聚氯乙烯塑料中多种邻苯二甲酸酯类增塑剂的同时测定

为了在线监控聚氯乙烯塑料中增塑剂的含量,利用傅立叶变换红外光谱法-ATR技术测定样品的红外光谱,采用偏最小二乘法对所测红外光谱进行分析,建立了一种无损快速分析方法,定量地测定聚氯乙烯塑料中多种邻苯二甲酸酯类增塑剂的含量。该方法测量精密度的变异系数小于6%,测量准确度的变异系数小于3%。该方法不受基体的干扰,简单快速,适合于流水线的质量控制。     

Heterogeneous oxidation of indoor surfaces by gas‐phase hydroxyl radicals

We investigate heterogeneous oxidation kinetics of monolayer‐thick, surface‐sorbed organics, namely di‐n‐octyl phthalate (DnOP) and palmitic acid (PA), with gas‐phase OH. The pseudo‐first order rate constants for organic loss at OH concentrations of 1.6 × 10⁸ molecules/cm³ are: (2.3 ± 0.1) × 10^?4 to (4.8 ± 0.8) × 10^?4 s^?1, and (1.3 ± 0.5) × 10^?4 s^?1 for DnOP and PA, respectively. Films developed in indoor office environments over a few weeks are also oxidized using the same OH concentration. Heterogeneous decay rate constants of mass signals from these films, attributed to phthalates (MW = 390.6) and to PA, are similar to those for the single‐component films, ie, (1.9 ± 0.4) × 10^?4 to (3.4 ± 0.5) × 10^?4 s^?1, and (1.1 ± 0.4) × 10^?4 s^?1, respectively. These results suggest that the lifetimes for OH heterogeneous oxidation of monolayer‐thick indoor organic films will be on the timescale of weeks to months. To support this argument, we present the first analysis of the mass transfer processes that occur when short‐lived gas‐phase molecules, such as OH, are taken up by reactive indoor surfaces. Due to rapid chemical production, the diffusion limitation to mass transfer is less important for short‐lived molecules than for molecules with little chemical production, such as ozone.     

A general mechanistic model for predicting the fate and transport of phthalates in indoor environments

A mechanistic model that considers particle dynamics and their effects on surface emissions and sorptions was developed to predict the fate and transport of phthalates in indoor environments. A controlled case study was conducted in a test house to evaluate the model. The model‐predicted evolving concentrations of benzyl butyl phthalate in indoor air and settled dust and on interior surfaces are in good agreement with measurements. Sensitivity analysis was performed to quantify the effects of parameter uncertainties on model predictions. The model was then applied to a typical residential environment to investigate the fate of di‐2‐ethylhexyl phthalate (DEHP) and the factors that affect its transport. The predicted steady‐state DEHP concentrations were 0.14 μg/m³ in indoor air and ranged from 80 to 46 000 μg/g in settled dust on various surfaces, which are generally consistent with the measurements of previous studies in homes in different countries. An increase in the mass concentration of indoor particles may significantly enhance DEHP emission and its concentrations in air and on surfaces, whereas increasing ventilation has only a limited effect in reducing DEHP in indoor air. The influence of cleaning activities on reducing DEHP concentration in indoor air and on interior surfaces was quantified, and the results showed that DEHP exposure can be reduced by frequent and effective cleaning activities and the removal of existing sources, though it may take a relatively long period of time for the levels to drop significantly. Finally, the model was adjusted to identify the relative contributions of gaseous sorption and particulate‐bound deposition to the overall uptake of semi‐volatile organic compounds (SVOCs) by indoor surfaces as functions of time and the octanol‐air partition coefficient (K_oa) of the chemical. Overall, the model clarifies the mechanisms that govern the emission of phthalates and the subsequent interactions among air, suspended particles, settled dust, and interior surfaces. This model can be easily extended to incorporate additional indoor source materials/products, sorption surfaces, particle sources, and room spaces. It can also be modified to predict the fate and transport of other SVOCs, such as phthalate‐alternative plasticizers, flame retardants, and biocides, and serves to improve our understanding of human exposure to SVOCs in indoor environments.     

儿童用品中邻苯二甲酸盐的检测

文章采用超声震荡萃取—气相色谱法建立测定儿童用品中邻苯二甲酸酯的方法;以正己烷为萃取溶剂,然后采用气相色谱法—氢火焰离子检测器,进行检测分析,该方法的平均回收率为69.0%~103.2%,相对平均偏差为1.8%~5.9%。该方法用于儿童用品样品中14种邻苯二甲酸酯的测定,具有较好的准确性。     

室内空气中酞酸酯类物质分析的研究

以固相微萃取（SPME）方法为前处理和分离手段采集室内空气中的酞酸酯类物质，进而在GC／MS上对其进行分析测定。通过对SPME中使用的极性与非极性纤维萃取头的萃取效果进行对比．确立了该类室内空气中酞酸酯类物质的分离和分析方法．并且比较了不同环境中室内各种邻苯二甲酸酯类的相对浓度大小。实验发现．与用传统的有机溶剂吸收空气中的化合物的方法相比．该方法可以检测出低浓度邻苯二甲酸二（2-乙基己基）酯（DEHP）．并且简化了实验过程．减少了干扰及有机溶液的使用量．并可以测定出浓度较低的酞酸酯类物质。     

Oestrogenicity of paper and cardboard extracts used as food containers

Bisphenol-A (BPA), dibutyl phthalate (DBP), and di-2-ethylhexyl phthalate (DEHP), which are common chemical residues in food-packaging materials, were investigated in paper and cardboard containers used for take-away food. The oestrogenicity of aqueous extracts was tested in E-Screen bioassay and analysis carried out by high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC/MS). Oestrogenicity was demonstrated in 90% of extracts (geometric mean [GM] = 11.97 pM oestradiol equivalents g^-1). DEHP, DBP, and BPA (GM = 341.74, 37.59, and 2.38 ng g^-1 of material) were present in 77.50, 67.50, and 47.50% of samples, respectively. In bivariate analyses, no significant association was found between the levels of these chemicals and oestrogenicity in cardboard/paper extracts. A close-to-significant association was found between oestrogenicity and DBP (β = 1.25; p = 0.06) in paper extracts, which reached statistical significance in multivariate analysis (β = 1.61; p = 0.03). Paper and cardboard used in food packaging may contribute to the inadvertent exposure of consumers to endocrine-disrupting chemicals.     

基于斑马鱼幼鱼的塑化剂肝毒性危害识别研究

目的 采用塑化剂邻苯二甲酸二乙基己酯（DEHP）和邻苯二甲酸二丁酯（DBP）作为阳性对照,建立斑马鱼幼鱼脂肪肝毒性风险评估模型进行塑化剂邻苯二甲酸丁酯苯甲酯（BBP）肝毒性危害识别。方法 分析DEHP和DBP暴露后斑马鱼肝脏脂肪信号强度及过氧化物酶体增殖物激活受体（PPAR）靶基因CD36的表达,初步构建斑马鱼幼鱼肝毒性模型;基于此模型对BBP进行肝毒性评价,此外采用肝脏表达绿色荧光转基因斑马鱼幼鱼进行肝密度分析、甘油三酯（TG）定量检测以及成鱼肝脏病理检查进一步验证模型的可靠性,应用基准剂量法（BMD）推导关键效应点。结果 DEHP、DBP表现出极显著诱发脂肪肝风险（均P<0.01）,显著上调CD36相对表达量（P<0.001,P<0.05）,提示造模成功。BBP（0.000 012 5%、0.000 025%、0.000 05%）诱发斑马鱼幼鱼显著的脂质沉积（P<0.05,P<0.001,P<0.001）、显著影响密度（P<0.05,P<0.01,P<0.01）、显著增加TG蓄积（P<0.05,P<0.05,P<0.01）、上调CD36基因表达。此外,BBP（≥0.000 012 5%）诱发斑马鱼成鱼肝脏部位脂质空泡形成、空泡间隙和数量减少,提示BBP具有明显的肝毒性。关键效应为肝脏脂肪信号强度（S）,基准剂量下限（BMDL）值为0.013 mg/L。结论 本研究成功构建了一种通过肝脏脂肪信号强度来识别塑化剂肝毒性的斑马鱼幼鱼模型,结合基准剂量法进一步为塑化剂肝毒性危害识别提供科学依据。     

新型固相萃取-高效液相色谱检测饮用水中的 邻苯二甲酸脂类物质

目的建立基于新型高效的样品前处理技术即固相萃取-高效液相色谱联用技术同时检测饮用水中七种邻苯二甲酸酯类物质的方法。方法以3-氨基丙基三乙氧基硅烷作为功能单体,四乙氧基硅烷作为交联体,并加入醋酸,合成新型的高选择性材料,并用作为固相萃取材料,吸附七种邻苯二甲酸脂类物质。结果高效液相色谱等度分析方法的最佳检测条件为:流动相为乙腈和水(96:4,V:V);运行时间20 min;检测波长为230 nm;流速1.0 m L/min;柱温30℃;进样量20μL。目标化合物线性范围较宽,其中DMP、DBP、DIDP为0.5~100 mg/L,DCHP、BBP、DEHP为0.5~25 mg/L,DEP为0.5~10 mg/L;该方法对7种目标化合物的检测限在0.18μg/L~1.86μg/L范围内,6次重复实验精密度在1.18%~5.20%之间,标准添加回收率在63.5%~108.4%之间。结论该方法可以用于饮用水中苯二甲酸脂类物质的定量检测。     

Migrated phthalate levels into edible oils

The determination of phthalates in edible oils (virgin olive oil, olive oil, canola oil, hazelnut oil, sunflower oil, corn oil) sold in Turkish markets was carried out using gas chromatography–mass spectrometry. Mean phthalate concentrations were between 0.102 and 3.863 mg L^?1 in virgin olive oil; 0.172 and 6.486 mg L^?1 in olive oil; 0.501 and 3.651 mg L^?1 in hazelnut oil; 0.457 and 3.415 mg L^?1 in canola oil; 2.227 and 6.673 mg L^?1 in sunflower oil; and 1.585 and 6.248 mg L^?1 in corn oil. Furthermore, the influence of the types of oil and container to the phthalate migration was investigated. The highest phthalate levels were measured in sunflower oil. The lowest phthalate levels were determined in virgin olive oil and hazelnut oil. The highest phthalate levels were determined in oil samples contained in polyethylene terephthalate.