SNT 1017.4-2002 出口粮谷及油籽中哒菌清残留量检验方法

1、SNT 1017.4-2002 出口粮谷及油籽中哒菌清残留量检验方法:才己中华人民共和国出入境检验检疫行业标准SN /T 1017. 4 -2002 出口粮谷及油籽中日达菌清残留量检验方法Method for the determination of diclomezine residues in cereals and oil seeds for export 2002 - 01-16 发布 2002 - 06- 01 实施中华人民共和国发布国家质量监督检验检菇总局SN/T 1017.4-2002 前言本标准是按照 GB/T 1. 1-1993<<标准化工作导则 第 1 单元 z

2、标准的起草与表述规则 第 1 部分 2标准编写的基本规定及 SN/T 0001-1995<<出口商品中农药、兽药残留量及生物毒素检验方法标准编写的基本规定的要求进行编写的。其中测定方法参考了国内外有关文献，经研究、改进和验证后而制定的。本标准同时制定了抽样和制样方法。测定低限是根据国际上对粮谷及袖籽中隧菌清残留量的最高限量和测定方法的灵敏度而制定的。本标准附录 A 是提示的附录。本标准由国家认证认可监督管理委员会提出并归口。本标准起草单位=中华人民共和国吉林出人境检验检疫局。本标准主要起草人 z荣会、徐立明、李庆才、吴剑、郑希铭。本标准系首次发布的检验检疫行业标准。1 范围中华人民

3、共和国出入境检验栓在行业标准出口粮谷及油籽中脏菌清残留量检验方法Method for the determination of diclomezine residu田 in 四reals and oil seeds for export SN/T 1017.4-2002 本标准规定了出口粮谷及油籽中她茵清残留量检验的抽样、制祥和气相色谱测定方法。本标准适用于出口糙米、大豆、玉米、小麦中瞌菌清残留量的检验。2 抽样和审j样2.1 检验批以不超过 200 t 为一检验批。 200 t 袋装玉米或大豆约 2200 袋 s袋装糙米或小麦约 4000 袋。玉米或大豆有时为散装品。同一检验批的商品应具有相

4、同特征，如包装、标记、产地、规格和等级等。2.2 抽样数量2.2.1 袋装货品按式(1)计算抽样袋数。a = ，;万.( 1 ) 式中 N 全批袋数 za一一抽样袋数(a 值取整数，小数部分向前进位为整数)。2.2.2 散积货品(玉米或大豆)货堆高度不超过 2m。按货堆面积划区设点。以 50 m 为一个取样区，每区设中心及四角(距边线1m 处)5 个点。每增加一个取样区，增设 3 个点。2.3 抽样工具2. 3- 1 金属单管取样器 2全长 55 cm(包括手柄) ，直径1. 5 cm-2. 0 cm，槽长度应超过袋对角线长度的一半。2. 3- 2 金属双套管取样器:全长分 1m 、 2 m(

5、均包括手柄两种。内、外管同部位分段开几个槽口，每个槽口长 15 口n.20 cm ，口宽 2.0 cm-2. 5 cm o 内管的内径为 2.5 cm-3. 0 cm，取样器的探头长约 7cm 。2.3.3 取样铲或取样勺。2.3.4 分样板。2. 3- 5 盛样器.简或袋，可密封。2.3.6 分样布或适用铺垫物。2.4 抽样方法2.4.1 袋装抽样2.4. 1- 1 倒包抽样中华人民共和国国家质量监督栓验撞疫总局 2002-01-16 批准 2002- 06- 01 实施l SN/T 1017.4-2002 从堆垛的各部位随机抽取 2.2.1 规定的应抽样袋数的 10%(每批一般不少于 3

6、袋) ，将袋口缝线全部拆开，平置于分样布或其他洁净的铺垫物上，双手紧握袋底两角，提起约成 45C倾角，倒拖约 1 m ，使袋内货物全部倒出。查看袋内和袋间品质是否均匀。确认情况正常后，用取样铲随机在各部位抽取样品，并立即将样品倒入盛样器内。每袋抽取样品的数量应基本一致。2.4.1.2 袋内抽样按 2.2.1 规定的应抽样袋数(扣除倒包抽样袋数)，在堆垛囚周的上、中、下各层以曲线形走向随机抽取。然后按糙米、小麦、玉米、大豆，用下述方法进行取样:对糙米、小麦，用金属单管取样器 (2.3. 1)槽口朝下，从每袋一角依斜对角方向插入袋内，然后将管槽旋转朝上，抽出取样器，立即将样品倒入盛样器内。对玉米、

7、大豆，用 1m 长的金属双套管取样器(2.3.2) ，关闭槽口，从每袋一角依斜对角方向插入袋内，然后旋转内管以开启槽口，待样品流满内管后，再旋转内管以关闭槽口。抽出取样器，立即将样品倒入盛样器内。每袋摘取样品的数量应与 2. 4. 1. 1 基本一致。每批所抽取的样品总量应不少于 4 kg 。2.4.2 散积抽样按 2.2.2 规定的取样点，逐点抽取样品。将取样器(2.3.2)槽口关闭，以倾斜 45C角度插入货堆至相应深度，旋转取样器内管以开启槽口，待样品流满内管后，再旋转内管以关闭槽口。抽出取样器，立即将样品倒入盛样器内，从各点所抽取样品的数量应基本保持一致。每批所抽取的样品总量应不少于 4

8、 kg 。2.4.3 大样缩分袋装样品:合并从倒包和袋内抽样所取全部样品，倒于分样布上，用分样板按四分法缩分样品至不少于 2 峙，倒入盛样器内，加封后标明标记，并及时送交实验室。散积样品.将抽取的全部样品，倒于分样板上，以下按上述袋装样品方法进行。2.5 试样制备2.5.1 制样工具2.5.1.1 磨碎机。2.5.1.2 筛子， 20 目筛。2.5.1.3 分样板。2.5.1.4 盛样瓶=具塞广口瓶。2.5.2 制样方法将样品按四分法缩分至 500 g，用磨碎机全部磨碎并通过 20 目筛。混匀，均分成两份作为试样，分装入洁净的盛样瓶内，密闭，标明标记。2.6 试祥保存将试样子一5C 以下避光保

9、存。注 z 在抽样及制样的操作过程中，必须防止样品受到污染或发生残留物吉量的变化。3 测定方法3.1 方法提要试样中残留的脸菌清用丙酣-石油隧(l十1)提取，提取液经氯化锁溶液洗涤后，浓缩，过硅胶柱净化。被测物用石油隧丙酣(95+5)洗脱。洗脱液蒸发至近干，用石油酶溶解并定容，榕液供配有电子俘获捡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，所用试剂均为分析纯，水为蒸馆水。3. 2.1 丙酣:重蒸馅。2 SN/T 1017.4-2002 3- 2. 2 石油隧 g重蒸馅。3.2.3 元水硫酸纳， 65 0;C灼烧 4 h ，贮于密封容器中备用。3.2.4 氯化纳溶液 z称取

10、 50 g 氯化铺溶解于 1 000 mL 水中.3.2.5 硅胶 z层析用，100200 日，用前于 120C活化 3 h，冷却后贮于密封容器中备用。3.2.6 睡在菌清标准品 2纯度;99 %。3.2.7 隧菌清标准溶液 2准确称取适量的磁菌清标准品，用少量的丙嗣溶解，并以石油隧配制成浓度为1. 00 mg/mL 的标准储备液。根据需要再用石油隧稀释成适用浓度的标准工作溶液。3.3 仪器和设备3. 3- 1 气相色谱仪 z配有电子俘获检测器。3- 3. 2 振荡器。3- 3. 3 旋转蒸发器。3. 3- 4 硅胶柱， 25 cmX l. 5 cm G.d.) 。自下而上依次填装 2cm 高

11、无水硫酸锅、 15 g 硅胶、2cm 高无水硫酸锅。使用前用 50 mL 石油酷预淋洗。3. 3- 5 微量注射器，10L。3- 4 测定步骤3- 4. 1 提取称取试样 20 g(精确至 0.1 g)至 250 mL 具塞锥形瓶中，加入 100 mL 丙阁石油醋。十1)混合液，振荡提取 30 min. 将提取液过滤于 500mL 分液漏斗中。用 50 时，丙阁分两次洗涤残渣，洗涤液经过滤后合并于上述分液漏斗中。3.4.2 净化于上述分液漏斗中加入 200 mL 氯化锅溶液(3.2.4) ，振摇 1 min，静置分层。收集上层有机相。水相再用 2X50 mL 石油酷重复提取两次。合并有机相，用

12、元水硫酸销脱水后，收集于梨形瓶中。于 40C水浴旋转浓缩至近干，加入 5 mL 石油酷溶解残渣。将溶解液倾入硅胶柱中，用 200mL 石油隧洗柱，弃去流出液。然后用 100mL 石油隧-丙阁 (95+引进行洗脱，收集洗脱液于梨形瓶，于 40C水浴中旋转浓缩至近干。用石油隧溶解残渣并移人容量瓶中定容至 5.00 mL，供气相色谱测定。3.4.3 测定3.4.3.1 色谱条件a) 色谱柱， 25 mXO. 53 mmG.d.) ，膜厚 1.0m ，BP10 石英毛细管柱，或相当者sb) 色谱柱温度 240C;c) 进样口温度， 280C;d) 检测器温度， 290C;e) 载气=氮气，纯度二三99

13、.99% , 10 mL/min; f)尾吹气:氮气，纯度二三99. 99 % , 50 mL/min; g) 进样量，1 L.3- 4. 3- 2 色谱测定根据样液中贴菌清含量情况，选定浓度相近的标准工作溶液。标准工作溶液和待测样液中农药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参插进样测定。在上述色谱条件下，由主菌清的保留时间约为 6.5 min. 标准品的气相色谱图见附录 A 中图 Al，3.4.4 空白试验除不加试样外，均按上述测定步骤进行。3-5 结果计算和表述用色谱数据处理机或按式(2)计算试样中贴菌清残留含量。3 SN/T 1017.4-2002 X=hcV

14、- h ,. ? m 式中 :X一一试样中暗自菌清残留含量 .mg/kg ，h一一样液中胎菌清的色谱峰高，mm;h.一一标准工作液中咙菌清的色谱峰高，mm;c一一标准工作液中险菌清的浓度，g/mL ，V 样液最终定容体积，mL;m一最终样液所代表的试样量 .go注 2 计算结果需将空白值扣除.4 测定低限、回收率4.1 测定低限本方法的测定低限为 0.10 mg/kg. 4.2 回收率4.2.1 糙米中瞌菌清的添加浓度及其回收率实验数据 g在 0.10 mg/kg 时，回收率为 83.0% ，在 0.50 mg/同时，回收率为 92.2% , 在 1.00 mg/kg 时，回收率为 84.2%

15、 0 4.2.2 玉米中眩菌清的添加浓度及其回收率实验数据 z在 0.10 mg/kg 时，回收率为 91.7% , 在 0.50 mg/kg 时，回收率为 93.4% ; 在1. 00 mg/kg 时，回收率为 89.6% 。4.2.3 小麦中险菌清的添加浓度及其回收率实验数据=在 0.10 mg/kg 时，回收率为 89.6% ，在 0.50 mg/kg 时，回收率为 94.4% , 在1. 00 mg/kg 时，回收率为 93.0% 。4.2.4 大豆中磁菌清的添加浓度及其回收率实验数据 g在 0.10 mg/kg 时，回收率为 81.8% ，在 0.50 mg/kg 时，回收率为 82

16、.2% ，在 1.00 mg/同时，回收率为 82.1% 。4 . ?.?. ( 2 ) SN/T 1017.4-2002 附录 A(提示的附录)昵菌清标准晶的气榈色谱回5 。由同.用主菌清标准品的气相色谱图图 AlSN/T 1017.4-212 Foreword This standard was drafted in accordance with the requirements of GB/T 1 .1-1993; Directives for the work of standardization-Unit 1: Drafting and presentation of standa

17、rds-Part 1: General rules for drafting standards;and SN/T 0001-199S;General rules for drafting the standard methods for the determination of pesticide. veterinary drug residues and biotoxins in commodities for export; . The method of determination of this standard was drafted by referring to relevan

18、t domestic and foreign literatures through research. modification and verification .In addition. methods of sampling and sample preparation are also speci币ed in this standard. This limit of determination is defined in this standard on the basis of the current international maximum limits for diclome

19、zine residues in cereals and oil seeds and the sensitivity of the method. Annex A of this standard is an informative annex This standard was proposed by and is under the charge of China National Regulatory Commission for certification and Accreditalion. This standard was drafted by Jilin Entry.Exit

20、Inspection and Quarantine Bureau of the People s Re-public of China The main drafters of this standard are Rong Hui , Xu li ming , Li qing cai , Wu jian and Zheng xi mmg. This standard is a professional standard promulgated for the first time. Note: This English ve陌ion. a translation from the Chines

21、e te:埠， is solely for guidance. 6 Professional Standard of the People s Republic of China for Entry-Exit Inspection and Quarantine Methods for the determination of diclomezine residues in cereals and oil seeds for export SN/T 1017.4-2002 1 Scope This standard specifies the method of sampling , sar节p

22、le preparation and determination of di-clomezine residues by gas chromatography in cereals and oil seeds for expo同.This standard is applicable to the determination of diclomezine residues content in unpolished rich soyabean , maize and wheat for expo同2 Sampling and sample preparation 2.1 Inspection

23、lot Each inspection lot should not exceed 200 tonnes. An inspection lot of 200 tonnes , for unpolished rich or wheat in bags ,shall 9be ca 4000 bags;for maize or soyabean in bags , shall ca 2 200 bags. The cargo of maize or soyabean is sometimes in bulk. The characteristics ofthe cargo within the sa

24、me inspection lot, such as packing , mark ,origin ,grade etc. , should be the sa;、e.2.2 Ouantity of sample taken 2.2.1 Cargo in bags Calculate the number of bags to be taken by formula( 1) = .,fN ) 1 ( . . . . where N-total number of bags in a lot; a-number of bags to be taken. Note: 时 value B is w忧

25、h decimal. round 0青 the decimal part ,which is added as unity to the integral part of B. 2.2.2 Cargo in bulk (maize or soyab回n)The height of the cargo pile should not exceed 2 m. Set up areas and spots for sampling on the pile surface. 50 m is considered as an area , in which 5 spots shall be fixed

26、, one in the centre and four at four corners (1 m from the margin) of the area. For an additional area , three m。陌 sam?Approved by General Administr剖ion of Ouality Implemented 行om 2也06-01Supervision , Inspection and Ouarantine of the Peoples Republic of China on 2002.01刊7 SN/T 1017 .4-2002 pling spo

27、ts shall be 币xed.2.3 Sampling tools 2.3.1 Metallic sampler:length (including handle) :55 cm;diameter: 1.5-2.0 cm ;groove length: longer than half the diagonal length of the bag. 2.3.2 Metallic double? casing sampler: length 1 m , 2 m (both including handle) with some slots on defferent sections and

28、respectively at the same heights for both inner and outer casings; lengh of slots:1 5-20 cm , width of the slots:2.o-2.5 cm;inside diameter of the inner casing:2. 5-3.0 cm;the probe.lengh of the sampler:ca 7 cm. 2.3.3 Sampling shovel or ladle. 2.3.4 Plate for quartering. 2.3.5 Sample container:Can o

29、r bag , which can be sealed. 2.3.6 Cloth (or other suitable material) sheet:For sample dividing (quartering). 2.4 Sampling procedure 2.4.1 For cargo in bags 2.4.1.1 Sampling by emptying out Draw 10 percent of the number of bags specified in 2.2.1(not less than 3 bags) at any pa同 ofthepile at random.

30、 Unseam and open the bag , and lay it on a clean cloth sheet (or other clean sheet). Grasp tight two corners of the bag bottom and raise up to an angle of 45;C, tug backward for ca 1 m until all content of the bag is emptied out.Check whether the quality of goods is uniform with-in and between the b

31、ags. After confirming the goods are in normal condition , scoop up the sample from different pa内s of the oupoured content at random , and promptly place in a sample contain-er. The quantity of the sample drawn from each bag should be basically the same 2.4.1.2 Sampling from inside the bags Draw the

32、samples from the number of bags specified in 2.2.1 (by deducting the number of bags drawn in 2.4.1 .1) Along the sine wave of the pile , draw the samples from the bags of the upper middle and lower parts around the pile at random. For unpolished rice , wheat , maize or soyabean proceed as follows: F

33、or unpolished rice or wheat , insert the metallic sampler (2.3.1) , with its groove facing down-ward , diagonally into each bag , then turn the sampler 180;C, draw out the sampler and promptly pour the sample into a container. B SN/T 1017.4-2002 For maize or soyabean , insert the metallic double? ca

34、sing sampler (2.3.2 , length 1 m)(the slots should be closed while inserting in) diagonally into each bag. Turn the inner casing to open the slo恒 so that the sample may fill up the inner tube. Again turn the inner casing to close the slots and draw out the sampler. Promptly pour the sample into a sa

35、mple container. The amount 01 sample drawn 1rom each bag should be basically the same as in (2.4.1. 1). The to-tal weight 01 the sample 01 each lot should be not less than 4 kg. 2 ,:4.2 Sampling,1rom the cargo in bulk Insert the double-casing sampler (2.3.2) successively into the pile at the spo胎 sp

36、由而ed in 2.2.2 , to appropriate depth at 450 (the slots should be closed while inserting in). Turn the inner casing to 。pen the slots so that the sample may 佣1 up the inner tube. Again turn the inner casing to close the slots and draw out the sampler. Promptly pour the sample into a sample container.

37、 The amount 01 sample drawn from all the spots shall be basically the same The total weight 01 the representative sample 01 each lot should be not le臼 than 4 kg. 2.4.3 Reduction 01 gross sample For cargo in bags: Pour all the samples (1rom both 2.4.1.1 and 2.4.1.2) on a clean sheet. Reduce to not le

38、臼 than 2 kg by quartering with a plate.Place in a sample container ,seal , label and send to the laboratory in time. For cargo in bags: Pour all the drawn sample onto a clean sheet and proceed as 10r cargo in bags deseribed above. 2.5 Preparation 01 test sample 2.5.1 Tools. 2.5.1.1 Grinder 2.5.1.2 S

39、ieve:20-mesh sieve. 2.5.1.3 Plate 10r quartering. 2.5.1.4 Sample container:Wide-moutl、 bottle ，with ground stopper. 2.5.2 Procedure Ruduce the sampe by quartering to ca 1 kg , grade with a grinder (2. 5. 1. 1) and let 811 pass through a 20 mesh sieve. Mix thoroughly and divide into two equal p。同ions

40、 as the test samples Place in sample containers , seal and label. 2.6 Storage 01 test sample 9 SN/T 1017 .4-2002 The test samples should be stored below - 5C and kept away from light Note: In the course of sampling and sample preparation. Precaution must be taken to avoid contamination or any factor

41、s that may cause the change of residue content. 3 Method of determination 3.1 Principle The diclomezine residues in the test sample are extracted with petroleum ether-acetone (1 + 1) , the extract , after washing with salt solution , is concentrated and cleaned up by passing through a silica gel col

42、umn. The diclomezine on the column is then eluted with petroleum ether-acetone (95 + 5) The eluate is evaporated to near dryness , dissolved and made up to a del日 nite volume with petroleum ether. Determination is made by means of a gas chromatograph equipped with electron capture detector, using ex

43、ternal standard method. 3.2 Reagents and materials Unless otherwise specified , all the reagents used should be analytically pure , ;water; is distilled water. 3.2.1 Acetone:Redistilled. 3.2.2 Petroleum ether: Redistilled 3.2.3 Anhydrous sodium sulfate:lgnite at 650C for 4 h and keep in a tightly cl

44、osed container. 3.2.4 Sodium chloride solution:Dissolve 50g of sodium chloride in 1 000 mL of water. 3.2.5 Silica gel: For chromatography , 100-200 mesh. Before use , heat at 120C for 3h , and keep in a tightly closed container. 3.2.6 Diclomezine standard:Purity ;, 99%. 3.2.7 Diclomezine standard so

45、lution:Accurately weigh an adequate amount of diclomezine stan-dard , dissolve in a small volume of petroleum ether. Dilute with petroleum ether to form a standard stock solution of O. 100 mg/mL in concentration. Then dilute the standard stock solution with petroleum ether to the required concentrat

46、ion as the standard working solution. 3.3 Apparatus and equipment 3.3.1 Gas chromatograph equipped with electron capture detector. 3.3.2 Shaker 3.3.3 Rotary evaporator. SN/T 1017 .4-2002 3.3.4 Silica gel column :25 cm x 1. 5 cm (id) , add in sequence 2 cm (height) of anhydrous sodi-um sulfate , 15 9

47、 of silica gel and 2 cm (height) of anhydrous sodium sulfate. Rinse the column with 50 mL of petroleum ether before use. 3.3.5 Micro-syringe: 10L. 3.4 Procedure 3.4.1 Extraction Weigh ca 20 9 (accurate to 0.1 g) ofthe test sample into a 250 mL conical flask with stopper , add 100 mL of petroleum eth

48、er-acetone (1 + 1) mixture and extract for 30 min. Filter the extract into a 500 mL separator. Wash the residue twice with 50 mL (in total) of acetone , filter and combine the washings in the same separator. 3.4.2 Cleanup Add 200 mL of sodium chloride solution into the separat肘， shake for 1 min , an

49、d let stand aside for separating.Collect the upper organic phase. Wash the aqueous phase with 2 x 50 mL petroleum ether. Combine the organic phase and washings and dehydrate with anhydrous sodium sulfate Transfer the dehydrated petroleum ether extract into a pear-shaped bottle , rotary-evaporate nea

50、r to dryness with a bath temperature below 4O;C. Dissolve the residue with 5 mL of petroleum ether. Transfer the above solution into the silica gel column , wash the column with 200 mL of petroleum ether and discard the effluent. Then elute with 100 mL of petroleum ether-acetone (95 + 5) and col lec

51、t the eluate in a pear-shaped bottle. Rotary-evaporate the eluate to near dryness with a bath temperature below 40;C leach and dilute exactly to 5.00 mL with petroleum ether. The solution is ready for GC determination. 3.4.3 Determination 3.4.3.1 GC operating condition a) Chromatographiccolumn:25 mx

52、O.53 mm (id) , 1.0m film thickness , BP10 , silica capillary col-umn or the equivalent; b) Column temperature:240;C; c) Injection temperature:280;C; d) Detector temperature:290;C; e) Carrier gas: Nitrogen , purity ;, 99.99% , 10 mL/min; f) Make-up gas: Nitrogen , purity主.99.99% ,50 mmin; g) Injectio

53、n volume: 1L 3.4.3.2 GC determination According to the approximate concentration of pesticide in the sample solution , select the standard working solution with similar peak height to that of the sample solution. The responses of di 11 SN/T 1017.4-2002 clomezine in the standard working solution and

54、sample solution should be within the linear range ofthe instrumental detection. The standard working solution should be randomly injected in-be-tween the injections of the sample solution of equal volume. Under the above Chromatographic condition , the retention time of diclomezine is ca 6.5 min.For gas chromatogram of the standard , see figure A1 in annex A. 3.4.4 Blank test The operation of the blank test is the same as that described in the method of determination , but with omission of sample addition. 3.5 Calculation and ex