Abiotic association of phthalic acid esters with humic acid of a sludge landfill

The abiotic association between phthalic acid esters (PAEs) and humic substances (HS) in sludge landfill plays an important role in the fate and stability of PAEs. An equilibrium dialysis combined with ¹⁴C-labeling was used to study the abiotic association of two abundant PAEs (diethyl phthalate and di-n-butyl phthalate) with humic acid (HA) isolated from a sludge landfill with different stabilization times and different molecular weights. Elemental analysis and Fourier Transform Infrared Spectrophotometer (FTIR) suggested that high K _A value of HA was related to the high aromatic content and large molecular weight of HA. The results indicated that the association strength of PAEs with HA depended on both the properties of the PAEs and the characteristics of HA. The K _A values of the association were strongly dependent on solution pH, and decreased dramatically as the pH was increased from 3.0 to 9.0. The results suggested that nonspecific hydrophobic interaction between PAEs and HA was the main contributor to the association of the PAEs with HA. The interactive hydrogen-bonds between the HA and the PAEs molecules may also be involved in the association.     

增塑剂邻苯二甲酸二（2-乙基己基）酯的危害、分布及生物降解

邻苯二甲酸二（2-乙基己基）酯（DEHP）广泛用于塑料产品、皮革、建筑材料、个人护理产品、洗涤剂、油漆和药物等产品中。作为最常用的增塑剂,DEHP一直是备受关注的人工合成物。本文在国内外已有研究成果的基础上,综述分析了DEHP的危害、分布和生物降解等,为今后的研究提供思路。许多动物实验研究结果显示,DEHP具有生殖发育毒性、免疫毒性、胚胎毒性、肝脏毒性及致癌性等多种毒性,并具有引起甲状腺素代谢改变的类雌激素活性。虽有针对 DEHP 与乳腺癌、胰腺癌、睾丸癌、呼吸系统癌症和多发性骨髓瘤等的关系之间的研究,但无足够证据表明 DEHP 会导致人类患上这些癌症或其他疾病。由于人体实验数据的严重缺乏,DEHP对人体的毒性并未得到完全确认,因此WHO将DEHP列为2B类物质,意为可能的致癌物质。作者认为DEHP的人体毒性实验是有关DEHP研究的前提和首要任务,因此建议对DEHP接触人群开展追踪研究,以获得基础性数据。另外鉴于环境中存在多种污染物质,因此建议开展 DEHP 与其他物质的协同毒性的研究。检测数据表明,DEHP已经广泛存在于水、食品容器、空气和土壤中。我国松花江、黄河和长江等多处采样点的数值超出了国家规定的生活饮用水水源水标准或国家地表水水质标准。DEHP 也是污水中最为常见的内分泌干扰物质。DEHP也广泛存在于牛奶、肉、奶酪、谷物、鱼和各种海产品等,且脂类含量越高,如牛奶、肉类和鱼类等,则DEHP的含量越高。塑料包装的食品如果放置时间过长,则会导致更多的DEHP释放到食品中。家具及装修材料也会释放DEHP,因此室内空气中也会含有一定量的DEHP。目前,美国、澳大利亚、日本等大多数国家规定DEHP在空气中的职业暴露限值为5 mg·m^-3,WHO建议饮用水中DEHP的限值为8μg·L^-1,我国也?     

珠江流域湖库型水源集水区酞酸酯(PAEs)类污染物环境健康风险评估

以饮用水源集水区为中心,沿支流采集水样,采用美国环境保护署(USEPA)暴露风险评价方法,结合该地区的参数计算环境健康风险。结果表明:(1)所有采样点均检出PAEs类污染物邻苯二甲酸正丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DOP)和邻苯二甲酸二乙酯(DEP),其中DOP高于DBP和DEP。(2)该饮用水源集水区3种PAEs污染物质量浓度均高于流域内其他乡镇饮用水源,在国内外同类地区也属于中上水平。DOP是集水区内需首要控制的PAEs类污染物。(3)在人类活动干扰少的地区河流污染物的环境健康风险水平较低,而在人口密集区和工业集中区风险水平较高。河流上游风险值低,中游高,下游和库区又逐渐回落。该水源集水区的PAEs类污染物环境健康风险值未超过USEPA规定,但与国内外其它地区相比属于中上水平,存在一定的潜在健康风险,需要根据PAEs的可能来源在水源地环境风险管理中加以防范。     

邻苯二甲酸酯暴露的大鼠尿液生物标志物研究

建立了检测尿液中邻苯二甲酸酯类化合物(PAEs)共同水解产物邻苯二甲酸(PA)的分析方法;通过雄性成年SD大鼠代谢试验,检测了邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)单独暴露、以及联合暴露条件下大鼠尿液中PA总量,并分析了PA与暴露总量之间的关系.结果显示,随着暴露剂量的增大,尿液中排出的PA总量也不断增大;DBP单独暴露、DEHP单独暴露以及两者联合暴露时尿液PAEs代谢物平均排泄总量占摄入量的百分比分别为65.04%、55.00%和38.35%;大鼠尿液中PA的摩尔总量与DBP、DEHP、以及两者联合暴露的摩尔量之间的相关系数分别为0.92(P<0.01)、0.56(P<0.01)、0.93(P<0.01).尿液水解后的PA能够反映PAEs类物质的总暴露水平,将来可能作为一种潜在的暴露生物标志物用于人群的PAEs暴露监测.     

高纯二氧化锆生产过程中污染的防治

对高纯二氧化锆的生产工艺进行了改革,采用了新型反应器及胶凝除硅,直接酸溶重结晶,直接煅烧等技术,降低了原材料消耗及能耗,减少了废液排放量,并将回收的废物加工成副产品白炭黑,实现了在生产过程中防治污染。     

固相萃取-气相色谱法检测水中的邻苯二甲酸酯

利用固相萃取技术富集了水中4种邻苯二甲酸酯类（PAEs）化合物：邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二乙酯（DEP）、邻苯二甲酸二丁酯（DBP）、邻苯二甲酸二（2-乙基己基）酯（DEHP）。借助均匀设计法及计算机回归建模优化技术对4种PAEs的固相萃取条件进行了设计与优化，得到的最佳固相萃取条件：洗脱剂配比（正己烷与丙酮的体积比）30：1，洗脱体积2mL，洗脱速率4mL／min，上样速率8mL／min。富集后的试样用带电子捕获器的毛细管气相色谱仪检测，方法的线性范围为1～1000μg／L（DMP，DEP），0．2—100μg／L（DBP，DEHP），线性回归方程的相关系数为0．9970～1．0000，检出限为0．02-0．4μg／L，4种PAEs的回收率为69％～117％，相对标准偏差为2．5％～9．5％。[关键词]     

Reaction mechanism and process safety assessment of acid-catalyzed synthesis of tert-butyl peracetate

Esterification during the synthesis of tert-butyl peracetate (TBPA) is highly exothermic. Since peroxides (tert-butyl hydroperoxide TBHP and TBPA) are intrinsically thermosensitive, this synthesis process is potentially dangerous. In this work, the exothermic process and mechanism of TBPA synthesis using acetic anhydride (Ac₂O) and TBHP under the catalysis of sulphuric acid (H₂SO₄) were clarified by calorimetry, infrared spectroscopy, and high-performance liquid chromatography. To substantially alleviate the thermal risk of the reaction, and to feasibly select appropriate synthesis conditions for ensuring the process safety of the synthesized products, several sets of isothermal and isoperibol experiments were performed using calorimetry. The intermediates formed and concentration changes during the reaction were monitored using in-situ Fourier-transform infrared spectroscopy. Differential scanning calorimetry and adiabatic calorimetry were used to assess the thermal hazard of the materials during the synthesis process. The reaction mechanism was verified using density functional theory calculations. The results revealed that a controlled increase in exothermicity could be achieved by adding aqueous TBHP to Ac₂O in semi-batch experiments in isothermal mode, and accordingly, the highest yield was 95.71%. Experiments combined with theoretical calculations revealed that the primary exothermic event was the TBPA formation reaction, and the removal of a large amount of water from TBHP prior to this is favourable for the reaction. The criticality classes of this reaction were of Grade 2.     

Concentration and source identification of polycyclic aromatic hydrocarbons and phthalic acid esters in the surface water of the Yangtze River Delta, China

The pollution from polycyclic aromatic hydrocarbons (PAHs) and phthalic acid esters (PAEs) in the surface water of the rapidly urbanized Yangtze River Delta region was investigated. Fourteen surface water samples were collected in June 2010. Water samples were liquid-liquid extracted using methylene chloride and analyzed by gas chromatography-mass spectrometry. Concentrations of PAHs and PAEs ranged 12.9-638.1 ng/L and 61-28550 ng/L, respectively. Fluoranthene, naphthalene, pyrene, phenanthrene, di-2-ethylhexyl phthalate, and di-n-butyl phthalate were the most abundant compounds in the samples. The water samples were moderately polluted with benzo[a]pyrene according to China's environmental quality standard for surface water. The two highest concentrations of PAHs and PAEs occurred in samples from Taihu Lake, Wuxi City and the western section of Yangchenghu Lake. Potential sources of pollution at S7 were petroleum combustion and the plastics industry, and at Yangchenghu Lake were petroleum combustion and domestic waste. Pollution in samples from the Beijing-Hangzhou Grand Canal originated from diesel engines. There were no obvious sources of pollution for the other water samples. These results can be used as reference levels for future monitoring programs of pollution from PAHs and PAEs.     

千岛湖水体中邻苯二甲酸酯(PAEs)的分布特征及健康风险评价

为揭示千岛湖水体中邻苯二甲酸酯(PAEs)的污染情况和风险水平,对枯水期和丰水期千岛湖湖区及入湖河流共计17个采样点水体中6种PAEs进行了检测,分析了 PAEs的污染水平,并开展健康风险评价.结果表明,枯水期和丰水期6种PAEs 均有检出,ρ(Σ PAEs)分别为0.98～5.33μg·L-1(平均值为2.63μg·...     

南京市大气气溶胶中酞酸酯的分布特征

利用分级采样器采样 ,高效液相色谱检测 ,研究了南京市春夏秋冬四季六大功能区 (工业区 ,交通区 ,文化区 ,商业区 ,园林风景区和居民生活区 )大气气溶胶中的酞酸酯 .结果表明 :南京市大气气溶胶中检出的酞酸酯有 :邻苯二甲酸二甲酯 (DMP)、邻苯二甲酸二丁酯 (DBP)和邻苯二甲酸二辛酯 (DEHP) ,其含量随功能区和季节而变化 ,平均浓度具有工业区 >居民区 >交通区 >商业区 >文化区 >园林风景区和秋、冬季浓度高于春、夏季的分布特征