1月天津市大气PM_(2.5)中邻苯二甲酸酯污染特征及暴露分析

本文研究了2014年1月天津市大气PM2.5中邻苯二甲酸酯(PAEs)的污染状况.结果表明,天津市大气PM2.5中PAEs污染以邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二异辛酯(DEHP)为主;PM2.5上载带的∑6PAEs浓度与PM2.5浓度存在相关关系;文教区PAEs浓度低于工业及居住区浓度;大气PM2.5中PAEs经呼吸的日均暴露量邻苯二甲酸二甲酯(DMP)和邻苯二甲酸二丁酯(DBP)较高,且男性高于女性.     

PAEs胁迫对高/低累积品种水稻根系形态及根系分泌低分子有机酸的影响

以前期筛选获得的邻苯二甲酸酯(PAEs)高/低累积基因型水稻(Oryza sativa L.)品种(培杂泰丰/丰优丝苗)进行水培试验,分别于分蘖期和拔节期采集样品,采用根系扫描仪分析根系形态学特性、高效液相色谱法测定根系分泌物中低分子有机酸成分,以及采用气相色谱-质谱仪(GC-MS)测定水稻根、茎、叶中PAEs质量分数。对比研究两种基因型水稻的根系形态特征和根系分泌物(低分子有机酸)的差异,初步探讨两种基因型水稻吸收累积PAEs差异原因,为保障农产品质量安全提供科学依据。结果表明,随着培养液中PAEs质量浓度增加,两种基因型水稻总根长、根表面积和根体积先增大后减小;相同PAEs质量浓度下,高累积型品种培杂泰丰根系形态指标大多高于丰优丝苗。两种水稻体内的PAEs质量分数均随污染物浓度增大而升高,高PAEs水平(80 mg·L-1)处理是低PAEs水平(20 mg·L-1)处理的3.8~7.3倍(邻苯二甲酸二丁酯(DBP))和2.7~20.4倍(邻苯二甲酸二(2-乙基己基)酯(DEHP)),培杂泰丰高于丰优丝苗。植物体内DBP和DEHP质量分数呈现根叶≥茎。分蘖期两种水稻体内DBP和DEHP质量分数高于拔节期,且与营养液中PAEs的质量浓度呈显著相关,但拔节期的相关程度减弱。拔节期两种水稻根系分泌物中低分子有机酸质量浓度随培养液中PAEs质量浓度升高呈现不同的变化规律,但二者草酸质量浓度均增加(在1.11~8.13 mg·L-1之间),并与根系中DBP和DEHP的质量分数呈显著正相关。说明PAEs胁迫会影响水稻根系形态和低分子有机酸分泌,进而影响水稻对PAEs的吸收累积。     

日常衣物中的邻苯二甲酸酯污染及其人体暴露风险

邻苯二甲酸酯(PAEs)作为一类内分泌干扰物,被广泛应用于工业生产。为了查明日常衣物中PAEs的污染状况,并评估其通过衣物的皮肤接触可能造成的人体暴露风险,本研究检测了日常生活中的新、旧衣服中7种典型PAEs的浓度,并通过实验模拟研究了衣料中PAEs向汗液的析出行为。结果表明,邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二异辛酯(DEHP)分别是旧衣服和新衣服中的代表性PAE。旧衣服中DEHP的浓度显著高于新衣服;婴儿衣服中DEHP的浓度高于成人衣服。穿着和清洗过程中的二次污染可能对衣服中的PAEs有显著影响,衣服材质可能是影响旧衣服中PAEs浓度的重要因素。汗液会导致衣物中的PAEs析出,从而明显增加PAEs的人体暴露风险。     

长江干流、嘉陵江和乌江重庆段邻苯二甲酸酯污染特征及生态风险评估

以重庆境内长江干流及其主要支流嘉陵江和乌江,作为研究对象,系统分析了沿江不同监测位点水体和沉积物中16种邻苯二甲酸酯(phthalic acid esters,PAEs)的含量、组成和分布;同时开展了水体和沉积物中PAEs的生态风险评估。水体中共检出7种PAEs,总浓度范围为6.18～81.8μg·L-1,主要污染物为邻苯二甲酸二丁酯(dibutyl phthalate,DBP)、邻苯二甲酸丁基苄基酯(butyl benzyl phthalate,BBP)和邻苯二甲酸二甲酯(dimethyl phthalate,DMP)。长江干流中游水体中PAEs的浓度明显高于上游和下游,在乌江汇入长江干流的监测位点水体中也检出了较高浓度的PAEs,主要原因可能与其受周围工业园区所排放废水的影响有关。沉积物中共检出8种PAEs,浓度范围为2.24～12.26μg·g-1,污染物以邻苯二甲酸二(2-乙基己基)酯(bis(2-ethylhexyl) phthalate,DEHP)、BBP和DBP为主;沉积物中PAEs的沿江分布均未发现明显规律,其受工业废水排放的影响相对较小。生态风险评估结果表明,水体中DBP在大部分位点,以及邻苯二甲酸二异丁酯(DIBP)和DEHP在少数位点,均存在一定程度的潜在生态风险,而DMP、邻苯二甲酸二乙酯(DEP)、BBP和邻苯二甲酸二正辛酯(DOP)的生态风险均处于可接受范围;沉积物中DEHP对生物体存在一定的潜在影响,而DBP的潜在风险相对较小。     

汾河流域邻苯二甲酸酯的分布特征及生态风险评价

本文以汾河流域作为研究对象,系统研究了水相及沉积物中6种邻苯二甲酸酯(PAEs)的含量、组成和空间分布,同时对汾河流域水体和沉积物中PAEs进行生态风险评价.研究表明,汾河流域丰水期水相中PAEs总量为2.79—206.33μg·L~(-1),平均浓度按DEHP(邻苯二甲酸(2-乙基己基)酯)DBP(邻苯二甲酸二丁酯)BBP(邻苯二甲酸丁基节基酯)DEP(邻苯二甲酸二乙酯)DMP(邻苯二甲酸二甲酯)DNOP(邻苯二甲酸二正辛酯)的顺序递减.其空间分布结果表现为,干流PAEs浓度低于支流,从上游到下游干流PAEs浓度呈现先升后降的趋势.依据国家地表水环境质量标准(GB3838—2002)对DBP、DEHP标准限值的规定,丰水期有60%的站点超过3μg·L~(-1)和8μg·L~(-1)的限值.丰水期沉积物中PAEs浓度范围为0.064—3.551μg·L~(-1),平均浓度按DEHPDBPDMPDEPBBP的顺序递减,干流PAEs高于支流,中下游PAEs含量高于上游,其中中游的太原段沉积相中PAEs污染相对严重.生态风险评价结果表明,汾河流域水相中PAEs的生态风险大小排序依次为DBPDEHPDEPDMP,DBP和DEHP在大部分采样点存在一定的潜在生态风险,DMP和DEP的生态风险在可接受范围;沉积物PAEs中所有种类的平均含量未超过风险评价的低值(ERL),对生物的潜在危害较小.     

番茄对污染土壤中邻苯二甲酸酯的吸收累积特征

利用盆栽实验研究了番茄对污染土壤中邻苯二甲酸酯(PAEs)的吸收积累特征。结果表明,番茄根系、茎、叶和果实均可以吸收累积PAEs化合物,其含量与土壤污染程度成正相关;相同处理的番茄茎、叶和果实中邻苯二甲酸正丁酯(DBP)含量均高于邻苯二甲酸异辛酯(DEHP),而番茄根系中DBP的含量低于DEHP; 4个不同处理方式土壤中DBP和DEHP的残留量顺序均为:灭菌土壤组灭菌土壤种植番茄苗组未灭菌土壤组未灭菌土壤种植番茄苗组。无论是灭菌处理还是未灭菌处理,有番茄苗组土壤中PAEs含量均低于无番茄苗组,未灭菌土壤种植番茄苗组土壤中PAEs残留量最低,PAEs削减率高达96.39%,有番茄苗组微生物数量大于无番茄苗组。这些说明土壤中PAEs的削减是番茄植物和微生物协同作用的结果。     

典型废旧塑料处置地土壤中邻苯二甲酸酯污染特征及健康风险

对河北某典型废旧塑料处置地土壤中邻苯二甲酸酯污染水平及分布特征进行了研究.结果表明,废旧塑料处置地土壤中∑_(16)PAEs含量0.517—30.1μg·g~(-1),平均为6.98μg·g~(-1),与电子垃圾处理地土壤PAEs含量处于同一个数量级,高出一般土壤1—2个数量级.邻苯二甲酸二(2-乙基)己酯(DEHP),邻苯二甲酸二异丁酯(DIBP)和邻苯二甲酸二丁酯(DBP)为PAEs污染的主要同系物,其中DEHP对总量贡献率最大,平均为68.8%.废旧塑料回收利用过程中的污染排放是该研究区土壤中PAEs的主要来源.对美国EPA和欧盟优先控制的6种PAEs(邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-乙基)己酯、邻苯二甲酸二正辛酯)同系物进行了风险评价,结果表明成人和儿童对DEHP暴露的致癌风险超出了可接受水平.废旧塑料处置地土壤的PAEs污染应引起高度重视.     

最大累积率识别中国地表水中邻苯二甲酸酯类关键污染物和复合污染生态风险

邻苯二甲酸酯类物质(phthalic acid esters,PAEs)环境存在量大,研究表明其能对水生生物造成寿命减少、发育不良、细胞受损等负效应.因此,为保护水生生物,我国地表水中PAEs的生态风险需要科学评估.本文利用了风险商法(risk quotient,RQ)、最大累积率法(maximum cumulative ratio,MCR)、联合概率曲线法(joint probability curve,JPC)结合毒性当量的概念构建了三层级生态风险评价体系,借此评估了我国地表水中PAEs的分布情况与生态风险.结果显示,我国地表水中共检出19种PAEs,浓度范围为ND—5616.80μg·L^-1.邻苯二甲酸二(2-乙基)己酯(di(2-ethylhexyl)phthalate,DEHP)和邻苯二甲酸二丁酯(dibutyl phthalate,DBP)环境存在量最高,且DEHP为PAEs风险的主要贡献者.以DEHP为参照物,JPC的结果显示我国PAEs对5%生物造成急性影响的概率为6.25%—24.02%,造成慢性影响的概率为8.05%—27.79%.PAEs对我国水生生态系统,尤其是西北、东北、中部及华东地区存在较高的生态风险.     

江苏省不同地区设施菜地土壤-蔬菜中邻苯二甲酸酯分布特征

在江苏省设施菜地共采集50个表层土壤样品和50个蔬菜样品,采用加速溶剂萃取-气质联用仪技术,对土壤-蔬菜中邻苯二甲酸酯(PAEs)含量进行分析,并对其污染分布和污染程度进行评价。结果显示:江苏省设施菜地土壤样品中6种w(PAEs)范围为42.46~276.76μg·kg~(-1),平均值为116.7μg·kg~(-1),检出率为100%,以邻苯二甲酸二正丁酯(DBP)和邻苯二甲酸(2-乙基己基)酯(DEHP)为主,分别占w(PAEs)的64.49%和23.92%;4个产区土壤中w(PAEs)平均值从大到小依次为苏州、淮安、盐城和宿迁,与美国土壤6种优控的PAEs控制标准相比,w(DBP)超过控制标准,超标率为24%。蔬菜样品中w(PAEs)范围为38.31~241.87μg·kg~(-1),平均含量为104.25μg·kg~(-1),检出率为100%,以DEHP和邻苯二甲酸二正辛酯(Dn OP)为主,分别占w(PAEs)的25.34%和24.59%,不同产区蔬菜中w(PAEs)平均值从大到小依次为苏州、盐城、淮安和宿迁,蔬菜中PAEs含量及各组分含量均低于美国和欧洲的建议摄入标准。土壤-蔬菜中w(PAEs)、w(DBP)和w(DEHP)存在显著正相关,不同蔬菜对土壤中6种PAEs化合物的富集能力存在明显差异,对PAEs的富集系数约为1。因此,在设施菜地土壤质量评价过程中,应重视蔬菜自身特性对PAEs吸收和富集的影响。     

内河螺蛳（Margaryamelanioides）对水环境中邻苯二甲酸酯类的富集

为探索内河底栖生物对水环境中PAEs的富集规律,采用气相色谱质谱法定量测定宁波城市内河回龙段水体、底泥、螺蛳肉与壳中DMP、DEP、DIPP、DPP、DBP、BBP、DEHP和DOP的浓度。结果表明研究河域底泥、水样、螺蛳（Margaryamelanioides）肉和螺壳样品主要存在DMP、DBP、DEHP3种PAEs,DMP的平均浓度分别为3．435μg／g、0．023μg／g、1．239μg／g和0．712μg／g,DBP为2．613μg／g、0．484μg／g、6．984μg／g和0．282μg／g;DEHP为13．891μg/g、0．030μg／g、4．938μg／g和0．156μg／g,∑PAEs表现为底泥〉螺蛳肉〉螺壳〉水样。螺蛳肉及螺蛳壳对酯类富集能力分别表现为DEHP〉DBP〉DMP,DMP〉DEHP〉DBP,且螺蛳肉的富集能力明显强于螺蛳壳。螺蛳肉与水样DMP浓度呈显著的正相关,DBP和DEHP不相关;螺蛳壳中3种PAEs均与采样位点水样的PAEs呈显著的相关性;螺蛳肉、螺蛳壳与底泥的PAEs浓度均呈显著的相关性;各位点的螺蛳肉与螺蛳壳富集的3种PAEs浓度均呈显著的正相关。     

Distribution and sources of phthalate esters in the topsoils of Beijing,China

Phthalate esters in the topsoil samples collected from Beijing were determined by derivatization and gas chromatography–mass spectrometry techniques. The results showed that diethyl phthalate (DEP), diisobutyl phthalate ester (DIBP), dibutyl phthalate ester (DBP), dibutyl (2-ethyl hexyl) phthalate (DEHP), and dimethyl phthalate (DMP) were found in the topsoils. The total concentrations of the five phthalate esters varied from 2.30 to 24.71 μg g^?1. According to phthalate esters (PAEs) control standards in soil of the USA, the standard exceeding rates of DMP, DBP, and DEHP were 100 %, 100 %, and 4.84 % in soils of Beijing, respectively. The rate of DBP exceeding soil remediation standard was 12.9 %. Overall, concentrations of PAEs in Beijing were at a high level in China. The concentrations of DBP, DEHP, and DIBP were high, and the total concentrations of all the phthalate esters were higher in the areas with intensive human activities than in the other areas, which may be related to the use of phthalate compounds (such as the use of plastic products). The total and individual concentrations of phthalate compounds were relatively low in the areas that used plastic films compared with other samples due to the diffusion of atmospheric motion, categories, and amounts of plastic products and other factors. The greatest contributor may be the usage amount of plastic products in people’s daily lives.     

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     

Investigating into composition,distribution, sources and health risk of phthalic acid esters in street dust of Xi’an City,Northwest China

Phthalic acid esters (PAEs) are widely used as plasticizers and in consumer products, which may enter the environment and present risks to human health. U.S. EPA classifies six PAEs as priority pollutants, which could be accumulated in street dust at the interface of atmosphere, biosphere and geosphere. This study collected a total of 58 street dust samples from Xi’an City in Northwest China and analyzed for concentrations of the priority PAEs. Composition, distribution, sources and health risk of the PAEs were further examined. All the priority PAEs were detected in the street dust. The concentrations of individual PAEs varied between not detected and 183.19 mg/kg. The sum of the 6 priority PAEs (∑6PAEs) ranged from 0.87 to 250.30 mg/kg with a mean of 40.48 mg/kg. The most abundant PAEs in the street dust were di-n-butyl phthalate and di (2-ethylhexyl) phthalate (DEHP). Higher concentrations of ∑6PAEs in the street dust were found in the south and west parts of Xi’an City as well as its urban center, which were possibly attributed to the prevailing northerly Asian winter monsoon. The PAEs in the street dust originated mainly from wide application of plasticizers as well as cosmetics and personal care products. The main pathways of human exposure to PAEs in the street dust were ingestion and dermal adsorption of dust particles. The non-cancer risk of human exposure to PAEs in the street dust was relatively low, while the risk to children was higher than that to adults. The cancer risk of human exposure to DEHP in the street dust was lower than the standard limit value of 10^?6.     

Occurrence and migration of microplastics and plasticizers in different wastewater and sludge treatment units in municipal wastewater treatment plant

● Reduce the quantifying MPs time by using Nile red staining. ● The removal rate of MPs and PAEs in wastewater and sludge were investigated. ● MPs and PAEs were firstly analyzed during thermal hydrolysis treatment. ● The removal of PAEs from wastewater and sludge was mainly biodegradation. Microplastics (MPs) and plasticizers, such as phthalate esters (PAEs), were frequently detected in municipal wastewater treatment plants (MWTP). Previous research mainly studied the removal of MPs and PAEs in wastewater. However, the occurrence of MPs and PAEs in the sludge was generally ignored. To comprehensively investigate the occurrence and the migration behaviors of MPs and PAEs in MWTP, a series of representative parameters including the number, size, color, shape of MPs, and the concentrations of PAEs in wastewater and sludge were systematically investigated. In this study, the concentrations of MPs in the influent and effluent were 15.46±0.37 and 0.30±0.14 particles/L. The MP removal efficiency of 98.1% was achieved and about 73.8% of MPs were accumulated in the sludge in the MWTP. The numbers of MPs in the sludge before and after digestion were 4.40±0.14 and 0.31±0.01 particles/g (dry sludge), respectively. Fourier Transform Infrared Spectroscopy (ATR FT-IR) analysis showed that the main types of MPs were polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), and polystyrene (PS). Six PAEs, including phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), ortho dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), and bis(2-ethyl) hexyl phthalate (DEHP), were detected in the MWTP. The concentrations of total PAEs (ΣPAEs) in the influent and effluent were 76.66 and 6.28 µg/L, respectively. The concentrations of ΣPAEs in the sludge before and after digestion were 152.64 and 31.70 µg/g, respectively. In the process of thermal hydrolysis, the number and size of MPs decreased accompanied by the increase of the plasticizer concentration.     

水体中悬浮颗粒物对酞酸酯的吸附和解吸特性

选择水体中的悬浮颗粒物(SPM)--沉积颗粒物和浮游植物颗粒(铜绿微囊藻和普通小球藻),研究它们对邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异辛酯(DEHP)的吸附和解吸行为.结果表明,SPM对DBP 和DEHP的吸附在很短的时间内即可达到平衡,沉积颗粒物约为2h,浮游植物颗粒约为0.5h;SPM对DEHP的吸附能力明显大于DBP;不同SPM对同一种化合物的吸附能力差异较大,这与颗粒物中有机质的类型和结构有关;在实验浓度范围内,SPM对DBP和DEHP的吸附和解吸等温线具有较好的线性关系,解吸过程存在明显的迟滞现象,且沉积颗粒物比浮游植物颗粒物具有明显的迟滞效应,DBP比DEHP具有较大程度的迟滞效应.     

Bestimmung von Phthalsäureestern in Lebensmitteln, Frauenmilch, Hausstaub und Textilien

25 food samples, 5 mother’s milk specimens, 4 dust samples, and 16 textiles were analysed for phthalic acid esters. Phthalic acid esters were detected in all samples, with di (2-ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DBP) being the most abundant phthalates. Raw milk samples revealed average concentrations of total phthalate of 0.1 mg/kg. Retail milk did not contain higher loads than raw milk, even storing samples until their “best-before” date did not result in elevated levels. Skimmed milk was less contaminated than whole milk. The higher concentrations of DEHP and total phthalates in cream samples are due to their higher fat content. With concentrations up to 1.54 mg/kg, ground hazelnuts, almonds, and nutmeg in plastic packagings showed relatively high levels. In infant food, only traces of DEHP and DBP could be found while other phthalic acid esters were not detectable. The mother’s milk samples also exhibited only low amounts of approx. 0.1 mg/kg, thus indicating that there is no accumulation of phthalate esters in the human body. Extraordinarily high concentrations were found in dust samples; with the levels ranging from 300 to 5370 mg/kg and DEHP being the major compound. This leads to the conclusion that the air path must play a considerable role in the transfer of phthalic acid esters. As dust contains considerable amounts of textile fibres, textiles were also included in the investigation. The phthalic ester levels in the textile samples ranged from 3.42 to 34.44 mg/kg. Therefore, the high phthalate contaminations of dust cannot be explained by textile fibres.     

Occurrence of estrogenic endocrine disrupting chemicals concern in sewage plant effluent

The purpose of this study was to give a worldwide overview of the concentrations of typical estrogenic endocrine disrupting chemicals （EDCs） in the effluent of sewage plants and then compare the concentra- tion distribution of the estrogenic EDCs in ten countries based on the survey data of the estrogenic EDCs research. The concentrations of three main categories （totally eight kinds） of estrogenic EDCs including steroidal estrogens （estrone （El）, estradiol （E2）, estriol （E3） and 17a- ethynylestradiol （EE2））, phenolic compounds （nonylphe- nol （NP） and bisphenol A （BPA）） and phthalate esters （dibutyl phthalate （DBP） and dibutyl phthalate （2- ethylhexyl） phthalate （DEHP）） in the effluents of sewage plants reported in major international journals over the past decade were collected. The statistics showed that the concentration distributions of eight kinds of EDCs were in the range of ng·L^-1 to μg·L^-1. The concentrations of steroidal estrogens mainly ranged within 50.00 ng. L-1, and the median concentrations of El, E2, E3 and EE2 were 11.00, 3.68, 4.90 and 1.00 ng·L^-1, respectively. Phenolic compounds and phthalate esters were found at pg. L-1 level （some individual values were at the high level of 40.00 μg·L^-1）. The median concentrations of BPA, NP, DBP and DEHP were 0.06, 0.55, 0.07 and 0.88 μg·L^-1, respectively. The concentrations of phenolic compounds and phthalate esters in the effluents were higher than that of steroids estrogens. The analysis of the concentration in various ten countries showed that steroids estrogens, phenolic compounds and phthalate esters in sewage plant effluents were detected with high concentration in Canada, Spain and China, respectively.