Association between Phthalate Exposure and the Use of Plastic Containers in Shanghai Adults

Objective Consuming phthalates may be due to the presence of food contact materials, such as plastic containers. In this study, we investigated the association between plastic container use and phthalate exposure in 2,140 Shanghai adults. Methods Participants completed a questionnaire on the frequency of using plastic containers in different scenarios in the previous year （e.g., daily, weekly） and on the consumption of plastic-packaged foods in the previous three days （yes or no）. Urinary phthalate metabolites were used to assess the association between phthalate exposure and the use of plastic containers. Results The metabolites of di-（2-ethylhexyl） phthalate （DEHP） were the most frequently detected in urine. The results revealed that phthalate exposure was associated with consumption of plastic-packaged breakfast or processed food items in the previous three days. The consumption of these two food items had strong synergistic effects on increasing urinary concentrations of most phthalate metabolites. Conclusion Our results of plastic-packaged breakfast and processed food may be explained by the use of flexible plastic containers, indicating the importance of risk assessment for the application of flexible plastic containers.

Analysis of Phthalate Esters in Air, Soil and Plants in Plastic Film Greenhouse

The phthalate esters such as DMP, DEP, DBP and DEHP in air, soil and plant samples in plastic film greenhouse were clean up with fine silica gel column and determined with HPLC. It was found that the concentrations of PEs in air and soil samples in plastic film greenhouse are much higher than those of contrast samples. But concentrations of PEs in plants in plastic film greenhouse are not remarkably affected by the pollution of air and soil.

Irradiation Effect on Photodegradation of Pure and Plasticized Poly (4-Methylstyrene) in Solid Films

The photodegradation of irradiated thin films of poly (para-methylstyrene) with 265 nm radiations in the presence of airand as a function of irradiation time has been studied using UV-VIS, fluorescence and FT-IR Spectroscopic techniques. The influence of phthalate and terephthalate plasticizers on stability of poly (para-methylstyrene) towards irradiations was also investigated. Blending with phthalate plasticizers was found to cause a higher efficiency of photodegradation than that obtained in doping with terephthalate plasticizers. The intensity of absorption was also found to increase with time of irradiation and in change in the shape of the spectra at longer wavelength, thus indicating a possibility of photodegradation of polymer chains. The analysis of the FT-IR spectra of the irradiated and non-irradiated samples, shows a predominant absorption associated with carbonyl compounds with 1740 cm-1. In addition, the observed increase in the intensities of the carbonyl and hydroxyl regions of the FT-IR spectra, have provided an evidence for the photodegradation as well as photo-oxidation of polymeric chains. The presence of the plasticizer in the polymer backbone was found to accelerate the photodegradation of polymeric chains.

Study the Influence of UV-Irradiation on the Photo Stability of Pure and Plasticized Poly (4-Vinyl Biphenyl) in Solid Films

The effect of UV irradiation and blending with phthalate and terephthalate plasticizers on the photo-stability of Poly (4-vinyl biphenyl) was studied at different intervals of irradiation time and in presence of air. The increase in irradiation time on the photodegradation of polymer thin films caused a change in the intensity and shape of the fluorescence band. It has been found that the stability of the polymer decreases with the increase of irradiation time, and to increases with the increase of the amount of added phthalate and terephthalate plasticizers, which is evidence of polymer photodegradation. The FT-IR spectra of irradiated pure and blended polymer with phthalate and terephthalate plasticizers showed a decrease in some absorption bands and increase in the other bands, this is also another factor for the occurrence of photo degradation of the irradiated polymer. The increase in the intensity of absorption of carbonyl and hydroxyl region, indicates a possible photogegradation of polymeric chains and the formation of alcohols, aliphatic ketones and to the increase in the number of (C=C) that resulted from hydrogen abstraction during chains-scission.

食品接触材料中非邻苯类塑化剂迁移及潜在危害的研究进展

近年来,邻苯类塑化剂不断被曝出各式各样的安全隐患问题,其使用已经被严格限制。与此同时,非邻苯类塑化剂由于具有比邻苯类塑化剂更低的毒性,在实际应用中越来越受到厂家的青睐,被广泛使用于食品接触材料当中。然而,伴随着其使用范围的不断拓展以及使用量的持续增加,食品接触材料中非邻苯类塑化剂的迁移情况以及其可能带来的危害绝不能忽视。本文对食品接触材料中非邻苯类塑化剂的相关概念及种类、迁移情况、潜在危害、检测方法进行了综述,旨在为针对食品接触材料中非邻苯类塑化剂进行准确的风险评估提供重要的参考依据。

解淀粉芽孢杆菌W48对大蒜产量品质及土壤质量提升效果研究

为明确微生物菌剂改善大蒜产地环境、提升产量品质的效果,利用常规施肥结合解淀粉芽孢杆菌W48发酵液进行大蒜田土壤处理,测定大蒜产量和品质相关指标,监测土壤理化性质及生物转化相关酶活性变化,定量分析菌剂处理后土壤和大蒜中邻苯二甲酸酯类塑化剂(PAEs)含量差异。结果表明,W48菌株具有分泌吲哚乙酸的能力,同时具备溶磷和产铁载体的潜力。施用W48微生物菌剂显著增加了植物根际土壤有机质、碱解氮、有效磷和速效钾含量,改善根际区域营养环境,提高了土壤碱性磷酸酶、蔗糖酶和脲酶等生物转化相关酶活性,提高了土壤氮、磷元素利用效率;与对照相比,微生物菌剂处理的小区大蒜增产10%,可溶性糖和维生素C含量等品质指标均有提高,其中可溶性糖显著增加了30%;邻苯二甲酸二正丁酯(DBP)和邻苯二甲酸二(2-乙基)己酯(DEHP)是土壤和大蒜中PAEs的主要检出类型,土壤中的平均浓度分别达到1874.05和337.12μg/kg,大蒜中几种PAEs残留量普遍较高,DBP最高为666.57μg/kg,其次为邻苯二甲酸二异丁酯(DIBP)409.93μg/kg和邻苯二甲酸丁苄酯(BBP)433.65μg/kg。菌剂对PAEs具有显著的体外降解能力,土壤处理后能够显著降低土壤中PAEs浓度,对DBP、DEHP和邻苯二甲酸二甲酯(DMP)的去除率分别为25.5%、76.1%和48.4%,但对大蒜中的PAEs含量影响不显著。以上结果为大蒜产地土壤污染物修复及改良提供了技术支撑。

乳品中邻苯二甲酸酯类塑化剂的检测与安全控制研究进展

乳品是合理膳食的重要组成部分,是人类重要的营养源之一。乳品从生产到上市需要经过多重环节,极易在生产、加工以及包装过程中受到塑化剂的污染,需要引起重点关注。邻苯二甲酸酯(phthalates,PAEs)类化合物是最常用的塑化剂之一,能够提高材料的耐久性和弹性,但由于PAEs和塑料基质连接不够紧密,可从基质迁移到环境或食品中,因此有必要对乳品中的PAEs进行检测和风险评估。本文阐述了乳品中塑化剂的来源和危害,介绍了PAEs在国内外采集工具、护理品、食品中的限量要求,针对乳品中PAEs的多种检测方法展开文献调研,包括气相色谱法、液相色谱-串联质谱法、免疫分析法等,通过总结、归纳、比较现阶段各类方法的优缺点,以及适用情况和场合,以期为不同需求的乳品中塑化剂检测提供有效的方法选择。

Analysis of the influencing factors of PAEs volatilization from typical plastic products

The primary emphasis of this research was to investigate the foundations of phthalate（PAEs） pollutant source researches and then firstly confirmed the concept of the coefficient of volatile strength, namely phthalate total content in per unit mass and unit surface area of pollutant sources. Through surveying and evaluating the coefficient of volatile strength of PAEs from typical plastic products, this research carried out reasonable classification of PAEs pollutant sources into three categories and then investigated the relationship amongst the coefficient of volatile strength as well as other environmental factors and the concentration level of total PAEs in indoor air measured in environment chambers.Research obtained phthalate concentration results under different temperature, humidity,the coefficient of volatile strength and the closed time through the chamber experiment. In addition, this study further explored the correlation and ratio of influencing factors that affect the concentration level of total PAEs in environment chambers, including environmental factors, the coefficient of volatile strengths of PAEs and contents of total PAEs in plastic products. The research created an improved database system of phthalate the coefficient of volatile strengths of each type of plastic goods, and tentatively revealed that the volatile patterns of PAEs from different typical plastic goods, finally confirmed that the coefficient of volatile strengths of PAEs is a major factor that affects the indoor air total PAEs concentration, which laid a solid foundation for further establishing the volatile equation of PAEs from plastic products.

氯化石蜡/DOTP复合增塑体系在PVC中的应用

为得到低成本的PVC增塑剂配方,对氯化石蜡(CP-52)和对苯二甲酸二辛酯(DOTP)在聚氯乙烯(PVC)中的协同增塑性能进行研究,对比氯化石蜡复配前后,PVC制片的性能变化,包括热稳定性能、耐热老化性能、力学性能和增塑剂的耐迁移性能。结果表明,由于氯化石蜡具有耐挥发和阻燃性较好的特点,CP-52/DOTP复合增塑体系增塑的PVC制片具有较好的热稳定性能,其耐热老化性能和耐挥发性能均提高。另外,复配氯化石蜡后,可以显著提高PVC制片的力学性能,当复配比例为40%时,断裂伸长率和拉伸强度提高最显著,分别为0-CP-52/DOTP试片的1.92倍和2.28倍。复配氯化石蜡后,对PVC制片的耐迁移性能也有提高,在无水乙醇和石油醚中,当复配比例为50%时,PVC制片的质量损失率分别降低了6.87%和17.16%(6 h)。在食品模拟液中的耐迁移性能也得到提升,在正己烷中,当复配比例为50%时,PVC制片的质量损失率降低了14.97%。最后,对CP-52/DOTP复合增塑体系提出对应的增塑机理。

火锅底料包装材料中邻苯二甲酸酯类塑化剂迁移的研究

目的火锅底料中的油脂含量较高,复合塑料内包装袋中的塑化剂对火锅底料存在一定污染风险。研究不同内包装材料、灌装温度、存放温度及存放时间对包装材料中邻苯二甲酸酯类塑化剂迁移的影响,为火锅底料内包装袋材料的选择和火锅底料灌装工艺条件的设置提供科学依据。方法采用气相色谱–质谱联用技术,定性、定量研究各种邻苯二甲酸酯类塑化剂的迁移量。结果火锅底料常使用PA/PE类型的复合包装,其塑化剂迁移量相较于PA/PP、PET/PA和BOPA/PE包装更高。随着灌装温度和存放温度的升高,以及存放时间的延长,塑化剂的迁移量不断增大,不同灌装温度、存放温度对邻苯二甲酸酯类塑化剂迁移量的影响较大。在火锅底料中,最易发生DBP、DEHP的迁移,未检出其他指标。结论直接接触火锅底料的包装材料、灌装温度、存放温度、存放时间均会对邻苯二甲酸酯类塑化剂的迁移造成显著影响。为了减少包装材料中邻苯二甲酸酯类塑化剂的迁移量,建议避免使用PA15/PE65作为火锅底料的内包装材料,灌装温度不宜超过70℃,在低温下存放,并尽快食用。

纳米塑料-重金属-塑化剂联合暴露对儿童肠道微生物菌群及代谢的影响

[目的]探究纳米塑料(NPs)、镉(Cd)和邻苯二甲酸二丁酯(DBP)污染对儿童肠道菌群多样性、氨基酸代谢及短链脂肪酸(SCFAs)含量的影响.[方法]利用16S rRNA高通量测序技术和高效液相色谱-质谱法LC-MS/MS分析NPs、Cd、DBP单一污染及纳米塑料聚丙烯(PP)、Cd、DBP复合污染对儿童肠道细菌群落及肠道微生物代谢产物中短链脂肪酸及氨基酸含量的变化.[结果]高通量检测结果显示,与对照相比,在门属水平上,单一污染的优势菌门属无明显变化,PP+Cd、PP+DBP+Cd复合污染优势菌门属水平丰富度与多样性显著下降;LC-MS/MS检测结果显示,在肠道微生物代谢产物中,经NPs与DBP暴露后,氨基酸含量呈现不同程度的下降,而Cd、PP+Cd、PP+Cd+DBP处理后,大多数氨基酸的含量显著增加;同时检测到丁酸、戊酸的含量也发生变化.[结论]与单一污染物处理相比NPs相关复合污染物暴露处理后其肠道微生物紊乱程度更强,且不同污染物处理均会影响肠道微生物的氨基酸代谢和SCFAs产量.肠道菌群与人体健康密切相关,探究肠道菌群及代谢功能在NPs、Cd、DBP影响下的变化,从肠道菌群层面评价NPs、Cd、DBP单一暴露和复合暴露污染下的危害和风险具有重要意义.

气相色谱-质谱法测定电线电缆中苯二甲酸酯类增塑剂

在电线电缆中大量应用的苯二甲酸酯类增塑剂可能造成人体内分泌失调,但目前研究主要集中于邻苯二甲酸酯类的检测。随着法规趋严,替代品的应用随之增加,为此建立了测定电线电缆中14种邻、间、对苯二甲酸酯增塑剂含量的气相色谱-质谱检测法。将电线电缆外皮冷冻粉碎至粒径小于1 mm,以10 mL乙酸乙酯为提取溶剂,60℃下超声萃取40 min,提取液用0.45μm有机相滤膜过滤后,选择离子监测(SIM)模式下,以特征碎片离子丰度比定性,内标法定量。结果显示,14种苯二甲酸酯增塑剂在0.20~20.0 mg/L浓度范围内具有较好的线性,相关系数均大于0.995,检出限为0.2~1.0 mg/kg,对空白样品进行加标回收实验,回收率为93.1%~120.2%,相对标准偏差为0.8%~7.6%。本方法用10个样品分析,均检出苯二甲酸酯增塑剂。

水果浆软糖中邻苯二甲酸酯类塑化剂的来源分析

以芒果浆软糖、番茄浆软糖、柳橙浆软糖为研究对象,采用气相色谱-质谱联用方法测定水果浆软糖生产过程中原辅料、加工助剂、各工序产品的塑化剂(DEHP、DBP)含量及与各工序产品直接接触的塑料材料中塑化剂(DEHP、DBP)迁移量,探究原辅料、加工助剂、与产品直接接触的塑料材料等对水果浆软糖中邻苯二甲酸酯类塑化剂含量的影响。

Validated Method for the Detection of Three Phthalates Derived from Marine Invertebrates

This study represents, detailly, the validated method for the extraction and quantification of widespread phthalic acid esters (PAEs) bis(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DBP) and di-n-octyl phthalate (DnOP) from solitary ascidians collected from a marine environment. The extraction was based on a pressurized liquid extraction method, using n-hexane as the solvent to extract the target PAEs from dry biological tissues, and was performed in an accelerated solvent extraction instrument. The average recovery of 89.2% was obtained from samples subjected to a pressure of ~1500 psi and 120°C in two 10-min cycles. GC-MS was used for quantification, conducted in single-ion monitoring mode. Following careful and rigorous cleanup procedures to prevent cross-contamination from laboratory glassware, PAE standards showed signals with good specificity. The obtained limits of detection were 130, 122 and 89 ng/g for DEHP, DBP and DnOP, respectively. Accordingly, the calculated limits of quantification were 394, 370 and 270 ng/g for DEHP, DBP and DnOP, respectively. The obtained linearity ranged from 5.4 to 269 ng/ml (equivalent to 135 - 6725 ng/g dry weight), with R2 ≥ 0.998. Concentrations in the range of 200 to 9000 and 400 to 5000 ng/g sample dry weight, for DEHP and DBP, respectively, were obtained from the ascidians. No DnOP was detected in any of the samples. These results indicate that the method presented in this study is applicable for detection of low and trace concentrations of the target PAEs in samples collected from a marine organism, which can serve as a bioindicator of plastic contamination.

化妆品中邻苯二甲酸二异已酯的高效液相色谱检测及质谱确证

本研究建立了化妆品中邻苯二甲酸二异已酯的高效液相色谱分析及质谱确证方法。膏霜和乳液类样品经氯化钠破乳后用甲醇进行超声辅助溶剂萃取,液体类样品直接用甲醇进行超声辅助溶剂萃取,提取液离心处理,取上清液经微孔滤膜过滤后上机测定。采用Innoval C_(18)(4.6 mm×250 mm,5μm)色谱柱进行分离,以乙腈∶水=90∶10(体积比)为流动相进行等度洗脱,外标法定量。化妆品中邻苯二甲酸二异已酯的方法检出限为2 mg/kg,定量限为5 mg/kg,在5~500 mg/kg线性范围内,呈现良好线性关系(r>0.999)。在低、中、高3个添加水平范围内平均回收率在86.7%~107.6%之间,相对标准偏差为2.9%~6.9%。对于疑似阳性样品,进一步采用液相色谱-串联质谱法进行确证分析。该方法准确、稳定,适用于化妆品中邻苯二甲酸二异已酯的分析测定。

食品中邻苯二甲酸酯类塑化剂检测方法研究进展

塑化剂作为一种加工助剂,可增加聚合物的可塑性,目前已被广泛应用于化工、医药、日用品和食品包装等各领域。邻苯二甲酸酯是最常用的一种塑化剂,其可在生产、流通等过程中迁移到食品内部,对人体造成不可逆伤害。总结了食品中邻苯二甲酸酯类塑化剂检测的前处理方法及传统检测方法的原理、优缺点及适用性,并按照输出信号种类不同分类,综述了几种邻苯二甲酸酯快速检测方法的原理、特点和应用,总结和比较了几种快速检测方法的优缺点,并对其发展方向进行展望,以期为塑化剂检测方法的研究和开发新型快速的检测方法提供参考思路。

白腐真菌对邻苯二甲酸二甲酯的降解与机理研究

文章以黄孢原毛平革菌(Phanerochaete chrysosporium)作为白腐真菌的代表,研究其对邻苯二甲酸二甲酯(dimethyl phthalate,DMP)的降解效果与机理。实验结果表明,在最佳条件(pH=5.6,温度为30℃,DMP初始质量浓度为10 mg/L)下,7 d后DMP的去除率为75%。进一步优化反应条件发现:体系中初始葡萄糖质量浓度为5 g/L时,反应结束时DMP降解效率为95%;当反应中加入20μg/L H_(2)O_(2)或27.0 mg/L Mn^(2+),反应7 d后DMP的降解效率显著提升到100%。此外,过氧化物酶在DMP降解过程中起重要作用,实验证明DMP的降解更多地由锰过氧化物酶(manganese peroxidase,MnP)驱动;傅里叶红外光谱证实氨基、羧基、羟基等还原性官能团参与了DMP的去除。文中通过液相色谱-质谱(liquid chromatography-mass spectrometry,LC-MS)联用仪确定DMP的降解产物,并讨论3种可能的降解途径。

GC-MS法测定酊剂中4种邻苯二甲酸酯类塑化剂

目的:探索一种新的、可靠的、用于检测酊剂中4种邻苯二甲酸酯类塑化剂含量的方法。方法:样品采用正己烷超声提取,色谱柱为TM-5MS(30 m×0.25 mm×0.25μm),载气为氦气,流速为1.2 mL·min^(-1),进样口温度为260℃,柱温为程序升温,电子轰击电离方式(EI),离子源温度为230℃,离子监测(SIM)模式。结果:4种PAEs分离良好,在0~1.00μg·mL^(-1)内呈良好的线性关系,相关系数r>0.99,检出限为0.038~0.081 mg·kg^(-1),加样回收率在85.0%~104.7%,相对标准偏差在0.5%~6.0%。结论:该法分离效果好、准确、灵敏度高,可同时检测塑料包装酊剂中4种邻苯二甲酸酯类塑化剂。

气质联用法同时测定纺织品中17种邻苯二甲酸酯类增塑剂

建立了气质联用法测定纺织品中17种邻苯二甲酸酯的分析方法,以四氢呋喃为萃取溶剂,采用超声萃取法提取纺织品中的17种邻苯二甲酸酯,优化了样品萃取溶剂的选择和仪器分析条件。结果表明:本方法17种邻苯二甲酸酯的检出限在7.2~66.1 mg/kg之间,加标回收率为90.5%~99.7%,相对标准偏差为2.8%~7.8%。本方法仪器分析时间短,回收率高,重复性好,结果可靠,适用于纺织品中17种邻苯二甲酸酯的检测。