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.     

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。     

城市污泥中邻苯二甲酸酯(PAEs)的厌氧微生物降解

邻苯二甲酸酯(PAEs)是城市污泥中普遍存在的一类具有内分泌干扰性作用的有机污染物.研究污泥厌氧生物处理过程中PAEs的微生物降解对保障污泥农用的安全性十分必要.本文以污泥中两种主要的PAEs——邻苯二甲酸二丁酯(DBP)和邻苯二甲酸(2-乙基己)酯(DEHP)为研究对象,通过比较PAEs在污泥厌氧消化系统与发酵产氢系统中降解过程的差异及系统污泥特性的变化,分析不同污泥厌氧生物处理系统中影响PAEs降解的可能因素.结果表明: 在污泥厌氧发酵系统中,DBP在6 d内降解率达99.6%, DEHP在整个14 d的培养期间也降解了46.1%;在发酵产氢系统中,在14 d培养过程DBP的降解率仅为19.5%,DEHP则没有明显的降解.与厌氧消化系统相比,PAEs在发酵产氢系统中的降解受到明显抑制,这与发酵产氢过程中微生物量下降、革兰氏阳性菌/革兰氏阴性菌(G⁺/G^-)和真菌/细菌变小及挥发性脂肪酸(包括乙酸、丙酸及丁酸)浓度升高有关.     

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.     

一株高效DEHP降解菌的分离、鉴定及其降解特性

【目的】分离得到高效的邻苯二甲酸二乙基己基酯(DEHP)降解菌。【方法】采用富集培养法筛选分离菌株,并对菌株进行驯化;通过PCR扩增得到其16S rRNA和gyrB基因序列,进行同源序列分析及分子系统发育树的构建,同时结合形态学观察和生理生化实验对菌株进行初步鉴定;采用高效液相色谱(HPLC)分析菌株对DEHP的降解特性。【结果】分离得到一株能以DEHP为唯一碳源和能源生长的菌株,命名为HS-NH1,初步鉴定其为戈登氏菌(Gordoniasp.)。菌株HS-NH1最适的生长和降解条件为30°C、pH 7.0,在此条件下,该菌株60 h内能够将浓度为500 mg/L的DEHP降解90%以上。高效液相色谱(HPLC)分析表明,菌株HS-NH1在降解DEHP过程中产生了一种重要的中间代谢产物——邻苯二甲酸。底物广谱性试验证明,菌株HS-NH1能够有效地利用多种常见的邻苯二甲酸酯(PAEs)与芳香族衍生物。【结论】筛选得到了一株DEHP降解菌Gordonia sp.HS-NH1,该菌降解效率高,具有良好的底物广谱性,在邻苯二甲酸酯类化合物的污染治理中将会有一定的应用潜力。     

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。     

一株DMP降解菌的分离鉴定及其降解特性

从山东省潍坊市污染河流底泥中筛选到1株能够以酞酸酯(Phthalic acid esters, PAEs)为唯一碳源和能源生长的微生物, 命名为JDC-3, 根据形态学观察、生理生化指标测定和分子生物学鉴定结果, 将该菌株初步鉴定为戴尔福特菌属(Delftia sp.), 以一对简并引物, 首次在该属中扩增出编码邻苯二甲酸双加氧酶的基因片段。同时以邻苯二甲酸二甲酯(Dimethyl phthalate, DMP)为目标测试物, 利用高效液相色谱(HPLC)测定了JDC-3的降解性能, 得出该菌对DMP降解的最佳条件为: pH 7.0~8.0、温度30°C~35°C; 在不同DMP初始浓度下研究了该菌的降解动力学, 结果表明当浓度低于300 mg/L时的降解动力学方程为ln C = - 0.06837 t + A, 半衰期为12.48 h, 当初始浓度不断增加, DMP对JDC-3的抑制能力增强, JDC-3对DMP的降解速率不断下降, 半衰期增大。     

食品包装用塑料中八种邻苯二甲酸酯的检测方法

反相液相色谱串联质谱(LC-MS-MS)分析方法,采用振荡萃取,LC-MS-MS,MRM多反应监测模式,对食品包装用塑料中(国内外作为环境污染物优先控制的)八种邻苯二甲酸酯:邻苯二甲酸二异壬酯(D INP);邻苯二甲酸(2-乙基已基)酯(DEHP);邻苯二甲酸二正辛酯(DNOP);邻苯二甲酸二异癸酯(D IDP);邻苯二甲酸丁基苄酯(BBP);邻苯二甲酸二正丁酯(DBP);邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)同时进行检测,线性相关较好,方法回收率在80~120%之间,最低检出限为0.01 mg.kg-1.     

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。     

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。     

Biodegradation of phthalic acid esters (PAEs) in soil bioaugmented with acclimated activated sludge

The degradation characteristics of four phthalic acid esters (PAEs), i.e. di-methyl phthalate (DMP), di-ethyl phthalate (DEP), di-n-butyl phthalate (DBP) and di-n-octyl phthalate (DOP) in the soil augmented with acclimated sludge was investigated in order to assess the efficacy of bioaugmentation as a strategy for remediating PAEs-contaminated soil and correlate the degradation rate of PAEs with their alkyl chain length. The results demonstrated that PAEs with shorter alkyl chain, that is, DMP and DEP could be degraded more quickly than DBP and DOP. The degradation of four PAEs in the soil conformed to a first-order reaction kinetic equation. The half-lives of PAEs degradation decreased significantly with increasing carbon number of the alcohol moiety. Half-lives decreased from 2.29 days for DMP to 28.4 days for DOP when the carbon number of alkyl chain increased from one for DMP to eight for DOP. The degradation rate of PAEs and the corresponding half-lives could correlate with the alkyl chain length and their octanol–water partition coefficients (K_ow) quite well for the four PAEs tested in this study.     

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.     

Enhanced degradation of petrol (Slovene diesel) in an aqueous system by immobilized Pseudomonas fluorescens

The rate of degradation of n -alkanes C₁₂-C₁₈, in petrol (Slovene diesel) in an aqueous system, by free and immobilized Pseudomonas fluorescens in shaking flasks was investigated. Cells were immobilized to a biosupport, Biofix, and a biosorbant, Drizit. Analysis of cellular growth of the free and immobilized bacteria over 8 d of incubation with diesel as the sole carbon source, showed a reduction in the lag phase in the immobilized cultures in comparison to the free system. The free system degraded 52·3% of C₁₂ and 11·6% of C₁₃, but C₁₄-C₁₈ were not degraded. In comparison to the free system and diesel which had not been exposed to experimental conditions (unexposed), the immobilized systems degraded significantly more of C₁₃-C₁₈. Biofix-immobilized cells degraded 14·8% of C₁₂ and an average of 53·5% of C₁₃-C₁₈. Drizit-immobilized cells degraded 24·5% of C₁₂, 52·4% of C₁₃ and an average of 91·2% of C₁₄-C₁₈. This study shows the successful use of immobilized bacteria technology to enhance the degradation of diesel in an aqueous system.     

ASSESSING THE CONTAMINATED LEVELS AND RISK OF TYPICAL CONTAMINANTS IN THE UPPER REACHES OF THE YANGTZE RIVER北大核心CSCD

We generally reviewed the distributions and potential risks of heavy metals, polycyclic aromatic hydrocarbons (PAHs) and phthalic acid esters (PAEs) in the upper reaches of the Yangtze River based on recent studies. The distribution of heavy metals varied significantly with locations and types of mediums, and contents of some metals exceeded the limits in food. The contents of PAHs in the upper reaches of the Yangtze River were in line with those in the lower reaches. Low molecular weight PAHs were predominant in surface water, while high molecular weight PAHs were predominant in sediments, indicating low molecular PAHs may pose greater risks to aquatic ecosystems. DEHP and DBP were the predominant monomers of PAEs in surface water and sediments, and BBP and DBP ranked first and second respectively in fish bodies. The results of risk assessment also indicated that monomers such as DBP and DnBP had greater risk than DEHP. Over all, heavy metals and organic pollutants were widely distributed in the aquatic environment in the upper reaches of the Yangtze River, which may pose potential risks to the ecosystem. © 2019, Institute of Hydrobiology, Chinese Academy of Sciences. All rights reserved.     

Study on immobilization of marine oil-degrading bacteria by carrier of algae materials

This study investigated the immobilizations with of bacteria two kinds of algal materials, Enteromorpha residue and kelp residue. The lipophilicity of them were compared by diesel absorption rates. The immobilization efficiency of Bacillus sp. E3 was measured to evaluate whether these carriers would satisfy the requirement for biodegradation of oil spills. The bacteria were immobilized through adsorption with the sterilized and non-sterilized carriers to compare the differences between the two treatments. Oil degradation rates were determined using gravimetric and GC–MS methods. Results showed the absorption rates of Enteromorpha residue and kelp residue for diesel were 411 and 273% respectively and remained approximately 105 and 120% after 2 h of erosion in simulated seawater system. After immobilized of Bacillus sp. E3, the oil degradation rates of them were higher than 65% after 21 days biodegradations. GC–MS analysis showed that two immobilizations degraded higher than 70% of the total alkane and the total PAHs, whereas the free bacteria degraded 63% of the total alkane and 66% the total PAHs. And the bacteria immobilized with the carriers degraded more HMW–alkanes and HMW-PAHs than the free bacteria. The bacteria immobilized by non-sterilized kelp residue showed a considerably higher degradation rate than that using sterilized kelp residue. A considerably higher cells absorption rate of immobilization was obtained when using kelp residue, and the preparation of immobilization was low cost and highly efficient. The experiments show the two algae materials, especially the kelp residue, present potential application in bioremediation of marine oil spills.     

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     

Degradation of an endocrine disrupting chemical,DEHP [di-(2-ethylhexyl)-phthalate], by<Emphasis Type="Italic"> Fusarium oxysporum</Emphasis> f. sp.<Emphasis Type="Italic"> pisi</Emphasis> cutinase

The efficiency of two lypolytic enzymes (fungal cutinase, yeast esterase) in the degradation of di-(2-ethylhexyl)-phthalate (DEHP) was investigated. The DEHP-degradation rate of fungal cutinase was surprisingly high, i.e. almost 70% of the initial DEHP (500 mg/l) was decomposed within 2.5 h and nearly 50% of the degraded DEHP disappeared within the initial 15 min. With the yeast esterase, despite the same concentration, more than 85% of the DEHP remained even after 3 days of treatment. During the enzymatic degradation of DEHP, several DEHP-derived compounds were detected and time-course changes in composition were also monitored. During degradation with fungal cutinase, most DEHP was converted into 1,3-isobenzofurandione (IBF) by diester hydrolysis. In the degradation by yeast esterase, two organic chemicals were produced from DEHP: IBF and an unidentified compound (X). The final chemical composition after 3 days was significantly dependent on the enzyme used. Fungal cutinase produced IBF as a major degradation compound. However, in the DEHP degradation by yeast esterase, compound X was produced in abundance in addition to IBF. The toxic effects of the final degradation products were investigated, using various recombinant bioluminescent bacteria and, as a result, the degradation products from yeast esterase were shown to contain a toxic hazard, causing oxidative stress and damage to protein synthesis.