BP人工神经网络预测邻苯二甲酸酯光化学降解

将反向传播人工神经网络（BP－ANN）用于邻苯二甲酸酯类化合物的光化学降解的预测中，选取正交设计的试验点作为反向传播人工神经网络的训练集，实现对全实验域试验点的预测，并与实测的试验数据比较。结果表明反向传播人工神经网络（BP－ANN）具有良好的预测能力。     

贵州省部分地区土壤中酞酸酯类污染现状调查

对贵州省部分地区表层土壤中酞酸酯类的污染状况进行了调查。分别在遵义地区、黔南地区、黔东南地区和毕节地区采集483个土壤样品分析,结果表明,样品中酞酸酯总质量比(ΣPAEs)为未检出~8.22 mg/kg,均值为0.63 mg/kg。其中DEHP和DBP为主要污染物,均值分别为0.32 mg/kg和0.24 mg/kg,检出率分别为90.89%和97.10%。     

Canine toys and training devices as sources of exposure to phthalates and bisphenol A: Quantitation of chemicals in leachate and in vitro screening for endocrine activity

Chewing and mouthing behaviors exhibited by pet dogs are likely to lead to oral exposures to a variety of environmental chemicals. Products intended for chewing and mouthing uses include toys and training devices that are often made of plastics. The goal of the current study was to determine if a subset of phthalates and bisphenol A (BPA), endocrine disrupting chemicals commonly found in plastics, leach out of dog toys and training devices (bumpers) into synthetic canine saliva. In vitro assays were used to screen leachates for endocrine activity. Bumper leachates were dominated by di-2-ethylhexyl phthalate (DEHP) and BPA, with concentrations reaching low μg mL⁻¹ following short immersions in synthetic saliva. Simulated chewing of bumpers during immersion in synthetic saliva increased concentrations of phthalates and BPA as compared to new bumpers, while outdoor storage had variable effects on concentrations (increased DEHP; decreased BPA). Toys leached substantially lower concentrations of phthalates and BPA, with the exception of one toy which leached considerable amounts of diethyl phthalate. In vitro assays indicated anti-androgenic activity of bumper leachates, and estrogenic activity of both bumper and toy leachates. These results confirm that toys and training devices are potential sources of exposure to endocrine disrupting chemicals in pet dogs.     

Intake of phthalates and di(2-ethylhexyl)adipate: results of the Integrated Exposure Assessment Survey based on duplicate diet samples and biomonitoring data

Phthalates are ubiquitous environmental chemicals with potential detrimental health effects. The purpose of our study was to quantify dietary intake of phthalates and of DEHA (Di-ethylhexyl adipate) using duplicate diet samples and to compare these data with the calculated data based on urinary levels of primary and secondary phthalate metabolites. 27 female and 23 male healthy subjects aged 14-60 years collected daily duplicate diet samples over 7 consecutive days. Overall, 11 phthalates were measured in the duplicates by GC/MS and LC/MS methods. Urinary levels of primary and secondary phthalate metabolites are also available. The median (95th percentile) daily intake via food was 2.4 (4.0) microg/kg b.w. (Di-2-ethylhexyl phthalate, DEHP), 0.3 (1.4) microg/kg b.w. (Di-n-butyl phthalate, DnBP), 0.6 (2.1) microg/kg b.w. (Di-isobutyl phthalate, DiBP) and 0.7 (2.2) microg/kg b.w. for DEHA. MEPH (Mono-2-ethylhexyl phthalate) was detectable only in minor concentrations in the samples, thus conversion of DEHP to MEHP and dietary intake of MEHP were negligible. When comparing back-calculated intake data of the DEHP metabolites with dietary DEHP intake from the day before significant correlations were observed for most of the metabolites. No correlation was found for DnBP and only a weak but significant correlation for DiBP. The median and 95th percentile daily dietary intake of all target analytes did not exceed the recommended tolerable daily intake. Our data indicated that food was the predominant intake source of DEHP, whilst other sources considerably contributed to the daily intake of DnBP and DiBP in an adult population.     

Designing green plasticizers: influence of molecular geometry on biodegradation and plasticization properties

The plasticizer di (2-ethylhexyl) phthalate (DEHP) and its metabolites are considered ubiquitous contaminants, which have a range of implications on the environment and human health. This work considered several alternative compounds with structural features similar to DEHP. This added to the understanding of why DEHP is so poorly biodegraded once it enters the environment. These alternative compounds were based on 2-ethylhexyl diesters of maleic acid (cis-isomer), fumaric acid (trans-isomer) and succinic acid (saturated analogue). The rates of biodegradation by the common soil bacterium Rhodococcus rhodocrous were shown to be dependent on the structure of the central unit derived from the diacid used to make the ester. The diacid components of DEHP and the maleate both had a cis orientation and they were the two that were slow to biodegrade. Plasticizing properties were also compared and, because the ester of the saturated succinic acid was degraded quickly and also had good plasticizing properties, it was concluded that the succinic esters of straight chain alcohols would make the best green plasticizers. The maleate ester had excellent plasticizing properties but this is mitigated by a significant resistance to biodegradation.     

A chemical and toxicological profile of Dutch North Sea surface sediments

Chemical and toxicological profiles were assessed in surface sediments (fraction <63 μm) from the southern North Sea. In extracts of freeze-dried samples, polybrominated biphenyl (PBB), Irgarol 1051 and phthalate concentrations were below the respective detection limits (except di(2-ethylhexyl)phthalate, which was between 170 and 3300 μg kg⁻¹ dry weight (dw)). Hexabromocyclododecane (HBCD) concentrations were between 0.8 and 6.9 μg kg⁻¹ dw, with highest concentrations at river mouths. Polybrominated diphenylethers (PBDE) concentrations were 0.4–0.6 μg kg⁻¹ dw, decabromodiphenylether (BDE209) 1–32 μg kg⁻¹ dw. The ratio BDE209/PCB153 was used as a tracer for recent emissions, and pointed towards a BDE209 source in the Western Scheldt’s upper estuary. PCBs and PAHs were between 0.19–4.7 and 2.6–200 μg kg⁻¹ dw respectively and generally had highest concentrations at near-shore locations and river mouths.

Responses in the Microtox broad-spectrum and the Mutatox genotoxicity assays were generally low, with near-shore locations giving higher responses. The umu-C genotoxicity and the ER-CALUX assay for estrogenicity showed no response, with the exception of one near-shore location (IJmuiden outer harbour, ER-CALUX).

Highest dioxin-like toxicity (DR-CALUX) was found at near-shore locations, in the outflow of the Rhine/Meuse estuary including a dumping site of harbour sludge. At the Oyster Grounds, DR-CALUX responses appeared to be linked to the occurrence of larger PAHs (4–6 rings). A new, non-destructive clean up procedure resulted in significantly higher DR-CALUX responses than the current protocol. The Dutch legislation on disposal of harbour sludge at sea, dictates the use of the conventional clean up procedure. Our results therefore indicate that probably more dioxin-like toxicity associated with harbour sludge is disposed off at sea than assumed.     

乌鲁木齐市饮用水源地中邻苯二甲酸酯健康风险评价

采用美国环保署(US EPA)推荐的健康风险评价模型,对乌鲁木齐市饮用水源地中的邻苯二甲酸酯(PAEs)通过饮水途径致人体健康危害风险进行初步评价。结果显示,乌鲁木齐市地表饮用水源地的2种PAEs[邻苯二甲酸(2-乙基己基)酯(DEHP)和邻苯二四酸二丁酯(DBP)]浓度全部达到《地表水环境质量标准》(GB 3838—2002)特定项目标准限值要求,DEHP总检出率达58.3%~100.0%,DBP总检出率达100%,DEHP通过饮水途径引起的致癌和非致癌总风险数量级达10^(-10)~10^(-8),DBP通过饮水途径引起的非致癌风险数量级达10^(-13)~10^(-11)。乌鲁木齐市地下饮用水源地的DEHP浓度全部达到《地下水质量标准》(GB/T 14848—2017)中Ⅰ类标准限值要求,总检出率达66.7%~100.0%,通过饮水途径引起的总风险数量级分布中,城市集中式饮用水源地为10^(-10)~10^(-9),县城(区)饮用水源地为10^(-10)~10^(-8)。地表和地下饮用水源地的致癌和非致癌总风险均低于US EPA和国际癌症机构(ICRP)的最大可接受风险水平,并低于瑞典环境保护署、荷兰建设和环境署以及英国皇家协会的最大可接受风险水平,处于Ⅰ级,低风险状态。     

Synthetic endocrine disruptors in the environment and water remediation by advanced oxidation processes

The present study is an overview of the literature on classes and types of compounds described as "endocrine disruptors" and their treatability in water by advanced oxidation processes, which generate hydroxyl radicals in water. The review is limited to details of the destruction of three classes of endocrine disruptors, namely bisphenols, alkylphenols and phthalates, which are among the most highly suspected endocrine disrupting compounds that interfere with the hormonal system of wildlife. It was found that photocatalysis with titanium dioxide was the most frequently tested advanced oxidation method most likely due its potential to render complete mineralization. There is sufficient research also with direct and indirect photolysis and ozonation, which were less effective for the overall mineralization but more representative of the conditions existing in real water treatment plants.