SN T 1738-2006 进出口粮谷和油籽中虫酰肼残留量的检验方法气相色谱串联质谱法.pdf

1、华人出入境检验检疫行业标准电出口糠谷和油籽中检验方法气相色谱串SN/T 1738-2006 残留量的谱法Inspection of tebufenozide residues in cereals and oH seeds for import and export-Gas chromatography mass spectrometry method 2006-01-26发布060712000069 2006-0816实施中华人民共和国发布国家质量监督检验梭痊总局目。自本标准的附录A为资料性附录。本标准出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入境检验检疫局

2、。本标准主要起草人:王明泰、牟峻、邹明强、卢利军、吕清双、刘洪涛。本标准系首次发布的出入境检验检疫行业标准。SN/T 1738-2006 I 1 范围进出口粮谷和油籽中虫酷月井残留量的检验方法气相色谱串联质谱法SNjT 1738-2006 本标准规定了进出口粮谷和油将中虫酷腾残留量检验的抽样、制祥和气相色i普质谱检测方法。本标准适用于进出口糙米、玉米、大豆、花生仁中虫酿腾残留量的检验。2 抽样和制样2.1 检验批以不超过200、t为一检验批。200t袋装糙米约4000袋;袋装玉米或大豆约2200袋;袋装花生约2400袋。玉米或大豆有时为散装品。间一检验批的商品应具有相同特征，如包装、标记、产地

3、、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z=守( 1 ) 式中:N一一全扯袋数:G一一抽样袋数。注2日值取整数.小数部分向前进位为整数。2.2.2 散和、货品(玉米或大豆)货堆高度不超过2mc按货堆面积划区设点。50 mZ为一个取样区，每区设中心及四角(距边线1 m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:全长55cm(包括手柄)，直径1.5 cm2. 0 cm，沟槽长度应超过袋对角线长度的半。2.3.2 金属双套管取样器:全长分1rn , 2 m(培包括乎柄)两种。内、外管商部位分段开几个槽口，每个槽口长15cm

4、20 cm，口宽2.0 cm2. 5 cmc内管的内径为2.5 cm3. 0 cm;取样器的探头长约7 CITlc 2.3.3 取样铲或取样勺。2.3.4 分样板。2.3.5 盛样器:筒或袋.可密封62.3.6 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: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45。倾角，倒拖约1m，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

5、样器内。每袋抽取样品的数量应基本一致。SN/T 1738-2006 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)，在堆垛四周的上、中、下各居以曲线形走向髓机抽取。然后按糙米、玉米、大豆、花生仁.用下述方法进行取样:对槌米.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主是内.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。对玉米或大豆，用1m长的金属双套管取样器(2.3.2)，关闭槽口，从每袋一角依销对角方向插入袋内，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。对花生仁，将应抽

6、各袋拆开袋口缝线3针5针，用取样勺从开口处抽取样品。立即缝好袋口.并将所取样品倒入盛样器内。每袋抽取样品的数量应与2.4. 1. 1基本一致。每批所抽取的样品总量应不少于4kg , 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45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。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峙。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2kg扣j入星

7、星样器内，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 粉碎机。2.5. 1. 3 筛子:2.0mm圆孔筛。2.5. 1. 4 分样极。2.5. 1. 5 盛样瓶:具塞广口瓶。2.5.2 制样方法2.5.2.1 槌米、玉米或大豆试样制备:将样品按四分法缩分至1kg，用磨碎机(2.5.1.1)全部磨碎并通过20目筛。?昆匀.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。2.5.2.2 花生仁试样制备:将样品按四分法缩分至500g，用粉碎机(2.5.

8、1.2)粉碎.使全部通过2.0 mm圆孔筛。i昆匀.均分成两份幅作为试样，分装入洁净的盛样瓶内，密闭.标明标记。2.6 试样保存将试样于OClC以下避光保存。在抽样及制样的操作过程中，应由止样品受到污染或发生残留物含量的变化。3 测定方法3.1 方法提要试样用水m丙酣提取.提取;夜经二氧甲:烧;夜-液分配后.以弗罗里硅土柱净化，用气相色i普质i普测定，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，水为工次蒸馆水。3.2.1 丙酿:重蒸铺。3.2.2 二氧甲烧:重蒸锚。3.2.3 正己烧:重蒸悔。3.2.4 乙酸乙醋:重蒸悔。3.2.5 无水硫酸纳:6500C灼烧4h，贮于密封

9、容器中备用。3.2.6 硫酸铀水i容液:20g/L。SN/T 1738-2006 3. 2. 7 弗罗里硅土:层析用，100目200目，650oC灼烧5h，用前于1300C活化4h，冷却后加入2%(质量分数)水脱活.贮于密封容器中备用。3.2.8 虫酷阱标准品:纯度二三99%。3.2.9 虫眈拼标准溶准:准确称取适量的虫眈脐标准品，用少量的丙酬溶解，并以丙酣配制成浓度为1.00 mg/ mL的标准储备液。根据需要再用两国稀释成适用浓度的标准工作语液。3.3 仪器和设备3.3. 1 气相色j普质谱仪:配有质量选择检测器(MSD)。3.3.2 振荡器。3.3.3 旋转蒸发器。3.3.4 无水硫酸铀

10、柱:7. 5 cm X 1. 5 cm (内径)，内装5crn高无水硫酸铀。3.3.5 弗罗里硅土柱:25cmX 1. 5 cm(内径)，自下而上依次填装2cm高无水硫酸锅、10g弗罗里硅土、2crn高无水硫酸纳。使用前用50mL正己烧预淋洗。3. 4 19m定步骤3.4.1 提取称取试样约20g(精确至0.1g)于250mL具塞锥形瓶中，加入40mL水，放置2h。然后加入100 mL丙翻，振荡提取30mino将提取液过滤于500mL分液漏斗中，残渣再用50mL丙隅重复提取一次，合并滤液于上述分液漏斗中。加入200mL硫酸纳水溶液和100mL工氯甲烧，振摇3min，静置分层.收集工氯甲;境相。

11、水相再用2X50mL二氯甲:境重复提取两次.合并二氧甲烧相。经无水硫酸铀柱脱水.收集于250mL 浓缩瓶中.于400C水浴中旋转浓缩至近干.加入5mL正己烧溶解残渣。3.4.2 净化将样?夜倾入弗罗里硅土柱中.依次用50mL正巳烧和50mL乙酸乙醋十正己烧(1十引进行淋洗.弃去流出液.再用50mL乙酸乙醋十正己烧(1十1)进行洗脱，收集全部洗脱液于250mL浓培瓶中，于400C水浴中旋转浓捕至近干，用内酣溶解并定容至5mL，供气相色谱-质谱i9l店。3.4.3 测定3.4.3. 1 气相色谱-质谱条件a) 色i普柱:30mXO. 25 mm(内径)，膜厚0.25r丑，DB-17石英毛细管柱.或

12、相当者;30C/min _ _ _ n_ _ 10C/ b) 色谱柱温度:500C (2 min)一一2000C(1 min)一一一一2700C(7 min) : c) 进样口温度:2700C : d) 色i普质谱接口温度:260oC:巳)载气:氮气.纯度二三99.999%,1. 2 mL/min: f) 进样量:1L: g) 进样方式:无分流进样，1.5 min店开l骂:h) 电离方式:EI:i) 电离能量:70eV: j) 电子倍增器电压:1.6kV:k) 测定方式:选择离子监测方式:1) 选择监测离子(m/z):193、207、278:3 SN/T 1738一2006m) 奋剂延迟:5r

13、nin。3.4.3.2 气相色谱，质谱测定根据样液中被测农药含量，选定浓度相近的标准工作榕液。标准工作搭液和待提j样液中农药的响应值均应在仪器检测的线性商围内。对标准工作溶液与样?夜等体积参插进样测定。在上述气相色谱质i普条件下，虫酷脏的保留时间约为17mino标准品的气相色谐-质i普选择离子包谱图和质谱图参见附录A中图A.1和附录B中因B.L3.4.3.3 气相色谱，质i普确证对标准洛液及样液均按3.4.3.1规定的条件进行腿走时，如果样被与栋准梅液的选择离子团中，在相同保留时间有峰出现.则根据选择离子m/z193、207、278(其丰度比86: 35 : 100)对其确证。3.4.4 空白

14、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)计算试样中虫黯腾残留量E式中:X一试样中虫酷脚残留量，单位为毫克每千克(mg/kg); A一一一样液中虫眈腾的色谱峰高，单位为毫米(mm);As. -一标准工作液中虫酷腾的色谱蜷高，单位为毫米(mm);C一一标准工作液中虫黠腾的浓度，单位为微克每毫升g/mU;V一一样液最终定容体积，单位为毫升(mU:1一一最终样液所代表的试样质量，单位为克(g)。4 测定低限、由收率4. 1 测定低限本方法的翻定低限为0.10mg/kg。4.2 阻收率4.2. 1 糙米中虫眈月井的添加放度及其回收率实验数据z在O.10

15、mg/kg 1. 00 mg/kg时，回收率为88.2%95. 4%。4.2.2 玉米中虫眈腾的添如放度及其回收率实验数据E在O.10 mg/kg 1. 00 mg/kg时.四收率为88.6%-94.4%0 4.2.3 大豆中虫耽腾的海加放度及其回收率实段数据z在O.10 mg/kg 1. 00 mg/kg时.四收率为92.7%97. 7%。4.2.4 花生仁中虫耽脐的添加浓度及其自收率实验数据:在0.10rng/kg1.00 mg/kg时，因收率为91.8% 94. 1%。4 ( 2 ) SN/T 1738-2006 附录A(资料性附录)虫酷鹏标准品的气相色i普栩质i普选择离子色i普回50

16、。口1105 (资料性附录)虫戳脐标准物的气相色i蕾质i昔圈133 50 。m!Z 5 SN/T 1738-2006 Foreword Annex A of this standard are inforrnative annex. 了hisstandard was proposed by and is under the charge of the Certification and Accreditation Adrnin istration of the Peoples Republic of China. 了hisstandard was drafted by the J ilin E

17、ntry-Exit Inspection and Ouarantine Bureau of the Peoples Republic of China. 丁hisrnain drafter of this standard is Wang Mingtai , Mu Jun , Zou Mingqiang , Lu Lijun , Lu Oing shuang , Li u Hongtao. This standa时isa professional standard prornulgated for the first tirne. Note: This English version , a

18、translation from the Chinese text , is solely for guidance. 6 SN/T 1738一2006Inspection of tebufenozide residues in cereals and oi I seeds for import and export-Gas chromatography mass spectrometry method 1 Scope This standard specifies the method of sampling , sarnple preparation and determination o

19、f tebufeno zide residues by gas chromatograph-mass spectrometry in cereals and oil seeds for import and ex port. 了hisstandard is applicable to the determination of residue content of tebufenozide in unpolished rice , rnaize , soybean and peanut for import and export. 2 Sampling and sample preparatio

20、n 2. 1 Inspection lot Each inspection lot should not exceed 200 t. An inspection lot of 200 t , for unpolished rice in bags shall be ca 4 000 bags; for maize or soybean in bags shall be ca 2 200 bags; and for peanut in bags shall be ca 2 400 bags. The cargo of maize or sobean is sometimes in bulk. 丁

21、hecharacteristics of the cargo within the sarne inspection 1时，such as packing , mark, origih , spec ification , grade etc. , should be the same. 2.2 Quantitof sample taken 2. 2. 1 Cargo in bags Calculate the number of bags to be taken by formula (1). where: N一-totalnurnber of bags in a lot; a一一numbe

22、rof bags to be taken. a=VN ( 1 ) Note: If value a is with decirnal , round off the decirnal part , which is added as unity to the integral part of a. 2. 2. 2 Cargo in bulk (maize or soybean) 丁heheight of the cargo pile should not exceed 2 rn. Set up areas and spots for sampling on the pile SN/T 1738

23、-2006 surface. 50 r丁)2is considered as an area , in which 5 spots shall be fixed , one in the center and four at four corners (1 m from the rnargins) of the area. For an additional area , three rnore sarnpling spots shall be fixed. 2. 3 Sampling tools 2.3. 1 Metallic sampler: Length Cncluding handle

24、): 55 cm; diameter: 1. 5 cm 2. 0 cm; groove length: longer than half the diagonal length of the bag. 2.3.2 Metallic double曲casingsampler: length 1 m , 2 m (both including handle) with sorne slots on different sections and respectivelat the sarne heights for both inner and outer casings; length of sl

25、ots: 15 crn ., 20 crn , width of the slots: 2.0 cm-2. 5 cm; inside diameter of the inner casing: 2. 5 cm 3. 0 crn; the probe length 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 or b吨，which can be sealed. 2.3.6 Cloth (or other su

26、itable rnateriaD sheet: For sample dividing(quartering). 2.4 Sampling procedure 2. 4. 1 For cargo in bags 2.4. 1. 1 Sampling by ernptying out: Draw 10 percent of the number of bags specified in 2.2.1 (not less than 3 bags) at anpart of the pile at random. Unsearn and open the bag , and lay it on a c

27、lean cloth sheet (or other clean sheet). Grasp tight two corners of the bag bottom and raise up to an angle of 45. tug backward for ca 1 m until all content of the bag is emptied out. Check whether the qualit of goods is uniform withn and between the bags. After confirming the goods are in norrnal c

28、ondi. tion. scoop up the sarnple from different parts of the out.poured content at random , and promptly place in a sample container. The quantity of sample drawn from each bag should be basicallthe sa口1e.2.4. 1.2 Sampling from inside the bags: Draw the sarnples from the number of bags specified in

29、2. 2. 1 (by deducting the number of bags drawn in 2. 4. 1. 1) as follows: Along the sine wave of the pi le. draw the sarnples from the bags of upper , rniddle and lower parts around the pile at random. For unpolished rice or rnaize proceed as follows: For unpolished rice , using the metallic sarnple

30、r(2. 3. 1) , insert it with its groove facing downward , diagonally into each bag , then turn the sampler 180 , draw out the sampler and promptly pour the sarnple into a container. 8 SN/T 1738-2006 For maize or soybean , using the metallic double-casing sampler (2.3.2) (the slots should be closed wh

31、ile inserting in)diagonally into each bag. Turn the inner casing to open the slots so that the sample mafill up the inner tube. Again turn the inner casing to close the slots and draw out the sampler. Promptly pour the sample into a sarnple container. For peanut , partially unseam岱stitches-5stitches

32、) the bag mouth, scoop out the sample frorn each bag (with a ladle)at the bag opening. Promptly close the bag bseaming， and pour the sample into a sample container. The arnount of sample drawn from each bag should be basically the same as in 2. 4. 1. 1. The total weight of the sample of each lot sho

33、uld be not less than.4 kg. 2.4.2 Sampling from the cargo in bulk: Insert the double心asingsampler(2. 3. 2) successively into the pile at the spots specified in 2. 2. 2 , to appropriate depth at 45 (the slots should be closed while inserting in). Turn the inner casing to open the slots so that the sam

34、ple mafill up the inner tube. Again如rnthe inner casing to close the slots and draw out the sarnpler. Promptly pour the sample into a sample container. The amount of sample drawn frorn all the spots shall be basically the same. The total weight of the sample of each lot should be not less than 4 kg.

35、2.4. 3 Reduction of gross sample For cargo in bags: Pour all the samplesfrom both a) and b) on a clean sheet. Reduce to not less than 2 kg by quartering with a plate. Place in a sample container , seal , label and send te the laborato ry in tirne. For cargo in bulk: Pour all the drawn sample onto a

36、clean sheet and proceed as for cargo in bags de scribed above. 2. 5 Preparation of test sample 2.5. 1 Sampling tools 2. 5. 1. 1 Grinder. 2.5.1.2 Pulverizer. 2. 5. 1. 3 Sieve: 2. 0 mm round.hole sieve. 2. 5. 1.4 Plate for quartering. 9 SN/T 1738-2006 2.5.1.5 Sarnple container: Wide-rnouth bottle, wit

37、h ground stoper. 2. 5. 2 Procedure 2.5.2. 1 For unpolished rice , rnaize or sobean: Reduce bquartering to ca 1 kg. Grind with a grinder(2. 5. 1. 1) to let all pass through a 20-rnesh sieve. Mix thoroughly and divide into two equal portions, place in clean sarnple containers as the test sarnples , se

38、al and label. 2.5.2.2 For peanut: Reduce by quartering to ca 500 g , pulverize with a pulverizer(2. 5. 1.2) to let all pass through a 2. 0 rnm round.hole sieve. Mix thoroughly and divide into two equal portions as the test samples , place in clean sample containers , seal and label. 2. 6 Storage of

39、test sarnple The test samples should be stored OoC _40C and kept awafrorn light. In the course of sarnpling and sarnple preparation , precautions must be taken to avoid contarnination or any factors that macause the change of residue content. 3 Method of determination 3. 1 Principle The test sarnple

40、 are extracted with water-acetone , the extract is partitioned with dichloromethane. Cleaned up by passing through a on Florisil colurnn. Deterrnination is rnade by means of a GC-MS，小sing external standard rnethod. 3. 2 Reagents and materials Unless otherwise specified , all the reagents used should

41、 be analytically pure , water is distilled wa ter. 3.2. 1 Acetone: Redistilled. 3.2.2 Dichlorornethane: Redistilled. 3.2.3 n-hexane: Redistilled. 3.2.4 EthI-acetate: Redistilled. 3.2.5 Anhydrous sodium sulfate: Ignite at 650C for 4 h,and keep in a tightly closed container. 10 SN/T 1738-2006 3. 2. 6

42、Sodium sulfate aqueous solution: 20 g/ L. 3. 2.7 Fiorisil: For chromatograph， 100 mesh-200 mesh , ignite at 650C for 5 h. Before use , heat at 130cC for 4 h and deactivate by adding 2% (m/m) water after cooling. Keep in a tightly closed con tamer. 3.2. 8 Tebufenozide standard: Purity二:0:99%.3.2. 9 T

43、ebufenozide standard solution: Accurately weigh an adequate amount of tebufenozide standard and dissolve in a small volurne of acetone. Dilute with acetone to forrn a standard stock so lution of 1. 00 mg/ mL in concentration. Then dilute the standard stock solution with acetone to the required conce

44、ntration as the standard working solution. 3.3 Apparatus and equiprnent 3.3. 1 Gas chrornatograph equipped with rnass selective detector(MSD). 3. 3. 2 Shaker. 3.3.3 Rotarvacuum evaporator. 3. 3. 4 Colurnn of anhdrous sodium sulfate: 7.5 cm x 1. 5 crn( i. d. ), packed with 5 cm height of anhdrous sod

45、ium sulfate. 3.3.5 Fiorisil column: 25 cm x 1.5 crn( i. d. ), add in sequence 2 crn (heighO of anhydrous sodiurn suifate , 10 9 of Florisil , 2 crn (height) of anhydrous sodiurn sulfate. Rinse the colurnn with 50 mL of n嗣hexanebefore use. 3. 4 Procedure 3.4. 1 Extraction Weigh ca 20 9 (accurate to O

46、. 1 g) of the test sample into a 250 mL co叫calflask with stopp肘，add 40 mL of water and let stand for 2 h. Add 100 rnL of acetone, extract for 30 rnin on a shaker. Filter the extract into a 500 mL separator. Extract the residue with 50 mL of acetone once more , filter and cornbine the washings in the

47、 same separator. Add 200 rnL of sodium sulfate aqueous solution and 100 mL of dichlorornethane , shake for 3 rnin and set aside for separating. Collect the dichioromethane phase. The water phase is again extracted with 2 x 50 rnL of dichloromethane. Cornbined the dichlorornethane phases , and let pa

48、ss through a column of anhydrous sodium sulfate to rernove the water. Collect the effluent in a 250 mL concentrate bottle and evaporate to near dryness in a rotary evaporator with a bath ternperature below 40C. Dissolve the residue with 10 rnL of n-hexane. 11 SNjT 1738，一20063. 4. 2 Cleanup 丁ransfert

49、he above solution into an Florisil column. Wash the column with 50 mL of n-hexane and 50 mL of eth1 acetate-仆hexane(1十9)and discard the effluent. Elute with 100 mL of eth1 acetate也门-hexane(l十1)，collect all the eluate in a 250 mL concentrate bottle and evaporate to dryness in a rotar龟vaporatorwith a bath temperature below 40C . Dissolve the residue and dilute exactly to 5 mL with acetone for GC翩MSdeterminaton. 3.