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Codeofchina.com is in charge of this English translation. In case of any doubt about the English translation, the Chinese original shall be considered authoritative. This document is drafted in accordance with the rules given in GB/T 1.1-2020 Directives for standardization - Part 1: Rules for the structure and drafting of standardizing documents. This document replaces GB/T 22048-2015 Determination of certain phthalate esters in toys and children’s products. In addition to structural adjustments and editorial changes, the following main technical changes have been made with respect to GB/T 22048-2015: a) DIBP ester and liquid materials are added in "Scope" (see Clause 1); b) GB 6675.2-2014, GB/T 454 and GB/T 27417-2017 are added in "Normative References" (see Clause 2); c) The composite test portion and limit of quantification in "Terms and definitions" are changed (see Clause 3; Clause 3 of Edition 2015); d) The description of ultrasonic extractor is added in "Principle" (see Clause 4); e) Apparatus used in ultrasonic method are added in "Apparatus" (see Clause 6); f) Preparation of liquid material is added in "Sample preparation" (see Clause 7); g) The reaction vessel, extraction procedure and quantification method for Method C are added (see 8.1, 8.2.3 and 8.3.2.2); h) "The volume of dichloromethane may be adjusted according to the extraction equipment" is added (see 8.2.1 and 8.2.2); i) The description of temperature setting for Method B is changed (see 8.2.2; 8.2.2 of Edition 2015); j) Instructions for use of centrifuge are added (see 8.3.1); k) Note on DPHP is added and the range of absolute deviation of retention time is deleted in "Qualitative analysis” (see 8.4.2; 8.4.2 of Edition 2015); l) Notes on Method A and Method B are deleted [see 12c) of Edition 2015]; m) Notes on external standard method and internal standard method are deleted [see 12d) of Edition 2015]; n) Information about DIBP is added (see Annex A); o) A normative annex for performance checking of ultrasonic extractor is added (see Annex E). This standard is modified in relation to ISO 8124-6: 2018 Safety of toys - Part 6: Certain phthalate esters in toys and children’s products. The technical differences with respect to ISO 8124-6: 2018 and their justifications are as follows: a) In accordance with the national standards of China, “This document specifies a method for the determination of esters in 5.3.7, GB 6675.1-2014” and “is applicable to 5.3.7, GB 6675.1-2014” are added in Clause 1 of this document to expand its applicability; b) In Clause 2 and Clause 3 hereof, three normative references, i.e., GB 6675.1-2014, GB 6675.4-2014 and GB/T 27417-2017, are added, among which, GB 6675.4-2014 replaces the international standard ISO 8124-3: 2010 to adapt to the technical conditions in China; c) Two normative references, i.e., GB 6675.2-2014 and GB/T 454, which replaces ISO 8124-1: 2018 and ISO 2758, are added in Clause 2 and E.3.1 hereof to adapt to the technical conditions in China; d) In accordance with the relevant national standards, in Clause 3 hereof, two terms and definitions, i.e., toy and children's product, are added, and the composite test portion and limit of quantification are modified; e) 0.2mL pipette, which is referred to in 5.5.3 of ISO 8124-6: 2018, is added in 6.11 hereof; f) Because different solvent extractors have different settings, the reasonable description of the temperature setting in Method B is changed in 8.2.2 hereof. The following editorial changes have been made in this document: a) This document is named as Determination of certain phthalate esters in toys and children’s products in accordance with relevant national standard; b) “Warning” is deleted in this document; c) The information in 6.13 is incorporated in 8.2.3; d) 8.4.2 lists a textual description of the allowable range of abundance ratio of diagnostic ions; e) The explanation of CAS numbers of DINP and DIDP is added in Table A.1; f) Five materials free of phthalate esters, i.e., ABS, GPPS, MIPS, HIPS and SHIPS are added in G.5 hereof; g) For the purpose of this document, ISO 8124-3: 2010, ASTMF963-11 and AfPS GS.2014: 01 PAK are replaced with ISO 8124-3: 2020, ASTM F963-17 and AfPS GS.2019:01 respectively. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. The issuing body of this document shall not be held responsible for identifying any or all such patent rights. This document was proposed by China National Light Industry Council. This standard is under the jurisdiction of National Technical Committee on Toys of Standardization Administration of China (SAC/TC 253). The previous editions of this document are as follows: ——This standard was firstly issued in 2008 with the serial number of GB/T 22048-2008 and firstly revised in 2015; ——This is the second revision. Determination of certain phthalate esters in toys and children’s products 1 Scope This document specifies a method for the determination of esters in 5.3.7, GB 6675.1-2014. This document specifies a method for the determination of di-iso-butyl ortho-phthalate (DIBP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis-(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DNOP), di-iso-nonyl phthalate (DINP), and di-iso-decyl phthalate (DIDP) (see Table A.1) in toys and children’s products. This document is applicable to toys and children’s products containing polymers and similar materials, textiles, coatings and liquid materials, and is applicable to 5.3.7, GB 6675.1-2014. This document has been validated for polyvinylchloride (PVC) plastics, polyurethane (PU) plastics, and some representative paint coatings (see Annex B). It might also be applicable to other materials of toys and children's products provided that adequate validation is demonstrated. It might also be applicable to other phthalate esters provided that adequate validation is demonstrated. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. GB/T 454 Paper - Determination of bursting strength (GB/T 454-2020, ISO 2758: 2014, MOD) GB 6675.1-2014 Toys safety - Part 1: Basic code GB 6675.2-2014 Safety of toys - Part 2: Mechanical and physical properties (ISO 8124-1: 2000, MOD) GB 6675.4-2014 Safety of toys - Part 4: Migration of certain elements (ISO 8124-3: 2010, MOD) GB/T 27417-2017 Confirmation assessment - Guidance on validation and verification of chemical analytical methods 3 Terms and definitions For the purposes of this document, the terms and definitions given in GB 6675.1-2014, GB 6675.4-2014 and GB/T 27417-2017 and the following apply. 3.1 toy all products and materials designed or intended for children under the age of 14 to play [Source: GB 6675.1-2014, 3.1] 3.2 children's product all products and materials specially designed or intended for children under the age of 14 to use, play and wear, including but not limited to school supplies, infant care products, children's clothing, children's shoes, children's furniture, child safety protectors, baby carriage toys and children's jewelry, etc. 3.3 laboratory sample product in the form in which it is marketed or intended to be marketed 3.4 base material material upon which coatings may be formed or deposited [Source: GB 6675.4-2014, 3.1] 3.5 coating all layers of material formed or deposited on the base material of toys or children’s products, including paints, varnishes, lacquers, inks, polymers, or other substances of a similar nature, whether they contain metallic particles or not, no matter how they have been applied to the toy or children’s product, and which may be removed by scraping with a sharp blade [Source: GB 6675.4-2014, 3.2, modified] 3.6 scraping mechanical removal of coatings down to but not including the base material [Source: GB 6675.4-2014, 3.6] 3.7 test portion portion of homogeneous material taken from a laboratory sample for analysis 3.8 composite test portion mixed test portion formed by physically mixing several test portions of similar material. However, dissimilar materials, for example, textiles and paint coatings, should not be composited 3.9 composite test test performed on the composite test portion 3.10 limit of quantification; LOQ lowest mass concentration or lowest amount of the analyte in the sample that can be quantitatively determined with defined accuracy and precision [Source: GB/T 27417-2017, 3.14, modified] 3.11 method blank aliquot of solvents that is treated exactly as a sample including exposure to glassware, apparatus, and conditions used for a particular test, but with no added sample, which is used to evaluate the contamination of the laboratory environment 4 Principle The phthalate esters in test portion are extracted through a Soxhlet extractor or solvent extractor (see Annex C) with dichloromethane; after which, the phthalate esters in the extract are determined qualitatively and quantitatively by gas chromatograph-mass spectrometer (GC-MS). 5 Reagents and materials 5.1 Dichloromethane, CAS No. 75-09-2, analytical grade or higher. Before being used, each batch of dichloromethane should be subjected to acceptance confirmation to avoid contamination. 5.2 Phthalate reference substances, minimum of 95% purity, see Table A.1. 5.3 Standard stock solution: Weigh accurately an appropriate amount of phthalate standard substance (5.2) to prepare standard stock solution, 100mg/L of DIBP, DBP, BBP, DEHP and DNOP each, and 500mg/L of DINP, DIDP each in dichloromethane (5.1). Standard stock solution should be properly stored at 0~8℃, with a shelf life of three months. 5.4 Standard working solutions (external standard method): A series of standard working solutions (at least five solutions in the range of 0.4~10mg/L for DIBP, DBP, BBP, DEHP and DNOP, 2~50mg/L for DINP and DIDP) is prepared by transferring 0.2~5mL of the standard stock solution (5.3) to a 50mL volumetric flask and making up to the mark with dichloromethane. Standard working solutions should be stored at 0~8℃, with a shelf life of one month. 5.5 Standard working solutions (internal standard method). 5.5.1 Internal reference substances, benzyl benzoate (BB, CAS No.120-51-4) or di-n-amyl phthalate (DAP, CAS No.131-18-0) [also known as di-n-pentyl phthalate (DPP)], minimum of 95% purity. The internal reference substances should not be present in the test portion matrix. 5.5.2 Internal standard stock solution: Accurately weigh an appropriate amount of internal standard substance (5.5.1), with 250mg/L of BB or DAP/DPP, in dichloromethane. Internal standard stock solution should be properly stored at 0~8℃, with a shelf life of three months. 5.5.3 Standard working solutions (internal standard method): A series of standard working solutions (at least five solutions in the range of 0.4~10mg/L for DIBP, DBP, BBP, DEHP and DNOP, 2~50mg/L for DINP and DIDP) is prepared by transferring 0.2~5mL of the standard stock solution (5.3) to a 50mL volumetric flask and adding 2mL of the internal standard stock solution (5.5.2) before making up to the mark with dichloromethane, each of the working solutions containing 10mg/L internal standard substance. The mass concentration of the internal standard solution may be adjusted according to the mass concentration of the test portion, but the mass concentration of internal standard substance of the final sample solution (8.3.3) shall be consistent with that in the standard working solution. Standard working solutions containing internal standard substance should be stored at 0~8℃, with a shelf life of one month. 6 Apparatus 6.1 Phthalate esters are common contaminants which can affect the quantification result even at a low level of concentration. Any type of plastic apparatus that could affect the analysis should be avoided, and glassware and equipment should be scrupulously cleaned before use. 6.2 Gas chromatography-mass spectrometer (GC-MS): with a capillary column coupled to a mass spectrometric detector (EI source) used for the analysis. 6.3 Soxhlet extractor, see Figure C.1. It is equipped with a refrigeration cycle device where necessary. 6.4 Solvent extractor (also known as fat extractor), see Figure C.2. It is equipped with a refrigeration cycle device where necessary. 6.5 Extraction thimble, cellulose. 6.6 Cotton wool. 6.7 Analytical balance, capable of measuring to an accuracy of 1mg. 6.8 Concentration apparatus, for example, a rotary evaporator. 6.9 Solid phase extraction (SPE) cartridge, 1g silica gel/6mL tubes, or equivalent. 6.10 Volumetric flasks, of 5mL, 10mL, 25mL, 50mL, and 100mL nominal capacity. 6.11 Pipettes, of 0.2mL, 0.5mL, 1mL, 2mL, 5mL, and 10mL nominal capacity. 6.12 Organic-phase microporous membrane filter, polytetrafluoroethylene (PTFE) membrane filter, of pore size 0.45μm. 6.13 Ultrasonic extractor, with the temperature controlled internally or externally, and the effective ultrasonic power density ranging from 0.25~2.0W/cm2. Example: The ultrasonic extractor with a gross power of 1,200W (including 200W ultrasonic power and 1,000W heating power) has a water bath area of 400cm2, and an ultrasonic effective power density of 0.50W/cm2(=200W/400cm2). 6.14 Ultrasonic basket, of which, the distance between the bottom of the basket and that of the ultrasonic water bath shall be 3~5cm when hanging on the ultrasonic extractor. 6.15 Sealed glass reaction vessel, which is capable of resisting a pressure of at least 0.2MPa, with a capacity of 2~10 times the volume of dichloromethane added. During ultrasonic extraction, the reaction vessel shall be sealed to prevent the evaporation of dichloromethane. 6.16 Centrifuge: with a centrifugal force of (5,000±500)g. Foreword i 1 Scope 2 Normative references 3 Terms and definitions 4 Principle 5 Reagents and materials 6 Apparatus 7 Test portion preparation 8 Analysis procedure 9 Result calculation 10 Quality control 11 Precision 12 Test report Annex A (Normative) Seven phthalate esters tested in this document Annex B (Informative) Precision Annex C (Informative) Diagrams of Soxhlet extractor and solvent extractor Annex D (Informative) Composite test Annex E (Informative) Performance checking of ultrasonic extractor Annex F (Informative) Example of determination on phthalate esters Annex G (Informative) Background and rationale Bibliography 玩具及儿童用品中特定邻苯二甲酸酯 增塑剂的测定 1 范围 本文件描述了对GB 6675.1—2014中5.3.7增塑剂要求的测定方法。 本文件描述了玩具及儿童用品中邻苯二甲酸二异丁献(DIBP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二(2-乙基)已酯(DEHP)、邻苯二甲酸二正辛酯(DNOP)、邻苯二甲酸二异壬酯(DINP)和邻苯二甲酸二异癸酯(DIDP)共7种邻苯二甲酸酯增塑剂(按照表A.1的规格)的测定方法。 本文件适用于含有聚合物及类似材料、纺织品、涂层和液体材料的玩具及儿童用品,适用于GB 6675.1—2014中5.3.7。本文件已对聚氯乙烯(PVC)、聚氨酯(PU)和部分典型油漆涂层进行验证,见附录B。其他玩具及儿童用品材料经过验证后可参照本文件进行测定。 其他邻苯二甲酸酯增塑剂的检测经过验证后可参照本文件进行。 2 规范性引用文件 下列文件中的内容通过文中的规范性引用而构成本文件必不可少的条款。其中,注日期的引用文件,仅该日期对应的版本适用于本文件;不注日期的引用文件,其最新版本(包括所有的修改单)适用于本文件。 GB/T 454 纸 耐破度的测定(GB/T 454—2020,ISO 2758;2014,MOD) GB 6675.1—2014 玩具安全 第1部分:基本规范 GB 6675.2—2014 玩具安全 第2部分:机械与物理性能(ISO 8124-1:2000,MOD) GB 6675.4—2014 玩具安全 第4部分:特定元素的迁移(ISO 8124-3:2010,MOD) GB/T 27417—2017 合格评定 化学分析方法确认和验证指南 3 术语和定义 GB 6675.1—2014、GB 6675.4—2014、GB/T 27417—2017界定的以及下列术语和定义适用于本文件。 3.1 玩具 toy 设计或预定供14岁以下儿童玩耍时使用的所有产品和材料。 [来源:GB 6675.1—2014,3.1] 3.2 儿童用品 children's product 设计或预定专供14岁以下儿童使用、玩耍、穿戴等的所有产品及材料,包括但不限于学生用品、婴幼儿护理用品、儿童服装、儿童鞋、儿童家具、儿童安全护具、童车玩具和儿童首饰等。 3.3 实验室样品 laboratory sample 包括在市场销售和待进入市场销售的产品。 3.4 基体材料 base material 可以在其表面形成或附着涂层的材料。 [来源:GB 6675.4—2014,3.1] 3.5 涂层 coating 在玩具或儿童用品的基体材料上形成或附着的所有材料层,包括色漆、清漆、生漆、油墨、聚合物或其他类似性质的物质,不管是否含有金属微粒,也不管是通过何种方法附着在玩具上的,且可用锋利的刀刃刮取。 [来源:GB 6675.4—2014,3.2,有修改] 3.6 刮削 scraping 将涂层从基体材料分离的机械过程,不应刮取基体材料。 [来源:GB 6675.4—2014,3.6] 3.7 试样 test portion 取自于实验室样品、用于分析的均匀材料。 3.8 混合测试试样 composite test portion 使用物理方法将几种类似的材料混合形成的测试试样,非类似材料(如纺织品和油漆涂层)不宜混合。 3.9 混合测试 composite test 将多个试样以混合的形式进行的一次测试。 3.10 方法定量限 limit of quantification;LOQ 样品中被测组分能被定量测定的最低质量浓度或最低量,此时的分析结果能确保一定的正确度和精密度。 [来源:GB/T 27417—2017,3.14,有修改] 3.11 方法空白 method blank 测试时除了不加样品外,使用的玻璃器皿,仪器等其他测试条件均与样品测试时一致,用于评估实验室环境的污染情况。 4 原理 用二氯甲烷在索氏(Soxhlet)抽提器、溶剂萃取器(见附录C)或者超声波萃取器中对试样中的邻苯二甲酸酯进行提取,用气相色谱/质谱联用仪(GC-MS)对提取液进行定性及定量分析。 5 试剂和材料 5.1 二氯甲烷:CAS号75-09-2,分析纯或以上级别,每批二氯甲烷使用前,宜进行验收确认以避免污染。 5.2 邻苯二甲酸酯标准物质:纯度不低于95%,按照表A.1的规格。 5.3 标准储备溶液:分别准确称取适量的邻苯二甲酸酯标准物质(5.2),用二氧甲烷(5.1)配制成DIBP、DBP、BBP,DEHP、DNOP质量浓度为100mg/L,DINP、DIDP质量浓度为500mg/L的标准储备溶液。标准储备溶液宜在0℃~8℃温度下保存,有效期3个月。 5.4 标准工作溶液(外标法):取0.2mL~5mL的标准储备溶液(5.3),用二氯甲烷定容至50mL,制备一组标准工作溶液(配制DIBP、DBP、BBP、DEHP、DNOP质量浓度为0.4mg/L~10mg/L,DINP、DIDP质量浓度为2mg/L~50mg/L的至少5个标准工作溶液)。标准工作溶液宜在0℃~8℃温度下保存,有效期1个月。 5.5 标准工作溶液(内标法)。 5.5.1 内标物:苯甲酸苄酯(BB,CAS号120-51-4)或者邻苯二甲酸酯二戊酯(DAP/DPP,CAS号131-18-0),纯度不低于95%。试样不能含有内标物。 5.5.2 内标储备溶液:分别准确称取适量的内标物质(5.5.1),用二氯甲烷配制成BB或者DAP/DPP质量浓度为250mg/L的内标储备溶液。内标储备溶液宜在0℃~8℃温度下保存,有效期3个月。 5.5.3 标准工作溶液(内标法):取0.2mL~5mL的标准储备溶液(5.3)至50mL容量瓶,分别加入2mL的内标储备溶液(5.5.2),用二氯甲烷定容至50mL,制备一组标准工作溶液(配制DIBP、DBP、BBP、DEHP、DNOP质量浓度为0.4mg/L~10mg/L,DINP、DIDP质量浓度为2mg/L~50mg/L的至少5个标准工作溶液),每个工作溶液含有10mg/L的内标物。 内标物的质量浓度可以根据测试试样的质量浓度相应进行调整,但是最终样品溶液中的内标质量浓度(8.3.3)应与标准工作溶液中的内标物质量浓度一致。含内标的标准工作溶液宜在0℃~8℃温度下保存,有效期1个月。 6 仪器和设备 6.1 实验室常用玻璃器皿,邻苯二甲酸酯是一种常见污染物,即使少量也会影响定量结果。建议避免使用任何可能对分析造成污染的塑料设备。玻璃器皿和设备在使用前宜清洗干净。 6.2 气相色谱/质谱联用仪(GC-MS):配石英毛细管色谱柱和质谱检测器(EI源)。 6.3 索氏(Soxhlet)抽提器:见图C.1。必要时,带冷冻循环装置。 6.4 溶剂萃取器(又称脂肪抽提器),见图C.2。必要时,带冷冻循环装置。 6.5 抽提纸筒:用纤维素制成。 6.6 脱脂棉。 6.7 分析天平:精确至1mg。 6.8 浓缩仪:如旋转蒸发器等。 6.9 固相萃取柱(SPE):1g硅胶/6mL柱子,或等同。 6.10 容量瓶:容量分别为5mL、10mL、25mL、50mL、100mL。 6.11 移液管:容量分别为0.2mL、0.5mL、1mL、2mL、5mL、10mL。 6.12 有机相微孔滤膜:孔径0.45μm,推荐使用聚四氟乙烯(PTFE)微孔滤膜。 6.13 超声波萃取器:可内部或外部控温,超声有效功率密度范围为0.25W/cm2~2.0W/cm2。 示例: 总功率为1200W(包括超声有效功率200W和加热功率1000W)的超声波萃取器,水浴面积为400cm2,其超声有效功率密度为0.50W/cm2(=200W/400cm2)。 6.14 超声波吊篮:当悬挂在超声波萃取器时,吊篮底面离超声波水浴底部的距离应为3cm~5cm。 6.15 可密封的玻璃反应容器:至少能抵抗0.2MPa压力,容量为所加二氯甲烷体积的2倍~10倍。在超声波萃取过程中,反应容器应密封以防止二氯甲烷的蒸发。 6.16 离心机:离心力(5000±500)g。 7 试样制备 样品制备过程不应改变样品材料的化学属性。 固体材料:使用刀刃或合适的切削工具从实验室样品(3.3)上刮削试样并剪碎。对油漆涂层取样时应小心地从样品的基体材料上刮削油漆涂层,尽量不要刮削到基体材料。将其制成最大尺寸不超过5mm的均匀碎片。也可使用合适的样品粉碎装置粉碎制备试样。 液体材料:使用合适的设备,如注射器,移取实验室样品(3.3)。宜特别注意避免交叉污染。 对于单一实验室样品中单一材料的取样量不足10mg时免除测试。 可以制备混合测试试样用于筛查测试,筛查测试过程见附录D。 8 分析步骤 8.1 样品称重 称取约1g(精确至0.001g)试样放入抽提纸筒(6.5)或可密封的玻璃反应容器(6.15)。若无法获得1g试样,最少应称取0.1g试样。 8.2 提取 可依实际情况任选以下一种方法进行提取。 8.2.1 方法A 将试样置于250mL索氏抽提器(6.3)的抽提纸筒(6.5)中。为了防止试样漂浮,可在抽提纸筒上层放置脱脂棉(6.6)。 在250mL圆底烧瓶中加入120mL二氯甲烷(5.1),提取6h,每小时回流次数不少于4次,必要时,使用冷却循环装置进行冷却回流。 二氯甲烷的体积可根据抽提设备相应进行调整。 冷却后,用合适的浓缩仪(6.8)浓缩至剩下约10mL左右的提取液,注意防止被完全蒸干。 建议控制旋转蒸发器水浴温度在40℃~50℃,同时保持压力在30kPa~45kPa。 注意控制回流和浓缩的温度,防止邻苯二甲酸酯的损失。 8.2.2 方法B 将试样置于溶剂萃取器(6.4)的抽提纸筒(6.5)中。为了防止试样漂浮,可在抽提纸筒上层放置脱脂棉(6.6)。 在萃取瓶中加入80mL二氯甲烷(5.1),设置合适温度(如80℃),使得二氯甲烷沸腾并回流,浸提1.5h,再淋洗1.5h,必要时,使用冷却循环装置进行冷却回流。最后浓缩至约10mL左右的提取液。 二氯甲烷的体积可根据抽提设备相应进行调整。 注意控制回流和浓缩的温度,防止邻苯二甲酸酯的损失。 8.2.3 方法C 8.2.3.1 固体材料 将试样置于可密封的玻璃反应容器(6.15)中,加入25mL二氯甲烷。将容器置于超声波萃取器(6.13)中,超声波水槽中的液面要高于反应容器中二氯甲烷的液面,起始温度(60±2)℃,连续超声60min。超声波萃取器的性能检查按附录E进行。 注:如材料在二氯甲烷中不溶解或者溶胀,方法A或方法B可能更合适。 8.2.3.2 液体材料 将试样置于可密封的玻璃反应容器(6.15)中,加入15mL二氯甲烷。将容器置于超声波萃取器(6.13)中,超声波水槽中的液面要高于反应容器中二氯甲烷的液面,起始温度(60±2)℃,连续超声60min。超声波萃取器的性能检查按附录E进行。 8.3 分析溶液准备 8.3.1 通则 由8.2.1,8.2.2或者8.2.3得到的提取液如出现浑浊,可在过滤前使用离心机(6.16)在离心力5000g条件下进行离心处理。必要时,可先用固相萃取柱(6.9)对提取液进行净化处理。净化前先用10mL二氯甲烷预洗活化,并丢弃活化液,然后上样,再用3mL二氯甲烷淋洗3次并收集洗脱液。 提取液或者净化液,在室温下,可依实际情况选择8.3.2外标法或者8.3.3内标法进行定容。 8.3.2 定容(外标法) 8.3.2.1 方法A和方法B 转移提取液或者洗脱液至25mL容量瓶中,并用二氯甲烷定容,经有机相微孔滤膜(6.12)过滤后,待GC-MS(6.2)分析。 最终定容体积可以根据测试试样的质量和浓度相应进行调整,注意不宜影响方法定量限(10.1)。 8.3.2.2 方法C 8.3.2.2.1 固体材料 不需要定容,经有机相微孔滤膜(6.12)过滤后,使用GC-MS(6.2)分析提取液或者洗脱液。 8.3.2.2.2 液体材料 转移提取液至25mL容量瓶中,并用二氯甲烷定容,经有机相微孔滤膜(6.12)过滤后,待GC-MS(6.2)分析。 最终定容体积可以根据测试试样的质量和浓度相应进行调整。注意不宜影响方法定量限(10.1)。 8.3.3 定容(内标法) 对于方法A和方法B,转移提取液或者洗脱液至25mL容量瓶中,加入1mL的内标储备溶液(5.5.2),并用二氯甲烷定容,定容后的溶液中含有10mg/L的内标物。经有机相微孔滤膜(6.12)过滤后,待GC-MS(6.2)分析。 最终定容体积和加入的内标储备溶液的体积都可以根据测试试样的质量和浓度相应进行调整,但是最终样品溶液中的内标质量浓度应与标准工作溶液(5.5.3)中的内标物质量浓度一致。 8.4 测定 8.4.1 GC-MS工作条件 由于测试结果取决于所使用的仪器,因此无法给出色谱分析的通用参数。设定的参数应保证色谱测定时被测组分与其他组分能够得到有效的分离。以下参数可供参考,具体实例见附录F。 a) 色谱柱:石英毛细管柱,非极性(5%苯甲基聚硅氧烷)或等效; b) 柱温:程序升温; c) 载气:恒定流量的氦气或氢气; d) 进样方式:分流或不分流进样; e) 电离方法:电子电离源(EI),70eV; f) 检测方式:全扫描模式(full scan)定性,选择离子监测(SIM)定量。 8.4.2 定性分析 通过对比试样和标准工作溶液中目标物的保留时间和特征离子的相对丰度来进行定性分析。 以下条件可用于判定样品中是否含相应的邻苯二甲酸酯: a) 样品中目标物的保留时间与标准工作溶液中目标物的保留时间的偏差在±0.5%范围内; b) 特征离子(见表F.1)在标准工作溶液中目标物的保留时间处出现; c) 特征离子的相对丰度与标准工作溶液中目标物的相对丰度相一致(相对丰度>50%,允许±10%的偏差;相对丰度在20%~50%之间,允许±15%的偏差;相对丰度在10%~20%之间,允许±20%的偏差;相对丰度≤10%,允许±50%的偏差)。 注:DINP或DIDP的某些同分异构体会干扰DINP或DIDP的定性定量。例如,邻苯二甲酸二(2-丙基庚)酯(DPHP,CAS号53306-54-0)是DIDP的异构体之一。很难将DPHP与DIDP分离,但可以通过峰型、保留时间和丰度比等特征来识别。 8.4.3 定量分析 8.4.3.1 综述 实验室可依实际情况任选外标法或者内标法进行定量,选择条件见G.4。 选取至少5个不同质量浓度的标准工作溶液(5.4或5.5.3)进行测定,以峰面积对质量浓度绘制标准曲线。标准曲线的线性相关系数不小于0.995,样品溶液中邻苯二甲酸酯的相应值应在仪器的线性范围内,如有必要,可用二氯甲烷进行稀释。 由于GCMS对不同CAS号的DINP、DIDP标准物质的响应不同,实验室应尽可能选择与试样相近的标准物质,同时应在报告中标明DINP和DIDP的CAS号,见第12章中f)。 对DINP和DIDP的同分异构体进行峰面积积分时,应将基线拉平后再积分。 注:由于不可分离的同分异构体的存在,DNOP、DINP和DIDP的出峰存在部分重叠,通过选用m/z=279(DNOP)、m/z=293(DINP)和m/z=307(DIDP)的定量离子可在最大程度上减少相互之间的干扰。 8.4.3.2 校准曲线(外标法) 按式(1)计算标准曲线的斜率和纵坐标截距: A=a1×ρ+b1 (1) 式中: A——标准工作溶液中特定的邻苯二甲酸酯的定量离子的峰面积或峰面积之和; a1——校准曲线的斜率,单位为升每毫克(L/mg); ρ——标准工作溶液中特定邻苯二甲酸酯的质量浓度,单位为毫克每升(mg/L); b1——校准曲线的纵坐标截距。 8.4.3.3 校准曲线(内标法) 按式(2)计算标准曲线的斜率和纵坐标截距: (2) 式中: A——标准工作溶液中特定的邻苯二甲酸酯的定量离子的峰面积或峰面积之和; AIS——标准工作溶液中内标物的定量离子的峰面积; a2——校准曲线的斜率; ρ——标准工作溶液中特定邻苯二甲酸酯的质量浓度,单位为毫克每升(mg/L); ρIS——标准工作溶液内标物的质量浓度,单位为毫克每升(mg/L); b2——校准曲线的纵坐标截距。 注:当样品溶液的内标质量浓度和标准工作溶液的内标质量浓度是一致的时候,一般设置内标法中内标物质量浓度ρIS=1。 9 结果计算 9.1 外标法 样品中特定邻苯二甲酸酯的含量按式(3)计算,保留3位有效位数。 (3) 式中: ws——试样中特定邻苯二甲酸酯的含量,%; A——试液中邻苯二甲酸酯的定量离子的峰面积或峰面积之和; b1——校准曲线的纵坐标截距,可从式(1)获得; a1——校准曲线的斜率,可从式(1)获得,单位为升每毫克(L/mg); V——试液定容体积,单位为毫升(mL); m——试样质量,单位为克(g); D——稀释倍数。 9.2 内标法 样品中特定邻苯二甲酸酯的含量按式(4)计算,计算结果表示为质量分数(%),保留3位有效位数。 (4) 式中: ws——试样中特定邻苯二甲酸酯的含量,%; A——试液中邻苯二甲酸酯的定量离子的峰面积或峰面积之和; AIS——试液中内标物的定量离子的峰面积; b2——校准曲线的纵坐标截距,可从式(2)获得; ρIS——样品溶液内标物质的质量浓度,单位为毫克每升(mg/L); a2——校准曲线的斜率,可从式(2)获得; V——试液定容体积,单位为毫升(mL); m——试样质量,单位为克(g); D——稀释倍数。 注:当样品溶液的内标质量浓度和标准工作溶液的内标质量浓度是一致的时候,一般设置内标法中内标物质量浓度ρIS=1。 10 质量控制 10.1 方法定量限 本文件中7种邻苯二甲酸酯增塑剂含量的方法定量限为; DIBP、DBP、BBP、DEHP、DNOP:0.001%; DINP、DIDP: 0.005%。 10.2 方法空白试验 每批样品均需做方法空白试验。除了不加样品外,采用与样品测试相同的测试程序。空白试验的结果可用来评估测试过程受到的污染。空白试验结果应小于方法定量限(10.1)。 10.3 回收率 将1mL标准储备溶液(5.3)当作样品按照第8章和第9章的步骤进行操作。每种邻苯二甲酸酯的回收率为80%~120%。 10.4 校准曲线核查 每20个样品需要测试一次标准工作溶液(中间点)以检查标准曲线,每种邻苯二甲酸酯的回收率为85%~115%。 11 精密度 本文件方法的精密度试验结果见附录B。 12 测试报告 测试报告应至少包括以下内容: a) 样品的完整信息; b) 本文件的编号(包括年号); c) 提取方法; d) 定量方法; e) 特定邻苯二甲酸酯的定量测试结果,数值以%表示; f) 使用到的DINP或DIDP标准物质的CAS号; g) 与本文件的任何偏离; h) 在测试中观察到的异常现象; i) 测试日期。 |
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