Determination of 48 fragrance allergens in toys using GC with ion trap MS/MS

This paper presents a method for the simultaneous determination of 48 fragrance allergens in four types of toys (plastic toys, play clays, plush toys, and paper toys) based on GC with ion trap MS/MS. Compared with single‐stage MS, MS/MS is superior in terms of the qualification and quantification of a large range of compounds in complicated matrices. Procedures for extraction and purification were optimized for each toy type. The method proved to be linear over a wide range of concentrations for all analytes with correlation coefficients between 0.9768 and 0.9999. Validation parameters, namely, LODs and LOQs, ranged from 0.005–5.0 and from 0.02–20 mg/kg, respectively. Average recoveries of target compounds (spiked at three concentration levels) were in the range of 79.5–109.1%. Intraday and interday repeatabilities of the proposed method varied from 0.7–10.5% and from 3.1–13.4%, respectively. The proposed method was used to monitor fragrance allergens in commercial toy products. Our findings indicate that this method is an accurate and effective technique for analyzing fragrance allergens in materials composed of complex components.     

玩具中苯酚和双酚A的高效液相色谱-荧光检测方法研究

采用高效液相色谱分离,荧光检测器检测,建立了三种不同类型的玩具中苯酚和双酚A的测定方法.用超声提取的方式处理样品,对提取溶剂和提取时间进行选择,确定以甲醇-水(65:35,V/V)作为提取溶液,超声提取20 min.苯酚和双酚A分别在0.012～1.0 mg/L、0.03～2.5 mg/L范围内线性良好,相关系数均达到0.9999,检出限分别为0.6 mg/kg和1.5 mg/kg,不同加标水平的回收率为90.5%～104.3%,其相对标准偏差为0.4%～3.8%.该方法操作简便,灵敏度高、重现性好,能有效提取和测定三类玩具中的苯酚和双酚A.     

气相色谱-质谱法测定玩具中的4种阻燃剂

建立了玩具中三(2-氯乙基)磷酸酯、磷酸三邻甲苯酯、2,2′,4,4′,5-五溴联苯醚、2,2′,3,3′,4,4′,6,6′-八溴联苯醚等4种阻燃剂的气相色谱-质谱分析方法。玩具样品以V(正己烷):V(二氯甲烷)=1:1混合溶液为提取溶剂,超声提取30min,提取液以DB-5HT石英毛细管色谱柱(15m×0.25mm×0.10μm)分离后进行选择离子监测模式下的定性及定量分析。4种阻燃剂的定量限为0.1mg/kg,在低、中、高3个添加水平范围内,4种阻燃剂的平均回收率为93.5%～97.3%,相对标准偏差在2.4%～4.1%之间。     

ICP-AES法测定玩具涂料中重金属元素总量

研究了不同消解方法对玩具涂料中As,Ba,Cd,Cr,Hg,Pb,Sb,Se有害重金属元素总含量测定结果的影响，确定以HNO3＋酒石酸＋H3PO4溶样并用全谱直读等离子体光谱仪同时测定其八种有害重金属元素总含量的方法。加标回收试验及模拟样品测定结果表明，该方法快速、准确、可靠，且能满足玩具安全标准对各元素的检出限要求，适于进出口玩具的日常检验。     

超高效液相色谱-串联质谱法同时测定玩具中的16种致癌和致敏染料

建立了同时测定玩具中16种致癌和致敏染料(酸性红26、碱性红9、分散蓝1、酸性紫49、分散蓝3、溶剂黄1、分散蓝106、分散橙3、分散黄3、碱性紫1、碱性紫3、分散红1、溶剂黄3、分散蓝124、溶剂黄2、分散橙37)的超高效液相色谱-串联质谱分析方法。纺织品、皮革、纸张、木材、气球、造型黏土、贴纸、可接触液体等不同类型的玩具材料经超声提取后,以Waters ACQUITY UPLC BEH C18色谱柱(50mm×2.1mm,1.7μm)分离后进行UPLC/MS/MS多反应监测模式下的定性及定量分析。16种致癌和致敏染料的方法检出限为1.0～8.0μg/kg;在5～100μg/kg范围内的低、中、高3个添加水平的平均回收率为81.3%～98.6%;日内精密度均小于11%,日间精密度均小于14%。本方法准确、快速、灵敏度高,可用于玩具的实际检验工作。     

Effect of several variables in the polymer toys additive migration to saliva

Capacity to migrate of a representative group of polymeric additives, dyes, antioxidants, hindered amine light stabilizers (HALS) or antistatics, from plastic toys to saliva was analyzed to protect children in their habits of sucking and biting. Most of target additives appear no-regulated in toys normative but adverse effects on human health of some of them have been demonstrated and their presence in others commercial articles normative has been included.In order to offer an effective and easy tool to perform these controls, migration tests by dynamic and static contact, followed by a preconcentration step by liquid-liquid extraction (LLE) and ultra performance liquid chromatographic analysis with ultraviolet-visible and evaporative light scattering detections (UPLC-UV/Vis-ELSD) have been optimized to evaluate the migrated amounts of the additives in saliva simulant. The detection limits of the migration methodologies were ranged from 8.68 × 10⁻² to 1.30 × 10⁻³ mg migrated (L simulant)⁻¹.Influence of several variables on this mass transport, as time, temperature and friction, was also analyzed to achieve the most aggressive methodology to protect consumers.Migration of several studied additives, whose presence has been demonstrated in several purchased commercial toys, has been observed.     

顶空气相色谱-质谱法测定玩具中10种有机物的迁移量

建立了顶空气相色谱-质谱测定玩具中10种有机物迁移量的方法.样品在30mL去离子水中迁移60 min,得到的迁移液经95℃、90 min静态顶空后,通过60 m DB-624色谱柱分离,质谱进行检测,外标法定量.方法对于不同有机物的定量限(LOQ)在16.7～83.3μtg/L之间,线性范围为0.0167～16.7 m...     

气相色谱-离子阱质谱联用测定玩具中8种酯类致敏性芳香剂

建立了气相色谱-离子阱质谱联用测定玩具中丙烯酸乙酯等8种酯类致敏性芳香剂的方法。对于布绒和贴纸玩具样品,采用丙酮超声提取20 min后过0.45μm滤膜直接进样,对于塑料玩具样品,经相应溶剂提取,离心后,澄清溶液经Envi-carb石墨化碳固相萃取小柱净化,丙酮定容,过0.45μm滤膜后通过30 m HP-5 MS色谱柱分离,质谱进行检测,外标法定量。方法对于不同物质的定量限(LOQ)在0.05～8.0 mg/kg之间,线性范围为0.005～50 mg/L,在3个添加水平的平均回收率在80.2%～105.9%之间,RSD在0.7%～8.9%之间。该方法可用于玩具中丙烯酸乙酯等8种酯类致敏性芳香剂的检测。     

EDXRF法快速测定玩具塑料中8种有害元素

铬、砷、硒、镉、锑、钡、汞和铅8种有害元素是玩具安全领域必检项目.目前,标准方法大多需采用湿化学法处理样品,再用仪器进行测试,前处理过程复杂,耗时长、成本高.EDXRF法具有无须样品前处理、对样品非破坏性、成本低、效率高等优点,已广泛用于电子电气产品中有害物质的快速筛选分析,但由于玩具材料和待测元素种类多,大多元素限量...     

Laser-induced breakdown spectroscopy and chemometrics for classification of toys relying on toxic elements

Quality control of toys for avoiding children exposure to potentially toxic elements is of utmost relevance and it is a common requirement in national and/or international norms for health and safety reasons. Laser-induced breakdown spectroscopy (LIBS) was recently evaluated at authors' laboratory for direct analysis of plastic toys and one of the main difficulties for the determination of Cd, Cr and Pb was the variety of mixtures and types of polymers. As most norms rely on migration (lixiviation) protocols, chemometric classification models from LIBS spectra were tested for sampling toys that present potential risk of Cd, Cr and Pb contamination. The classification models were generated from the emission spectra of 51 polymeric toys and by using Partial Least Squares - Discriminant Analysis (PLS-DA), Soft Independent Modeling of Class Analogy (SIMCA) and K-Nearest Neighbor (KNN). The classification models and validations were carried out with 40 and 11 test samples, respectively. Best results were obtained when KNN was used, with corrected predictions varying from 95% for Cd to 100% for Cr and Pb.