广东省典型区域农业土壤中邻苯二甲酸酯含量的分布特征

采用气相色谱方法,对广东省典型区域农业表层土壤(0～20cm)样品中的6种邻苯二甲酸酯(PAEs)进行了测定.结果表明:6种PAEs化合物的总含量(∑PAEs)为nd(未检出)～25.99mg.kg-1,其中92.8%的样品分布在≤1mg.kg-1的范围;各种土地利用类型中∑PAEs的顺序依次为水田>香蕉地>菜地>甘蔗地>果园地;不同地区土壤中∑PAEs的顺序依次为东莞市>汕头市>佛山市顺德区>湛江市>中山市>珠海市>惠州市.邻苯二甲酸二(2-乙基已基)酯(DEHP)的检出率最高(85.1%),邻苯二甲酸二正丁酯(DnBP)含量最高(nd～17.51mg.kg-1).与美国土壤PAEs控制标准相比,除邻苯二甲酸二正辛酯(DnOP)外,其余5种PAEs化合物均有不同程度的超标,其中DnBP、邻苯二甲酸二甲酯(DMP)和邻苯二甲酸二乙酯(DEP)3种化合物超标率较高.广东省典型区域农业土壤受到不同程度的PAEs污染.     

地膜使用年限对遵义市烟田土壤和烟叶邻苯二甲酸酯累积的影响

研究地膜使用年限对土壤和烟叶邻苯二甲酸酯(PAEs)积累的影响,以明确地膜持续使用条件下PAEs的土壤污染分布特征及在烟叶中的富集状况.在遵义市连阡村和沙湾村采集了不同覆膜年限的烟田土壤及相应的烟叶,采用气相色谱仪质谱联用技术(GC-MS),对土壤-烟叶中6种优先控制PAEs含量进行了测定.结果表明: 所有土壤和烟叶样品中6种邻苯二甲酸酯化合物累计(∑PAEs)分别为(2.66±0.60)和(3.58±0.64) mg·kg^-1,其中,邻苯二甲酸二(2-乙基己)酯(DEHP)含量最高,邻苯二甲酸正二丁酯(DBP)次之,二者之和分别占土壤和烟叶∑PAEs的92.7%和88.9%.DEHP、DBP、邻苯二甲酸二乙酯(DEP)和邻苯二甲酸丁基苄基酯(BBP)检出率均为100.0%,邻苯二甲酸二甲酯(DMP)的检出率略低,邻苯二甲酸正二辛酯(DnOP)检出率最低.随着地膜使用年限的增加,土壤和烟叶中PAEs含量显著增加,且在地膜使用的前1~ 8年增加更为明显,后期趋于平缓.土壤和烟叶中的PAEs含量与覆膜年限呈显著正相关关系,覆膜年限的增加会显著促进土壤和烟叶中PAEs的积累.烟叶与土壤之间∑PAEs的累积量相关性不显著.     

山东省花生主产区土壤和花生籽粒中邻苯二甲酸酯的分布特征

在山东省四大花生主产区采集耕层土壤(0～20 cm)和花生籽粒,应用气相色谱测定样品中美国国家环保署(EPA)优先控制的6种邻苯二甲酸酯(PAEs)化合物的含量.结果表明: 山东省花生主产区土壤中6种PAEs化合物累计(∑PAEs)含量范围为0.34～2.81 mg·kg^-1,平均含量为1.22 mg·kg^-1;四大花生主产区土壤∑PAEs含量为：鲁中南山区＞鲁西平原＞胶东半岛＞鲁北平原;与美国土壤PAEs控制标准相比,山东省四大花生主产区土壤中的邻苯二甲酸正二丁酯(DBP)超标严重.花生籽粒中∑PAEs含量范围为0.17～0.66 mg·kg^-1,平均含量为0.34 mg·kg^-1,低于美国和欧洲的建议指标,健康风险很小.邻苯二甲酸二(2-乙基己基)酯(DEHP)和DBP在土壤和花生籽粒中占∑PAEs的百分比、检出率均较高,是主要的污染物组分.覆膜种植模式下土壤和花生籽粒中的∑PAEs显著高于露地种植模式.花生籽粒和土壤中的∑PAEs、DBP及DEHP存在显著正相关性,Pearson相关系数分别为0.786、0.747和0.511.     

农业土壤中邻苯二甲酸酯污染研究进展

由邻苯二甲酸酯(PAEs)引起的环境污染和食品安全问题已经引起全球性关注.我国既是邻苯二甲酸酯生产大国,又是消费大国,其环境污染问题不容忽视.本文综述了美国国家环保署所列出的6种优先控制PAEs污染物在我国农田土壤中的污染现状,分析了其来源,重点阐述了不同类型农作物对PAEs化合物的吸收累积特征及PAEs类污染物的生物毒害效应.我国多数地区农业土壤中PAEs的含量显著高于美国和欧洲等国家.大气沉降、农用薄膜、施用污泥和污水灌溉是我国农业土壤中PAEs的主要来源.不同作物对PAEs的吸收、累积和分配特征具有显著的差异性.PAEs不但影响土壤质量、作物生长和生理生化性质,而且具有生物累积效应.最后指出了当前研究中的不足及对今后研究的展望,建议扩大PAEs污染调查范围,深入揭示PAEs对农作物的毒害机理,重点研发PAEs污染土壤的原位修复技术.     

城市污泥与稻草堆肥中邻苯二甲酸酯（PAEs）的研究

将广州城市污泥与稻草进行翻堆、接菌-翻堆、连续通气和间歇通气4种方式的堆肥,应用GC／MS技术对堆肥中6种属于USEPA优控污染物的邻苯二甲酸醇化合物(PAEs)进行分析,探讨堆肥产物中PAEs的含量分布以及不同方式堆肥对PAEs的降解效果,结果表明,4种方式堆肥中PAEs总含量(∑PAEs)在9．815～17．832mg·kg^-1之间,依次为翻堆(17．832mg·kg^-1)>接菌-翻堆(13．927mg·kg^-1)>间隙通气(10．765mg·kg^-1)>连续通气(9．815mg·kg^-1),堆肥中PAEs以邻苯二甲酸正二辛酯(DhOP)为主,占∑PAEs的82．2％～89．696,不同方式堆肥中∑PAEs的降解率为连续通气(45．71％)>间隙通气(40．4696)>接菌-翻堆(22．97％)>翻堆(1．3796)(平均降解率为27．63％),其中邻苯二甲酸二乙醇(DEP)、邻苯二甲酸正二丁酯(DnBP)和邻苯二甲酸丁基苄基酯(BBP)的降解率分别为95．7696～98．6896、79．5696～99．46％和87．42％～98．42％;但邻苯二甲酸二甲酯(DMP)和邻苯二甲酸正二辛酯的含量反而增加,邻苯二甲酸(2-乙基己基)酯(DEHP)在所有堆肥中均未检出。     

肉桂酸和邻苯二甲酸对沙芥属植物幼苗光合特性的影响

为探讨肉桂酸和邻苯二甲酸对沙芥属植物光合特性的影响，以沙芥和斧翅沙芥幼苗为试验材料，研究 0、0.01、0.1、1和10 mmol·L-1肉桂酸和邻苯二甲酸处理下其生长、叶绿素含量、叶绿素荧光参数和气体交换参数的变化。结果表明：（1）肉桂酸、邻苯二甲酸对沙芥幼苗生长均表现为低浓度促进高浓度抑制，而对斧翅沙芥生长则表现为抑制作用，肉桂酸、邻苯二甲酸浓度为10 mmol·L-1时对沙芥属植物的生长抑制作用最显著。（2）不同浓度肉桂酸和邻苯二甲酸处理后沙芥与斧翅沙芥的叶绿素a（Chl a）、叶绿素b（Chl b）、叶绿素总量(Chl.a+b)均出现不同程度的下降（3）沙芥和斧翅沙芥叶片净光合速率（Pn）、蒸腾速率（Tr）、气孔导度（Gs）在肉桂酸和邻苯二甲酸浓度为10 mmol·L-1显著低于对照，胞间 CO2浓度（Ci）无显著变化，其光合速率降低的主要原因是由非气孔因素所致。（4）沙芥和斧翅沙芥的最大光化学效率（Fv/Fm）、实际光化学效率（ФPSII）和光化学猝灭系数（qP）均在肉桂酸和邻苯二甲酸浓度为10 mmol·L-1显著低于对照，而非光化学荧光猝灭系数( NPQ ) 则显著高于对照。研究表明，高浓度邻苯二甲酸和肉桂酸抑制沙芥和斧翅沙芥幼苗的光合作用，降低其光合速率，导致沙芥和斧翅沙芥叶片的PSII反应中心活性和开放程度受损，进而影响沙芥和斧翅沙芥的生长。另外肉桂酸和邻苯二甲酸对沙芥属植物光合特性的影响表现出差异，这可能是由于植物类型和胁迫类型不同而表现出不同的变化趋势。     

大伙房水库3种邻苯二甲酸酯分布特征与风险评价

大伙房水库作为辽宁省重要饮用水源地,库区水质安全具有举足轻重的作用。本研究对不同季节大伙房水库库区及主要入库河流中3种主要邻苯二甲酸酯(PAEs)的空间分布及季节变化特征进行了分析,并利用风险暴露模型对库区水体PAEs的风险特征进行了评估。结果表明,大伙房水库库区及入库河流流域中的PAEs含量均处于较低水平,在空间分布上库区中PAEs分布呈自东向西先增大后减小的趋势,在季节上具有夏季春季秋季的变化特点;主要入库河流中PAEs浓度呈自河流上游至下游逐渐增高的趋势,秋季河流水体中PAEs含量最少。在PAEs组分上,邻苯二甲酸二正丁酯(DBP)在所有采样点均有检出,DBP和邻苯二甲酸二异辛酯(DEHP)具有一定的同源性且与水中总氮、总磷浓度呈负相关。风险暴露模型结果表明,大伙房水库中DBP的非致癌风险指数均远小于1,不会对人体产生健康危害。     

植物对土壤中铀的吸收与富集

核工业发展导致重金属铀排放和扩散,并造成了地表土壤的污染,对人类的生存环境产生了极其不利的影响。如何修复铀污染土壤成为亟待解决的问题。近年来发展起来的植物修复技术以其成本低廉、安全和环保的特点成为修复铀污染土壤的新选择。寻找理想的铀富集植物是这一技术的基础和关键。该文通过实验模拟铀污染的土壤（土壤中铀的浓度为100 mg.kg–1）,进行一次和二次铀污染土壤的植物修复后,从4个方面对植物修复铀污染土壤效果进行评估,即富集铀的浓度、生物提取量、生物富集系数（BFS）和转运系数（TFS）。实验结果表明：第1次修复时,四季香油麦菜（Lactuca dolichophylla）地上部富集铀的浓度为1.67×103 mg.kg–1,生物富集系数和转移系数均大于3;第2次修复时,麦冬（Ophiopogon japoni-cus）富集铀的浓度与第1次修复相比变化不大,而吊兰（Chlorophytum comosum）、四季豆（Phaseolus vulgaris）和艾蒿（Artemisia lavandulaefolia）富集铀的浓度与第1次修复相比均减少4–8倍;施加土壤改良剂鸡粪肥、海藻肥和柠檬酸后发现海藻肥和柠檬酸能够增强植物对铀污染土壤的修复;对两次修复土壤中铀的形态进行对比分析,发现二次修复时土壤中生物有效态铀的含量降低,造成第2次修复的难度增加。     

一株黄色杆菌的分离鉴定及对邻苯二甲酸酯的降解研究

邻苯二甲酸酯(PAEs)是环境中普遍存在的有机污染物,具有环境雌激素效应,对人体健康和生态安全造成严重威胁。菌株YC-JY1分离自受石油长期污染的土壤中,可以利用邻苯二甲酸二丁酯(DBP)作为唯一的碳源进行生长;经16S rDNA鉴定,确定其属于黄色杆菌属(Xanthobacter sp.)。菌株YC-JY1降解DBP的最适条件为30℃,pH 7.0,无NaCl添加;在此条件下,100mg/L DBP在5 d内能被完全降解。随着DBP浓度的升高,菌株YC-JY1在5 d内对200 mg/L-400 mg/L DBP的降解率在94%以上;通过底物谱实验发现,菌株YC-JY1对其它邻苯二甲酸酯具有广泛的利用能力,其中邻苯二甲酸二戊酯(DPeP),邻苯二甲酸二己酯(DHP)的降解率均在90%以上;通过高效液相色谱-质谱联用确定DBP中间代谢产物为邻苯二甲酸单丁酯(MBP),邻苯二甲酸(PA)。由此推断,在菌株YC-JY1的作用下,DBP的起始代谢途径为DBP首先水解为MBP,继而水解为PA。     

邻苯二甲酸酯类(PAEs)对三角鲂的急性毒性研究

为了研究邻苯二甲酸酯对水生态系统的危害,以三角鲂(Magalobrame Tarminalis)幼鱼为研究对象,探讨邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二-2-乙基己酯(DEHP)、邻苯二甲酸二乙酯(DEP)4种PAEs化合物对其急性毒性效应。结果表明:以上4种化合物在暴露24 h、48 h和96 h的半致死质量浓度(LC50)分别为2.75、2.41和2.08 mg/L;5.29、4.12和3.29 mg/L;6.56、6.15和5.41 mg/L和6.98、6.84和6.60mg/L。其安全浓度(SC)分别为0.55、0.79、1.62和2.00 mg/L。三角鲂幼鱼对4种PAEs化合物的中毒症状相似,但4种物质的致死浓度区间存在差别,4种物质对三角鲂幼鱼的毒性大小顺序为DBP>DMP>DEHP>DEP,三角鲂幼鱼对4种PAEs化合物均表现出显著的时间效应和剂量效应,呈正相关。结果表明,4种物质在试验浓度下对三角鲂幼鱼产生了明显的毒性作用,对水生生物存在危害,应对其水生态风险加以关注。为制定4种PAEs水质标准及对其进行生态风险评价提供科学依据。     

Contamination of Phthalate Esters (PAEs) in Typical Wastewater-Irrigated Agricultural Soils in Hebei,North China

The Wangyang River (WYR) basin is a typical wastewater irrigation area in Hebei Province, North China. This study investigated the concentration and distribution of six priority phthalate esters (PAEs) in the agricultural soils in this area. Thirty-nine soil samples (0–20 cm) were collected along the WYR to assess the PAE residues in soils. Results showed that PAEs are ubiquitous environmental contaminants in the topsoil obtained from the irrigation area. The concentrations of Σ₆PAEs range from 0.191 μg g⁻¹ dw to 0.457 μg g⁻¹ dw with an average value of 0.294 μg g⁻¹ dw. Di(2-ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DnBP) are the dominant PAE species in the agricultural soils. Among the DEHP concentrations, the highest DEHP concentration was found at the sites close to the villages; this result suggested that dense anthropogenic activities and random garbage disposal in the rural area are possible sources of PAEs. The PAE concentrations were weakly and positively correlated with soil organic carbon and soil enzyme activities; thus, these factors can affect the distribution of PAEs. This study further showed that only dimethyl phthalate (DMP) concentrations exceeded the recommended allowable concentrations; no remediation measures are necessary to control the PAEs in the WYR area. However, the PAEs in the topsoil may pose a potential risk to the ecosystem and human health in this area. Therefore, the exacerbating PAE pollution should be addressed.     

LEGUME-GRASS INTERCROPPING PHYTOREMEDIATION OF PHTHALIC ACID ESTERS IN SOIL NEAR AN ELECTRONIC WASTE RECYCLING SITE: A FIELD STUDY

A field experiment was conducted to study the phytoremediation of phthalic acid esters (PAEs) by legume (alfalfa, Medicago sativa L.)-grass (perennial ryegrass, Lolium perenne L. and tall fescue, Festuca arundinacea) intercropping in contaminated agricultural soil at one of the largest e-waste recycling sites in China. Two compounds, DEHP and DnBP, were present in the soil and in the shoots of the test plants at much higher concentrations than the other target PAEs studied. Over 80% of ‘total’ (i.e., all six) PAEs were removed from the soil across all treatments by the end of the experiment. Alfalfa in monoculture removed over 90% of PAEs and alfalfa in the intercrop of the three plant species contained the highest shoot concentration of total PAEs of about 4.7 mg kg^?1 DW (dry weight). Calculation of phytoextraction efficiency indicated that the most effective plant combinations in eliminating soil PAEs were the three-species intercrop (1.78%) and the alfalfa monocrop (1.41%). Phytoremediation with alfalfa was effective in both monoculture and intercropping. High bioconcentration factors (BCFs) indicated the occurrence of significant extraction of PAEs by plants from soil, suggesting that phytoremediation may have potential for the removal of PAEs from contaminated soils.     

Determination of PAEs in soil of municipal wards of Patna,India by microwave assisted extraction and LC-MS/MS

Phthalic Acid Esters (PAEs) have become ubiquitous in environment due to unrestrained manufacture and use of plasticizers. The occurrence of PAEs in food, beverages, environmental and biological samples has been reported worldwide. PAEs are widely used in plasticizers for imparting flexibility and are not covalently bonded with the polymers, enabling PAEs to leach out due to change in pH and temperature. This study attempts to identify and quantify the PAEs in soil of Patna, India. Soil samples were collected from 22 municipal wards of Patna, Bihar. Microwave-Assisted Extraction (MAE) technique was applied for the extraction of PAEs followed by LC-MS/MS with electrospray ionization for the identification of different PAEs. Mono(4-pentenyl)phthalate (M(4P)P), Bis(2-hydroxyethyl) phthalate (BHEP), 2-Methylbutyl benzyl Phthalate (MBBP), Octyl Decyl phthalate (ODP), Heptadecyl trimethylsilyl phthalate (HDTMP), Magnesium phthalate (MgP), Diethyl Phthalate (DEP) and Dibutyl phthalate (DBP) were identified by LC-MS/MS. Interestingly, it was observed that soil samples of nine municipal wards were contaminated with high levels of maximum number PAEs identified in the study. Conclusively, the assessment of PAEs in soils samples is imperative for the management of environmental pollution generated by human activity.     

Phthalic Acid Esters in Soils from Vegetable Greenhouses in Shandong Peninsula,East China

Soils at depths of 0 cm to 10 cm, 10 cm to 20 cm, and 20 cm to 40 cm from 37 vegetable greenhouses in Shandong Peninsula, East China, were collected, and 16 phthalic acid esters (PAEs) were detected using gas chromatography-mass spectrometry (GC-MS). All 16 PAEs could be detected in soils from vegetable greenhouses. The total of 16 PAEs (Σ₁₆PAEs) ranged from 1.939 mg/kg to 35.442 mg/kg, with an average of 6.748 mg/kg. Among four areas, including Qingdao, Weihai, Weifang, and Yantai, the average and maximum concentrations of Σ₁₆PAEs in soils at depths of 0 cm to 10 cm appeared in Weifang, which has a long history of vegetable production and is famous for extensive greenhouse cultivation. Despite the different concentrations of Σ₁₆PAEs, the PAE compositions were comparable. Among the 16 PAEs, di(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DnOP), di-n-butyl phthalate (DnBP), and diisobutyl phthalate (DiBP) were the most abundant. Compared with the results on agricultural soils in China, soils that are being used or were used for vegetable greenhouses had higher PAE concentrations. Among PAEs, dimethyl phthalate (DMP), diethyl phthalate (DEP) and DnBP exceeded soil allowable concentrations (in US) in more than 90% of the samples, and DnOP in more than 20%. Shandong Peninsula has the highest PAE contents, which suggests that this area is severely contaminated by PAEs.     

Anaerobic degradation of phthalic acid esters during digestion of municipal solid waste under landfilling conditions

Anaerobic microorganisms in municipal solid waste samples from laboratory-scale landfill reactors and a pilot-plant biogas digestor were investigated with the aim of assessing their ability to transform four commercially used phthalic acid esters (PAEs) and phthalic acid (PA). The PAEs studied were diethyl phthalate (DEP), butylbenzyl phthalate (BBP), dibutyl phthalate (DBP) and bis(2-ethylhexyl) phthalate (DEHP). No biological transformation of DEHP could be detected in any of the experiments. Together with waste samples from the simulated landfilling conditions, the PAEs (except DEHP) were hydrolytically transformed to their corresponding monoesters. These accumulated as end products, and in most cases they were not further degraded. During incubation with waste from the biogas digestor, the PAEs (except DEHP) were completely degraded to methane and carbon dioxide. The influence of the landfill development phase on the transformations was investigated utilizing PA and DEP as model substances. We found that during both the intense and stable methanogenic (but not the acidogenic) phases, the microoganisms in the samples had the potential to transform PA. A shorter lag phase was observed for the PA transformation in the samples from the stable methanogenic phase as compared with earlier phases. This indicates an increased capacity to degrade PA during the aging phases of the municipal solid waste in landfills. No enhancement of the DEP transformation could be observed as conditions in the methanogenic landfill model changed over a year's time. The results indicate that microorganisms developing in a methanogenic landfill environment have a substantially lower potential to degrade PAEs compared with those developing in a biogas reactor.Abbreviations BBP butylbenzyl phthalate - DEHP bis(2-ethylhexyl) phthalate - CoA coenzyme A - DBP dibutyl phthalate - DEP diethyl phthalate - DS dry solids - MBeP monobenzyl phthalate - MBuP monobutyl phthalate - MEP monoethyl phthalate - MSW municipal solid waste - PA phthalic acid - PAE(s) phthalic acid ester(s) - VFA volatile fatty acids     

城市污泥和化肥对水稻土种植的通菜中邻苯二甲酸酯（PAEs）的影响

对水稻土施用城市污泥和化肥盆栽通菜,应用GC／MS联机检测技术对通菜中6种邻苯二甲酸酯化合物(PAEs)进行分析,探讨施肥对通菜中PAEs含量的影响,结果表明,各处理通菜中6种PAEs化合物的总含量(∑PAEs)在2．129～7.111mg·kg^-1之间,依次为广州污泥+化肥(7．111mg·kg^-1)>广州污泥(4．767mg·kg^-1)>佛山污泥(3;569mg·kg^-1)>佛山污泥+化肥(3．305mg·kg^-1)>化肥(2．638mg·kg^-1)>空白对照(2．129mg·kg^-1)。显示了施肥造成通菜中∑PAEs不同程度的提高,各处理通菜中的PAEs均以个别化合物为主,其中空白对照、化肥、佛山污泥和广州污泥处理的通菜中邻苯二甲酸丁基苄基酯(BBP)占∑PAEs的40％～81％。佛山污泥+化肥处理的通菜中邻苯二甲酸正二丁酯(DnBP)占∑PAEs的56％,而广州污泥+化肥处理的通菜中邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸正二辛酯(DnOP)和邻苯二甲酸(2-乙基己基)酯(DEHP)各占∑PAEs的30％左右,通菜中∑PAEs和多数化合物的含量不同程度地大于其在根系中的含量。     

Polycyclic aromatic hydrocarbons and phthalic acid esters in the soil-radish (Raphanus sativus) system with sewage sludge and compost application

We studied the accumulation of polycyclic aromatic hydrocarbons (PAHs) and phthalic acid esters (PAEs) in a latosolic red soil and radish (Raphanus sativus) with application of sewage sludge at rates of 10, 20 and 40 g kg(-1) soil or compost at rate of 10 g kg(-1) soil. In radish the concentrations of individual PAHs and PAEs varied from non-detectable to 803 microg kg(-1) dry weight (d.w.) and from non-detectable to 2048 microg kg(-1) d.w., respectively. Compared to the control, higher application rates of sewage sludge resulted in pronounced increases in shoot, root and soil concentrations of PAHs and PAEs. PAE concentrations in radish grown in soil spiked with sludge compost were higher while the PAH concentrations were comparable to those receiving 10 g kg(-1) of sewage sludge. However, the root biomass of radish in soil amended with compost was significantly higher and the shoot-to-root ratio was significantly lower than in the other treatments. The bioconcentration factors (BCFs, the ratio of contaminant concentration in plant tissue to the soil concentration) of di-n-butyl phthalate and di(2-ethylhexyl) phthalate in both shoots and roots and of total PAH concentrations in roots were less than 1.0, but some BCFs for individual PAHs were high with a maximum value of 80.