珠江三角洲地区大气气溶胶中有机污染物背景研究

选择肇庆市鼎湖山自然保护区为珠江三角洲大气气溶胶有机污染评价的区域性环境背景．研究结果表明,珠江三角洲地区大气气溶胶中优控多环芳烃背景值萘、苊、二氢苊、芴、菲、蒽、荧蒽、芘、苯并（a）蒽、、苯并（b）荧蒽、苯并（k）荧蒽、苯并（a）芘、茚并（1,2,3-cd）芘、二苯并（a,h）蒽、苯并（ghi）分别为n.d.、n.d.、tr.、0.14、tr.、0．39、0.53、0.19、1.05、1.82、1.41、0.02、2.29、0.53和2．44ng/m³,总量为10.80ng/m³,其来源主要为高等植物排放.     

城市隧道汽车尾气中多环芳烃排放特征的研究

对广州市珠江隧道进行了汽车尾气中颗粒相多环芳烃(PAHs)的排放因子测试,研究了汽车组成、交通流量、隧道内微气象及PAHs成分和浓度水平,采用质量平衡模型和多元线性回归方法计算了8种车型共14种PAHs的综合排放因子.结果表明,汽车尾气颗粒相PAHs的主要检出物为萘、苊烯、苊、蒽、菲、荧蒽、芘、苯并(a)蒽、、苯并[a]芘、苯并(k)荧蒽、茚并(1,2,3-c,d)、二苯并(a,h)蒽、苯并(g,h,I)苝等14种成分,隧道进口处PM₁₀中∑PAHs浓度为(5.000±1.762)μg/m³,隧道出口处PM₁₀中∑PAHs浓度为(27.067±3.602)μg/m³,其中四环以上的PAHs含量占74.9%.在平均车速为46km/h条件下,隧道内机动车尾气颗粒物中∑PAHs平均排放因子高达16.20³mg/(km·辆),其中各PAHs化合物排放因子均超出欧洲或美国的100倍以上.     

混合表面活性剂对多环芳烃的增溶作用及机理

比较了研究了单一和混合表面活性剂对萘、苊、蒽、菲、芘的增溶作用及其机理。混合表面活性剂／单一表面活性对多环芳烃协同增溶／增溶作用的大小与水溶液中表面活性剂的结构、浓度、组成及有机溶质本身的性质有关。在临界胶束浓度（CMC）以上，单一表面活性剂对多环芳烃的增溶作用顺序为TritonX100＞Brij35＞TritonX305，与其亲水亲油平衡值（HLB）呈负相关；混合表面活性剂对多环芳烃能产生显著的增溶作用，其协同增溶作用顺序为SDS－TritonX305＞SDS－Brij35＞SDS－TritonX100，协同增溶作用的大小与其中的非离子表面活性剂的HLB值及多环芳烃的辛醇－水分配系数呈正相关。混合表面活性剂溶液的CMC值降低、溶质在胶束相／水相间分配系数Kmc的增大是产生协同增溶作用的主要原因。     

象山港海水和沉积物中多环芳烃分布特征和来源研究

本文研究了象山港多环芳烃（PAHs）在沉积物-海水中的分布特征,于2017年1月对港口9个采样点的沉积物和海水中16种优先控制PAHs进行分析,采用同分异构比值法和逸度方法进行来源分析和扩散行为研究。沉积物中PAHs范围为17.51×10–9～84.41×10–9,主要为高环PAHs,处于轻度污染等级。沉积物中多环芳烃主要来自高温燃烧源。表层水体、中层水体和底层水体中PAHs范围分别为41.78～105.72 ng/L、41.51～106.34 ng/L和9.18～145.17 ng/L,主要由低环PAHs组成。表层水体中PAHs主要来源于石油泄漏和石油燃烧。利用逸度系数判断PAHs扩散行为,萘（Nap）、苊（Ace）和芴（Flo）由沉积物向海水释放;苊烯（Acy）、菲（Phe）、蒽（Ant）和芘（Pyr）在沉积物和海水中处于动态平衡;荧蒽（Flu）、苯并[a]蒽（BaA）、?（Chr）和苯并[b]荧蒽（BbF）主要从海水向沉积物扩散并富集。     

超临界水氧化法降解氧乐果的研究

实验研究了有机磷农药氧乐果在超临界水中的氧化降解．结果表明,超临界水氧化技术能有效地降解氧乐果废水．随着反应温度的升高、压力的增大、停留时间的延长,COD去除率也随之提高氧乐果在超临界水中氧化降解的动力学方程为：－d［COD］/dτ＝1.60eｘp（－2.25×10⁴/RT）［COD］^0.90［O₂］₀^-0.38［H₂O₀^0.053.     

有机膨润土吸附水中多环芳烃的性能及机理研究

分别用溴化十二烷基三甲铵（ＤＴＭＡＢ），溴化十四烷基苄基二甲基铵（ＴＰＡＣ），溴化十六烷基三甲铵（ＣＴＭＡＢ），溴化十八烷基三甲铵（ＯＴＭＡＢ）改性膨润土研究了有机膨润土中吸附水中菲，萘，苊的适宜条件，性能及机理，结果表明，有机膨润土的层间距，有机碳含量，对多环芳烃的吸附能力与改性时所用表面活性剂的碳链长度及其在制德时的用量成正比；多环芳烃的去除效果还与其本身的性质有关；     

江苏省丰、沛、铜重氟病区动物体中氟的含量及其与环境的关系

丰、沛、铜重氟病区,禽、畜体内氟主要积聚在骨骼中（羊骨1096×10^－6～2001.9×10^－6,鸡骨335×10^－6～378×10^－6）及生理功能强的内脏（肝、心、肾等）器官中,氟的含量3.3×10^－6～7.17×10^－6,肌肉和蛋、奶品中氟的含量大多接近或低于氟的卫生标准,显然肉、蛋、奶食品不是该区地氟病的致病因子。研究表明,动物体内氟含量与环境水氟及叶菜和树叶（含水分高）中的氟含量呈明显的正相关。因而造成食草动物比以食粮食为主的家禽体内的氟含量明显偏高。说明水是氟的传播媒界,为该区地氟病的主要致病因子。     

硝基芳烃对鲤鱼鱼鳃ATPase的活性抑制和QSARs

在离体实验条件下,测定了20种硝基芳烃化合物对鲤鱼鱼鳃ATPase活性的半抑制浓度－logIC₅₀值,以一阶价分子连接性指数¹X^V,取代基常数总和∑σ^－、指示变量Ｉ、分子分支指数¹Ka、分子最低空轨道能ELUMO及辛醇─水分配系数logP为参数,进行定量结构活性相关性（QSAR）研究。结果表明,硝基芳烃的毒性和∑σ^－、Ｉ、ELUMO3个参数密切相关。在上述基础上,成功地建立了20种硝基芳烃的QSAR方程,其相关系数为0.927。     

北京东南郊污灌区PAHs垂向分布规律

采用Eijkelkamp土壤采样器对北京东南郊污灌区进行了3个钻孔剖面采样,分析了土壤样品的理化参数,并且采用气相色谱-质谱联用仪对土壤样品的多环芳烃（PAHs）进行了定量分析,研究了土壤理化参数和16种PAHs从表层到5.5 m深的范围内垂向变化规律.结果表明,污灌区表层土壤中有14种PAHs检出,检出浓度在4～428 μg/kg之间,表层以下PAHs的检出种类显著减少,主要以2环和3环的萘、菲、芴、苊烯、二氢苊、荧蒽6种为主.粘粒含量、粘土矿物总量、阳离子交换容量以及总有机碳4个理化参数相互之间在垂向变化上具有一致性,均在0.05水平上显著相关.表层以下粘粒含量与低环PAHs在垂向含量变化也有较好的一致性,粘粒含量高的层位,PAHs含量也较高.从剖面PAHs含量变化可以判断,低环PAHs较易迁移,它们的迁移性强弱顺序为：二氢苊>芴>萘>菲>苊烯>荧蒽,其它高环PAHs难以迁移,仅在表层土壤中检出,说明在长期污灌条件下,迁移性较好的低环PAHs能够迁移到较深的土层中,有可能导致浅层地下水的污染.     

典型石油化工污染场地多环芳烃土壤指导限值的获取与风险评价

尝试利用英国的污染土地暴露评价模型(CLEA模型)获取了典型石油化工污染场地中几种多环芳烃(PAHs)的土壤指导限值(SGVs),并用所得到的土壤指导限值对该场地的污染物风险进行了评价.结果表明,研究区域内萘、蒽、苯并［a］芘、苊、芴、芘的土壤指导限值分别为3.57×103,6.12×107,0.874,6.81×104,6.24×104和5.84×106　ng/g.特定场地表层土壤中萘、蒽、苊、芴、芘的实测浓度(MECs)大于其相应土壤指导限值的概率均趋于0,而苯并［a］芘的为0.225.这几种PAHs的风险从大到小依次为:苯并［a］芘萘>苊>芴>芘>蒽,说明该场地的优先控制污染物为苯并［a］芘.      

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.     

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

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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.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.