date , production industry, the sampling person and date on the cans. 3 Determination 3.1 Principle 6 SN/T0548.1-2002 The 1, 3-dichloro-2-propanol and 2 , 3-dichloro-1-propanol in the test sample are cleaned up by pass through a Celite 545 column. Coll
17、ected elute solution with n-Hexane-ether for determination by means of a gas chromatography equipped with electron capture detector, using external sta忏dard method. 3.2 Reagents and materials Unless otherwise specified , all the reagents should be analytically pure , water is redistilled wa ter. 3.2
18、.1 n-Hexane. 3.2.2 n胸Hexane-ether( V/V):9 + 1. 3.2.3 Anhydrous sodium sulfate: Ignite for 4 h at 650C, tightly closed keep in a container. 3.2.4 Celite 545: Ignite for 6 h at 600C for 6 h , tightly closed keep in a container. 3.2.5 1 ,3-DCP and 2,3-DCP standard: Purity99%. 3.2.6 1 ,3-DCP and 2,3-DCP
19、 standard solution:Accurately weigh an adequate amount of 1,3-DCP and 2, 3-DCP standard , dissolve them in a small volume of n-Hexane and dilute with n-Hexane to prepare a standard stock solution of 1 00。g/mLin concentration. Then dilute the standard stock solution with n-Hexane to the required conc
20、entration as the standard working solution. 3.3 Apparatus and equipment 3.3.1 Celite 545 column: 1.5 cmx20 cm (id) , packed with 2 cm (height) of anhydrous sodium sulfate ,5 9 Celite 545 , 2 cm (height) of anhydrous sodium sulfate. 3.3.2 Gas chromatograph: equipped with electron capture detector. 3.
21、3.3 Micro sringe: 10L 3.4 Procedure 3.4.1 Extraction and cleanup Weigh 10.0 9 (accurate to 0.1 g) of the test sample into a 150 mL beaker, add about 10 9 Celite 545 , mix thoroughly with a glass stick. Transfer it into the Celite column (3.3.1) , press with a glass stick , add 2 cm (height) of anhdr
22、ous sodium sulfate. Rinse the column with 100 mL of n-Hexane ether, the flow rate of rinse is 2 mL/min. collect 50 mL elute in a colorimetric cylinder, evaporate the elute with nitrogen less 10 mL, make up to 10.0 mL with n-Hexane-ether for GC determina tlon. 7 SN/T 0548.1-2002 3.4.2 Determination 3
23、.4.2. 1 GC operating condition a) Chromatographic column: HP-PAS-5 25 m x 0.32 mm (id) ，0.32m film thickness , or equiva lent; 10C /min b) Column temperature: Programmed , 60 C (3 min)一一一一.:.100C (0 min)一一一一220C(0 min); c) Injection port temperature: 250C ; d) I nterface tem pertu re : 300 c ; e) Ca
24、rrier gas:Nitrogen , purity;:99.999% , speed 5.0 mL/min; f) Make-up flow: speed 60 mUmin; g) Injection mode:Splitless; h) Injection volumn: 2L 3.4.2.2 GC determination According to the approximate concentration of the target compounds in the sample solution , select the standard working solution wit
25、h similar peak height to that of the sample solution. The respons瞌es of the standard working solution and the sample solution should be within the linear range of the instrumental detection. The standard working solution should be randomlinjected in between the injections of the sample solution of e
26、qual volume. The retention time of 1, 3-DCP is ca 3 min , 2,3-DCP is ca. 4 min under the above chromatographic condition. For gas chromatogram of the standard, see figure A1 in annex A. 3.4.3 Blank test The operation of the blank test is the same as that described in the method of determination but
27、with omission of sample. 3.5 Calculation and expression of the result Calculate the content of 1 ,3-DCP and 2,3-DCP in the test sample by GC Data processor or accord ing to the formula (2) below: A x C x V .( 2 ) As x m where X-the content of 1,3-DCP and 2,3-DCP in the test sample , mg/kg; A一thepeak
28、 area of 1 ,3-DCP and 2，3-DCP，g/mL; 8 SN/T0548.1一2002As-the peak area of 1 ,3-DCP and 2,3-DCP in the standard working solution，g/mL; c-the concentration of 1, 3-DCP and 2, 3-DCP in the standard working solution，g/mL; V-the final volume of the sample solution, mL; m-the corresponding mass of the test
29、 sample in the final sample solution , g. Note: The blank value should be subtracted from the above result of calculation. 4 Limit of determination and recovery 4. 1 Limit of determination The limit of determination of this method is 0.050 mg/kg. 4.2 R缸。veryAccording to the experimental data , the f
30、ortifying concentrations of 1, 3-DCP and 2, 3-DCP in soy sauce and its corresponding recoveries are: 0.050 mg/阅，therecovery 105.0% 1 ,3-DCP and 100.0% 2,3-DCP; 0.50 mg/kg, the recovery 96.4% 1 ,3-DCP and 95.3% 2,3-DCP; 1 .00 mg/kg, the recovery 99.8% 1, 3-DCP and 91.5% 2. 3-DCP. 9 SN/T 0548. 1-2002
31、Annex A ( informative) Chromatogram of the standard 咀EF 5Hz 1 frh el3 e-5001 四-eg z M 4001 的300 200 100 。2 3 4 mm 1-1 ,3-DCP; 2-2,3-DCP. Fig.A.1 Gas chromatogram of 1 ,3-DCP and 2,3-DCP standard no 1 NOON-F.写的。HZm 中华人民共和国出人境检验检疫行业标准出口酱油中1.3-二氯-2-丙醇和2.3-二氯-1-丙醇的检验方法SN/T 0548.1一一2002* 中国标准出版社出版北京复兴门外三里河北街16号邮政编码:100045 电话:6852394668517548 中国标准出版社秦皇岛印刷厂印刷* 开本880X1230 1/16 印张1字数17千字2002年11月第一版2002年11月第一次印刷印数1一20007巳哈定价10.00网址书号:155066 2-14764 版权专有侵权必究举报电话:(010)68533533
