空气和土壤中酞酸酯的污染及其相关性分析

对天津市11个采样点的空气颗粒物和土壤样品进行采样调查,采用气相色谱/质谱联用仪分析样品中15种酞酸酯类化合物(PAEs)的含量。结果表明,11个采样点空气颗粒物样品中总酞酸酯类化合物(TPAEs)以体积计质量浓度为90.87～1355.70ng/m3,以质量计质量浓度为783.84～8712.37mg/kg;土壤中TPAEs质量浓度为0.53～2.53mg/kg。邻苯二甲酸二丁酯(DBP)与邻苯二甲酸二(2-乙基己基)酯(DEHP)是空气颗粒物和土壤样品中的主要污染物。土壤与空气颗粒物中TPAEs和DBP存在相关关系,Pearson相关系数分别为0.825和0.864(双尾检验,显著性水平0.01),且空气颗粒物中各种PAEs浓度为土壤PAEs浓度的数百至数万倍,说明空气沉降可能是土壤PAEs污染的主要原因之一。     

邻苯二甲酸酯类环境激素的研究进展

邻苯二甲酸酯(PAEs)的环境行为和环境效应已成为当前环境激素类污染物研究的热点课题,介绍了PAEs的毒性危害,综述了当前不同环境样品PAEs研究的前处理技术、分析检测技术以及污染治理技术的研究情况,并指出了当前研究中存在的问题,提出了未来的研究重点。     

钦州湾入海口邻苯二甲酸酯分布特征及生态风险评价

为了解钦州湾入海口邻苯二甲酸酯(PAEs)污染情况,以钦州湾入海口沉积物为研究对象,对其中5种PAEs进行浓度及分布特征研究,并探讨PAEs与总有机碳(TOC)相关性,进行了PAEs生态风险评价。结果表明,钦州湾入海口沉积物中邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁苄脂(BBP)和邻苯二甲酸二(2-乙基)己脂(DEHP)均有检出,检出率为100%,PAEs总质量浓度(以干质量计)为4.158～8.455mg/kg,平均值为7.011mg/kg。钦州湾入海口沉积物中PAEs以DEHP与DEP为主,PAEs浓度表现为DEHPDEPDBPBBPDMP,平均值分别为3.932、2.212、0.580、0.241、0.047mg/kg。钦州湾入海口沉积物中PAEs主要分布在钦江、金鼓江和龙门港。钦州湾入海口沉积物中TOC质量浓度为0.912～19.305mg/g,平均值为7.162mg/g,TOC与PAEs总浓度的相关系数为0.609,无显著相关性(p0.05)。与国内外其他区域沉积物中PAEs浓度相比,钦州湾入海口沉积物中PAEs总浓度低于国内外大部分流域,但DBP、DEP和DMP浓度超过美国土壤PAEs控制限值,存在着一定的生态风险。     

土壤中邻苯二甲酸酯分布特征、来源及风险评价研究进展

邻苯二甲酸酯(PAEs)作为环境中广泛存在的一类内分泌干扰物,其污染问题已经引起广泛关注。针对土壤中PAEs的检测方法、分布特征、环境来源和风险评价等方面进行综述。土壤样品前处理及分析测试过程中环境、试剂等存在痕量的目标化合物会影响最终检测结果的准确性,排除此环节中的污染干扰尤为重要,色谱—质谱联用技术是精准分析此类化合物的发展方向。中国土壤中PAEs普遍检出,PAEs含量与人类活动和生产方式密切相关,其控制标准和风险评价大多采用国外标准,一定程度上影响了中国不同类型及功能区划土壤质量评价的科学性和客观性。环境友好分析测试技术的开发应用、风险评价体系的建立健全及环境溯源技术的发展将是今后土壤中PAEs研究的主要方向。     

土壤中邻苯二甲酸脂提取与检测方法的研究进展

邻苯二甲酸酯(PAEs)是一类环境激素类化合物,具有致畸、致癌和致突变的毒性。土壤中的PAEs可以通过食物链在人体内富集,威胁人类身体健康。当前土壤受PAEs污染现象日益普遍,选择合适的提取和检测方法评估土壤的PAEs污染程度显得至关重要。在前人研究成果的基础上,比较了索氏提取法、振荡提取法等传统方法与加速溶剂提取法等新型方法共7种土壤样品提取方法的优缺点,并综述了国内外检测土壤样品中PAEs含量的主要方法。展望了土壤中PAEs提取方法的发展趋势,为今后高效、快速检测土壤中的PAEs污染状况提供科学依据。     

重庆市交巡警体内邻苯二甲酸酯暴露水平分析

分析邻苯二甲酸酯(PAEs)在重庆市交巡警体内的暴露水平并对其可能的来源进行解析。采集重庆市某主城区和某郊县两地交巡警静脉血样60例(某主城区32例、某郊县28例),同时采集两地交巡警户外执勤点空气总悬浮颗粒物(TSP),采用气相色谱/质谱(GC/MS)技术检测血样和空气TSP中PAEs的种类和含量。14种PAEs在重庆市交巡警体内均有不同程度的检出,其中6种PAEs的检出率高达100.00%;检出浓度最高的4种PEAs质量浓度均值分别为611.17、610.53、193.91、150.83μg/L;14种PAEs在重庆市某主城区交巡警体内的均值均高于某郊县交巡警,其中4种PEAs具有统计学差异(P0.05);重庆市各交巡警户外执勤点空气TSP中均检出了14种PAEs,且某主城区空气TSP中PAEs浓度均高于某郊县;执勤点空气TSP和交巡警体内6种PAEs具有正相关性。重庆市某主城区和某郊县交巡警体内PAEs存在一定的差异,这种差异可能与其户外执勤点空气TSP中的PAEs具有相关性,提示交巡警执勤环境的空气质量对其健康可产生一定的影响。     

表面活性剂淋滤对土壤中邻苯二甲酸酯纵向迁移的影响

以无表面活性剂的去离子水为对照、设置1倍(1 CMC)和2倍临界胶束浓度(2 CMC)浓度,研究了单一和混合表面活性剂,包括十六烷基三甲基溴化铵(CTAB)、十二烷基苯磺酸钠(SDBS)和曲拉通X-100(TX-100)对人工污染土壤中邻苯二甲酸酯(PAEs)纵向迁移的影响,土柱中上层为PAEs污染土(3 cm),下层为清洁土(20 cm)。CTAB和SDBS在2 CMC时、TX-100为1 CMC时可增强污染土中PAEs的纵向迁移,其中DMP和DEP有无表面活性剂均可发生迁移,在相同表面活性剂条件下,延长老化时间对污染土中PAEs的迁移产生一定的影响。CTAB和SDBS在2 CMC时,清洁土中PAEs总含量较低,但TX-100在1 CMC时较低。清洁土中PAEs总含量均随土层深度的增加而降低。当老化时间较短时,土壤有机质对PAEs在清洁土柱的迁移影响较小,老化时间的延长对清洁土中的PAEs迁移影响较大。3种表面活性剂均可有效促进清洁土中DMP和DEP的迁移,CTAB和SDBS在2 CMC、TX-100在1 CMC时可促进DNBP和BBP的迁移,但3种表面活性剂对清洁土中DNOP迁移的影响较小。与单一表面活性剂相比,混合表面活性剂有助于污染土中PAEs的迁移,且随着浓度的升高,清洁土中PAEs的含量呈现降低的趋势。就整个土柱而言,单一表面活性剂CTAB和SDBS在较高浓度时、TX-100较低的浓度时对PAEs的淋滤效果更好;在较短老化时间下,土壤有机质含量的高低对淋滤率没有显著影响;老化时间延长有效降低了淋滤率;而混合表面活性剂的淋滤率有明显提高,更有助于PAEs的迁移。     

邻苯二甲酸酯对序批式活性污泥法运行的影响

环境内分泌干扰物邻苯二甲酸酯(PAEs)在废水处理系统中广泛存在,难降解且易产生累积。PAEs的长期积累难以从废水处理工艺上解决。以序批式活性污泥(SBR)工艺处理人工配置的氨氮废水为例,考察PAEs存在条件下对SBR反应器运行的干扰。结果表明:随着原水中PAEs浓度增加,SBR反应器的活性污泥中,微生物最终能够以PAEs为唯一碳源;PAEs为10～150mg/L时,其浓度的变化对SBR反应器内活性污泥性状有明显影响,悬浮固体(MLSS)最终维持在2 000mg/L;随PAEs浓度的改变,SBR反应器内COD去除率变化不显著,而氨氮去除率随着PAEs浓度的升高而降低,最低值约为50%;亚硝态氮出现积累现象,积累量最高时接近60mg/L。     

天津市大气PM_(10)与降尘中邻苯二甲酸酯的污染特征及相关性分析

采集天津市4个采样点的大气 PM_(10)与降尘样品,利用CH_2Cl_2和超声对样品中的邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸(2-乙基己基)酯(DEHP)和邻苯二甲酸二辛酯(DOP)等6种邻苯二甲酸酯(PAEs)进行提取分离,采用气相色谱/质谱联用仪(GC/MS)定量分析。结果表明,4个采样点大气 PM_(10)样品中6种PAEs总质量浓度为2.371~24.201ng/m3,降尘样品中6种PAEs总质量浓度为222.310~1 184.503ng/g。对于6种PAEs,夏季浓度均高于冬季浓度,且DBP与DEHP是大气 PM_(10)与降尘样品中的主要污染物。6种PAEs总浓度、DBP浓度、DEHP浓度在大气 PM_(10)与降尘样品中存在相关关系,斯皮尔曼相关系数分别为0.929、0.881、0.905(双尾检验,在显著性水平0.01下)。回归分析表明,大气 PM_(10)与降尘样品中6种PAEs总浓度、DBP浓度、DEHP浓度具有一定的共变趋势。     

CTMAB／SDS改性沸石对水中痕量邻苯二甲酸酯吸附机制

以季铵盐阳离子表面活性剂CTMAB及阴离子表面活性剂SDS对粉末状天然沸石进行复合改性,制备得到了CTMAB／SDS改性沸石。对改性沸石及天然沸石进行红外吸收光谱及XRD衍射表征,并研究了PAEs在天然沸石和CT-MAB／SDS改性沸石上的吸附机制。结果表明,阴阳离子表面活性剂没有对层状结构的键型造成较大的影响;PAEs在天然沸石和CTMAB／SDS改性沸石上的吸附更符合表面吸附一分配作用复合模型;PAEs的表面吸附和分配作用对吸附作用的贡献主要受吸附剂中有机质含量及吸附物质大小、极性及溶解度的影响。     

Sorption behavior of dibutyl phthalate and dioctyl phthalate by aged refuse

Sorption is a fundamental process controlling the transformation, fate, degradation, and biological activity of hydrophobic organic contaminants in the environment. We investigated the kinetics, isotherms, and potential mechanisms for the sorption of two phthalic acid esters (PAEs), dibutyl phthalate (DBP) and dioctyl phthalate (DOP), on aged refuse. A two-compartment first-order model performed better than a one-compartment first-order model in describing the kinetic sorption of PAEs, with a fast sorption process dominating. Both the Freundlich and Dubinin–Astakhov (DA) models fit the sorption isotherms of DBP and DOP, with the DA model being of a better fit over the range of apparent equilibrium concentrations. The values of the fitting parameters (n, b, E) of the PAEs suggest nonlinear sorption characteristics. Higher predicted partition coefficient values and saturated sorption capacity existed in refuse containing larger quantities of organic matter. The sorption capacity of DOP was significantly higher than that of DBP. PAE sorption was dependent on liquid phase pH. Desorption hysteresis occurred in PAE desorption experiments, especially for the long-chain DOP. PAEs may therefore be a potential environmental risk in landfill.     

Potential mechanisms of phthalate ester embryotoxicity in the abalone Haliotis diversicolor supertexta

The effects and associated toxicological mechanisms of five phthalate esters (PAEs) on abalone embryonic development were investigated by exposing the embryos to a range of PAEs concentrations (0.05, 0.2, 2 and 10 μg/mL). The results showed that PAEs could significantly reduce embryo hatchability, increase developmental malformations, and suppress the metamorphosis of abalone larvae. The possible toxicological mechanisms of PAEs to abalone embryos included, affecting the Na⁺-K⁺-pump and Ca²⁺-Mg²⁺-pump activities, altering the peroxidase (POD) level and the malondialdehyde (MDA) production, damaging the extraembryonic membranes structure, as well as disrupting endocrine-related genes (gpx, cyp3a, and 17β-hsd 12) expression properties. Taken together, this work showed that PAEs adversely affected the embryonic ontogeny of abalone. The abilities of PAEs affecting the osmoregulation, inducing oxidative stress, damaging embryo envelope structure, and causing physiological homeostasis disorder, are likely to be a part of the common mechanisms responsible for their embryonic toxicity.     

Effects of film mulching on the distribution of phthalate esters in wheat grains from dryland

The application of plastic film in field crop production elevated the phthalate esters (PAEs) accumulation in wheat grains, which poses potential risks to human health. However, the variation of grain PAEs contents in different dryland areas is not clear, and the distribution of PAEs in different tissues of grains has not been studied yet. In the present study, field experiments in five sites (three provinces) with two treatments (soil with and without film mulching) were carried out to study the concentration and distribution of PAEs in grains and the effects of environmental factors on them. Results showed that the total PAE concentration (∑PAEs) in wheat grains ranged from 445 to 764 μg/kg, mainly in the forms of di-(2-ethylhexyl)-phthalate (DEHP), dibutyl phthalate (DBP), and diisobutyl phthalate (DIBP). Compared with control, total PAE concentrations in soils and wheat grains were significantly higher in treatments with film mulching. The effects of film on the proportion of PAEs in the flour and bran varied with experiment sites. Grain PAEs in the control groups presented significantly negative correlation with annual temperature, while there was a positive correlation between soil PAEs and bran PAEs in the film treatment. Results in this study are of great significance to comprehensively evaluate the effect of film mulching on grain safety in dryland wheat production.

     

Determination of phthalates in particulate matter and gaseous phase emitted in indoor air of offices

Environmental Science and Pollution Research - Phthalate esters (PAEs) are endocrine disrupters and can disrupt the functioning of different hormones, causing adverse effects on human health. Due...     

环境中邻苯酸酯类化合物污染研究概况

邻苯酸酯类化合物在工农业及人们日常生活中均有广泛应用。近来它已被确认为环境激素。本文介绍该领域的研究概况,着重在北美和西欧地区对这类化合物的风险评价、雌激素活性体内和体外的测定结果以及对它的安全性看法。     

Biodegradation of four phthalate esters in sludge

This study investigated the effects of ultrasonic pretreatment and various treatments on the aerobic degradation of four phthalic acid esters (PAEs) such as diethyl phthalate (DEP), benzyl butyl phthalate (BBP), di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl)phthalate (DEHP) in sludge. The effect on PAE degradation of treating sludge with a 20 min sonication period at a power level of 0.1 W ml(-1) was evaluated. The degradation rates of the four PAEs were DBP>BBP>DEP>DEHP. Degradation rate constants (k(1)) and half-lives (t(1/2)) for the four PAEs (50 mg kg(-1)) ranged from 0.182 to 0.379 day(-1) and 1.8 to 3.8 days, respectively. The optimal pH for PAE degradation in sludge was 7.0 at 30 degrees C. PAE degradation was enhanced by the addition of yeast extract, brij 30 or brij 35 and inhibited by the addition of hydrogen peroxide. Our results show that a combination of ultrasonic pretreatment and biodegradation can effectively remove PAE from sludge.     

Current status and historical variations of phthalate ester (PAE) contamination in the sediments from a large Chinese lake (Lake Chaohu)

The residual levels of phthalate esters (PAEs) in the surface and two core sediments from Lake Chaohu were measured with a gas chromatograph–mass spectrometer (GC–MS). The temporal–spatial distributions, compositions of PAEs, and their effecting factors were investigated. The results indicated that di-n-butyl phthalate (DnBP), diisobutyl phthalate (DIBP), and di(2-ethylhexyl) phthalate (DEHP) were three dominant PAE components in both the surface and core sediments. The residual level of total detected PAEs (∑PAEs) in the surface sediments (2.146?±?2.255 μg/g dw) was lower than that in the western core sediments (10.615?±?9.733 μg/g) and in the eastern core sediments (5.109?±?4.741 μg/g). The average content of ∑PAEs in the surface sediments from the inflow rivers (4.128?±?1.738 μg/g dw) was an order of magnitude higher than those from the lake (0.323?±?0.093 μg/g dw), and there were similar PAE compositions between the lake and inflow rivers. This finding means that there were important effects of PAE input from the inflow rivers on the compositions and distributions of PAEs in the surface sediments. An increasing trend was found for the residual levels of ΣPAEs, DnBP, and DIBP from the bottom to the surface in both the western and eastern core sediments. Increasing PAE usage with the population growth, urbanization, and industrial and agricultural development in Lake Chaohu watershed would result in the increasing production of PAEs and their resulting presence in the sediments. The significant positive relationships were also found between the PAE contents and the percentage of sand particles, as well as TOC contents in the sediment cores.     

铜在沉积物不同稳定性组分上的吸附特征

沉积物中不同成分的稳定性对重金属的迁移转化有重要影响。按照在自然条件下不同成分的稳定性将沉积物分为3个组分(轻组(LF)、腐殖质(HS)、去除HS的重组(HFRHS))。研究了铜在沉积物及其不同组分上的吸附动力学、吸附等温线以及pH对吸附的影响。结果表明,在沉积物中,LF与HS对吸附铜的速率起控制作用,而HFRHS是主要的吸附组分,pH对铜的吸附有较大影响。在自然环境中,控制LF和HS的迁移转化,可以有效降低铜的迁移能力,减小对环境的影响。