沱江沉积物中有机氯农药分布特征及其与藻类有机质的关系和生态风险评估

使用气相色谱-质谱联用仪分析了长江支流沱江流域48个表层沉积物中有机氯农药(organochlorine pesticides, OCPs)的残留水平,探讨了其分布和组成特征及其与总有机碳(total organic carbon, TOC)、藻类有机质之间的关系,以及评估其生态风险.结果表明沱江流域表层沉积物中OCPs的总含量为3.17～127 ng·g^-1,其中六六六(hexachlorocyclohexane, HCHs)类农药的含量为2.83～86.0 ng·g^-1,滴滴涕(dichlorodiphenyltrichloroethane, DDTs)类农药的含量为0.340～40.9 ng·g^-1.OCPs空间分布特点为:上游<中游<下游<支流.HCHs和DDTs的组成成分分析表明,沱江流域存在林丹输入的现象,主要来自于历史残留,这与绝大多数流域的DDTs的输入状况相似.OCPs含量与TOC、藻类有机质含量之间存在着极显著的正相关性关系,表明藻类有机质在TOC对沉积物中的OCPs分配中起更为重要...     

固城湖及出入湖河道表层水体、沉积物和鱼体中有机氯农药分布及风险评估

为研究固城湖环境中有机氯农药(organochlorine pesticides,OCPs)时空分布、来源与生态风险,采用GC-μECD定性定量分析了固城湖及其出入湖河道12个监测点夏、冬两季水体、沉积物和鱼类体内19种OCPs的含量.结果表明,固城湖表层水、沉积物和鱼类中(以干重计)有机氯农药总量范围分别是26.74～48.12 ng·L^-1、 9.01～35.34 ng·g^-1和13.39～124.29 ng·g^-1.水中有机氯农药污染特征表现为夏季含量高于冬季,出入湖河道高于养殖塘和湖区;沉积物中季节性污染特征不明显.从组成特征上看,夏、冬两季水体、沉积物和生物体内19种OCPs均有不同程度地检出,均呈现以HCHs和DDTs为主的污染特征,其中,夏冬两季各监测点表层水和沉积物中HCHs以α-HCH为主,占HCHs总含量的21%～42%;表层水中DDTs以p,p′-DDD为主,占DDTs总含量的30%～76%,沉积物中以p,p′-DDT为主,占DDTs总含量的68%～93%.分析固城湖环境中OCPs来源,根据异构体比...     

水库淹没带土壤有机氯农药分布特征及风险评价

采用GC-MS气相色谱与质谱联用仪,分析了密云水库南水北调来水前高程130～150 m之间的淹没带表层土壤样品中17种有机氯农药(OCPs)的含量、残留特征,讨论了有机氯农药的可能来源,并对OCPs的潜在风险进行了评价.结果表明:①密云水库淹没带土壤有机氯农药残留以六六六(HCHs)和滴滴涕(DDTs)为主,含量均值分别为1. 74 ng·g-1和1. 01ng·g-1,与国内其他湖库区相比,ΣHCHs含量相近,ΣDDTs含量较低.②水库淹没带土壤有机氯农药残留具有一定的空间分布特征.水陆域交错处土壤OCPs含量普遍高于水域、陆域土壤中含量,且存在显著性差异性.水库东部及潮河入库区、独立小流域淹没区,OCPs残留以DDTs为主;库北山前平原淹没带及库西中部淹没区OCPs则以γ-HCH残留为主;白河入库处河滩淹没区HCHs及DDTs残留均有较高占比,这与其污染来源有关.③源解析结果表明,淹没带土壤HCHs来源主要与林丹类农药的输入有关,而DDTs主要来自于早期农药使用的残留.④生态风险评价表明,水库淹没带土壤中大部分样点OCPs生态风险低,白河入库区及库西中部淹没带滴滴涕有潜在风险性.     

衡水湖沉积物中典型持久性有机污染物污染特征与风险评估

在衡水湖布设11个点位,于2018年8月和2019年3月开展两次采样,对衡水湖沉积物中多环芳烃(PAHs)、有机氯农药(OCPs)和多溴联苯醚(PBDEs)这3类典型持久性有机污染物(POPs)进行污染特征分析及生态风险评价.结果表明:①8月和3月衡水湖沉积物中∑PAHs平均值分别为875.49 ng·g^-1和1 010.17 ng·g^-1,与国内外其他地区相比处于中等污染水平,∑PAHs空间分布存在差异,但是季节变化差异不明显; PAHs污染来源复杂,最主要为木材和煤燃烧,其次为石油污染; PAHs生态风险处于较低水平,建议加强对芴的防控.②8月和3月衡水湖沉积物中∑OCPs平均值分别为35.57 ng·g^-1和38.39 ng·g^-1,与国内外其他地区相比处于中等污染水平,∑OCPs空间差异较小,季节差异变化显著;沉积物中DDTs含量主要受土壤中长期分化残留的DDTs和新DDTs源输入的影响,HCHs含量同时受工业历史使用和农业林丹的输入的影响; OCPs总体生态风险处于中等水平,需加强对DDT...     

岩溶地下水水体中有机氯农药和多氯联苯的残留特征及健康风险评价

采用气相色谱-微池电子捕获检测器(GC-μECD)测定南山老龙洞岩溶地下水水体中有机氯农药(OCPs)和多氯联苯(PCBs)残留量,并探究了OCPs和PCBs的浓度、分布和来源等残留特征.结果表明,OCPs总浓度范围为34.8～623.2 ng·L^-1,均值为215.6 ng·L^-1,其中,HCHs、DDTs和其它类OCPs总浓度范围分别为8.2～23.6、4.5～363.7和22.2～235.9 ng·L^-1,均值分别为15.9、104.5和95.3 ng·L^-1; PCBs总浓度范围为6.0～40.7 ng·L^-1,均值为16.8 ng·L^-1.总体而言,OCPs和PCBs污染处于中上水平;多重比较结果显示部分OCPs和PCBs平均浓度具有统计学意义上的显著差异.研究区各采样点水体中污染水平差异较大,但OCPs和PCBs的季节分布相对均匀.源解析表明,HCHs源于周围环境中林丹的输入; DDTs源于近期工业DDT的非法使用;其它类OCPs源于大气沉降和...     

福建鹫峰山脉土壤有机氯农药分布特征及健康风险评价

采集福建鹫峰山脉81个表层土壤样品,利用气相色谱(GC-ECD)分析其中有机氯农药(OCPs)的含量,探讨该地区土壤中有机氯农药残留水平及分布特征,并采用美国EPA推荐的健康风险评价方法(USEPA 1991)对表层土壤中有机氯农药进行致癌风险评价.结果表明,土壤中HCHs和DDTs异构体或衍生物的检出率在77.78%~100.00%之间.HCHs及DDTs含量范围(平均值)分别为0.97~247.40 ng·g-1(10.17 ng·g-1)和0.01~384.75 ng·g-1(18.91 ng·g-1).与国内外相比,研究区土壤中OCPs含量属低污染区域.不同土地利用类型中,OCPs的残留依次为:水稻田>蔬菜地>茶叶地>林地.来源分析表明,研究区近期仍存在HCHs和DDTs输入,HCHs主要来源于林丹的使用,而DDTs可能与三氯杀螨醇的使用相关.风险评价结果显示,研究区表层土壤OCPs致癌风险值均在10-6~10-4之间,对当地居民基本不造成致癌风险.     

上海市稻米中有机氯农药残留水平及健康风险评价

中国作为农药的生产和使用大国,曾大量使用滴滴涕(DDTs)、六六六(HCHs)等有机氯农药.水稻是上海市的主要粮食作物,青浦和崇明区是其重要的水稻种植基地.本研究检测了上海市青浦和崇明区稻米样品中24种有机氯农药的残留水平,分析了OCPs的组成特征并对上海地区稻米中的OCPs残留进行了健康风险评价.结果表明,研究区稻米中OCPs以DDTs和HCHs为主要残留物.青浦和崇明稻米中24种OCPs的总平均残留量分别为6.53 ng·g-1和4.70 ng·g-1,低于食品安全国家标准中对应OCPs的再残留限值.青浦区稻米中4,4-DDE和β-HCH的残留水平最高,崇明区稻米则以2,4-DDT和β-HCH为主要成分.来源解析显示,上海市区域内近期可能仍有三氯杀螨醇和林丹的使用.健康风险评价结果表明,食用本研究区稻米因OCPs所产生的致癌与非致癌风险较低,处于可接受水平.     

珠江三角洲地区土壤有机氯农药分布特征及风险评价

在珠江三角洲经济区采集了7种典型农用地的605个表层样品,采用GC-ECD定量测定土壤中有机氯农药(OCPs)含量,并对其残留特征、区域分布、可能来源和潜在生态风险进行了分析.结果表明,研究区土壤中OCPs检出率达97.85%,残留浓度最高值为649.33μg·kg-1,平均值为20.67μg·kg-1,主要检出物是DDTs、HCHs、硫丹硫酸盐和甲氧滴滴涕.与国内其他地区相比,研究区土壤HCHs和DDTs残留属于中下水平.OCPs分布区域特征非常明显,高含量区主要分布在人口密集,工农业生产活动强度大的珠三角中心城市区域.不同土地利用类型土壤OCPs残留量差异较大,耕地残留量较高,且菜地土壤中有机氯农药残留量最高,其次是园地,林地残留量最低.来源分析表明,土壤中HCHs主要来源于林丹使用,DDTs主要来源于早期施用农药的残留,局部地区三氯杀螨醇已经成为土壤DDTs污染的主要来源.参照土壤环境质量标准,研究区HCHs残留量一级、二级标准合格率分别为97.5%和100%,DDTs一级、二级标准合格率分别为95.5%和97.7%.土壤HCHs残留属于低风险,DDTs类有机氯农药对研究区生物可能存在一定的生态风险,但危害性总体较低.     

土壤中OCPs残留特征及健康风险评价——以松花江佳木斯段为例

文章利用索氏提取技术,使用气相色谱-电子捕获检测器(GC-ECD)分析方法测定了佳木斯市松花江沿岸土壤中17种有机氯农药(OCPs)残留情况,并探讨该区土壤中OCPs的残留来源,运用健康评价模型对DDTs和HCHs对人体可能存在的健康风险进行了评价。17种OCPs的回收率为69.6%～112.4%,GC-ECD的仪器检出限为0.006～0.021 0 ng/g,方法检出限为2.05～12.83 pg/g,相对标准偏差为3.21%～11.37%,能够满足OCPs痕量分析的要求。研究结果表明,17种OCPs均有不同程度的检出,浓度较高的组分为滴滴涕(DDTs)、六六六(HCHs)和七氯,∑OCPs浓度为167.27～667.54 ng/g。研究区DDTs、HCHs的来源解析表明,DDTs、HCHs主要来自于早期农药的残留及林丹的使用。利用健康风险评价模型对土壤中HCHs、DDTs所致健康风险的评价结果表明,目前研究区土壤中HCHs、DDTs类污染物对人体健康的风险处于较低水平。     

丹江口水库迁建区土壤有机氯农药的分布特征及风险评价

利用GC-MS检测了丹江口水库迁建区26个表层土壤样品中的有机氯农药(OCPs),并对其分布特征、组成及来源进行了探讨,评价了OCPs的污染水平和生态风险.结果表明,丹江口水库迁建区土壤OCPs总含量范围为nd～249.37 ng.g-1,平均值为24.82 ng.g-1.其中HCHs与DDTs的含量较高,分别为nd～69.68 ng.g-1和nd～104.53 ng.g-1.土壤中的DDTs含量明显高于HCHs.OCPs可能主要来源于早期残留、大气沉降及近期新的含OCPs物质的输入等.土壤中有机质与OCPs总量之间无显著性相关关系,说明土壤中OCPs含量还受其他因素的影响.与国内其他区域表层土壤相比,丹江口水库迁建区土壤OCPs含量处于中等偏低水平.分析认为,丹江口水库迁建区土壤中有机氯农药风险较低,但局部土壤仍有一定风险.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

ＲｅｍｏｖａｌｏｆｈｅａｖｙｍｅｔａｌｓｆｒｏｍｓｅｗａｇｅｓｌｕｄｇｅｂｙｌｏｗｃｏｓｔｉｎｇｃｈｅｍｉｃａｌｍｅｔｈｏｄａｎｄｒｅｃｙｃｌｉｎｇｉｎａｇｒｉｃｕｌｔｕｒｅＷｕＱｉｔａｎｇ，ＮｙｉｒａｎｄｅｇｅＰａｓｃａｓｉｅ，ＭｏＣｅｈｕｉＦ...     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.