长白山雨养泥炭表层多环芳烃组成分布及来源分析

采用气相色谱-质谱法(GC-MS)对长白山圆池雨养泥炭表层16 种优控多环芳烃(PAHs)污染物进行分析并对其来源进行了探讨.结果表明,该区表层PAHs 含量为1404~1936ng/g,PAHs 以2~3 环为主,苯并(a)芘等强致癌性化合物均有不同程度的检出.结合菲/蒽、荧蒽/芘等参数值分析,推测该区泥炭表层PAHs 主要来源于化石燃料的不完全燃烧,生物合成作用产生的PAHs 也有一定的贡献.对泥炭表层单体PAH 与总PAHs 回归分析表明,苊烯、荧蒽、芘可以作为泥炭表层标志性PAHs 污染物.     

某油泥堆放场地中多环芳烃的污染及其垂向分布特征

通过采集某油田油泥堆放场地及其周边24个表层土壤样品和2个剖面土壤样品,采用超声波萃取-气相色谱/氢火焰离子化检测分析方法,对美国环境保护局(USEPA)优控的16种多环芳烃(PAHs)进行定量分析.结果表明:该研究区域的PAHs污染已较为严重,污染场地内16种PAHs的检出率为100%,w(PAHs)平均值为7 770.7 ng/g;周边土壤的16种多环芳烃的检出率为58.3%～100%,二苯并［a,h］蒽及茚并［1,2,3-cd］芘的检出率相对较低,w(PAHs)平均值为2 038.8 ng/g.研究区域内主要污染物为萘、苊、二氢苊、芴、菲、蒽、荧蒽、、芘、苯并［a］蒽和苯并［a］芘.从母体PAHs与污染物来源的关系和单组分比值可以看出,污染场地内及周边土壤的污染源是石油源和燃烧源的混合源.w(PAHs)在土壤剖面中的峰值出现在40～60及20～40 cm处,不同组分的PAHs在土壤剖面中的迁移能力表现为2～3环PAHs＞4环PAHs＞5～6环PAHs.      

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.     

蚊香燃烧产物中多环芳烃的分布规律及相关性研究

对蚊香燃烧后的烟气和灰烬样品进行采集,利用GC-MS方法分析其中16种优控多环芳烃(PAHs)的含量,并对烟气和灰烬中各PAHs组分及总量间的相关关系进行探讨.结果表明:蚊香烟气中16种PAHs均有检出,排放量较大的组分主要有萘、苊、二氢苊、菲和荧蒽,并以2～3环PAHs为主;灰烬中PAHs也以2～3环化合物为主,但排放总量仅为烟气中的4.7%～21.8%.通过与其他室内燃烧源PAHs排放量的对比发现,蚊香灰烬中总PAHs排放量低于卫生香源和木柴源,但比香烟源高一个数量级以上;烟气中总PAHs排放量低于燃煤源、木柴源和卫生香源,但明显高于烹调源.回归分析结果表明,烟气中总PAHs排放量与灰烬中的排放量表现出明显的线性关系(R2=0.9054).     

中国主要河流中多环芳烃生态风险的初步评价

以现有的中国主要河流中多环芳烃(PAHs)的浓度数据为基础,通过定义1个危害商,利用商值法筛选出菲、蒽、荧蒽、芘、苯并[a] 蒽、 和苯并[a]芘7种对水生生态具有潜在风险的PAHs.以河流水相中PAHs浓度数据为依据,结合毒性数据库中PAHs水相浓度对水生生物的毒性数据,用概率风险评价法分析了这7种PAHs对水生生物的生态风险.结果表明,7种筛选出的PAHs风险大小依次为：蒽>芘>苯并[a]蒽>荧蒽>苯并[a]芘>菲> .     

汽车尾气中多环芳烃(PAHs)成分谱图研究

采集并测定了不同型号、油品、里程数的汽车尾气中14种多环芳烃,对分析结果归一化处理后确定其多环芳烃成分谱图.研究表明,汽车在30rmin内排放的14种PAHs总浓度为41.53～121.1μg/m³;其中苯并(a)蒽(BaA)浓度最大,占总量的33.3%;萘(Naph)、苯并(ghi) (Bghip)、茚(1,2,3-cd)芘(In)分别为16.8%、12.9%和12.1%.相同里程数的柴油车排放PAHs总量大于汽油车;除BaA和Naph,柴油车主要排放苊(Ac)、芴(Fluor)、Bghip和In,而汽油车主要排放Bghip、In、苯并(k)荧蒽(BkF).柴油车排放3环PAHs的量大于汽油车,但5～6环PAHs的排放量小于汽油车;随着汽车里程数的增加,PAHs(特别是荧蒽(Flur)、芘(Py)、苯并(a)芘(BaP)、Bghip)的排放总量增加.     

嘉兴市城市河网区多环芳烃污染源解析及生态风险评价

为研究嘉兴市城市河网区水体中多环芳烃的污染水平和来源并进行生态风险评价,采用气相色谱-质谱法（GC-MS）对环境优控多环芳烃（PAHs）进行分析检测.结果表明,枯水期和丰水期分别检测出10种和16种优控PAHs,质量浓度范围分别为77.32~283.76ng ·L^-1和13.05~133.02ng ·L^-1,平均质量浓度分别为143.83ng ·L^-1和73.47ng ·L^-1;枯水期低环（2环和3环）占比79.18%,丰水期低环占比73.60%;嘉兴市河网区水体多环芳烃污染情况与国内外其他地区相比处于较低水平;采用同分异构比值法和主成分分析法进行污染来源分析,结果表明嘉兴市枯水期和丰水期河网水体中多环芳烃污染主要来源为城市面源污染、燃烧源以及交通污染源;Kalf风险熵值法评价结果表明,枯水期：萘（Nap）、苊烯（Acy）、二氢苊（Ace）、芴（Flu）、菲（Phe）、蒽（Ant）、荧蒽（Fla）、芘（Pyr）和苯并［a］蒽（BaA）以及∑PAHs为中等生态风险水平,丰水期：萘（Nap）、苊烯（Acy）、芴（Flu）、菲（Phe）、荧蒽（Fla）、芘（Pyr）、苯并［a］蒽（BaA）、苯并［b］荧蒽（BbF）、苯并［k］荧蒽（BkF）、苯并［a］芘（BaP）、茚苯［1,2,3-cd］芘（InP）和苯并［ghi］苝（BghiP）属于中等生态风险水平,∑PAHs为低生态风险水平;总体而言,嘉兴市河网水体中PAHs生态风险呈中等水平,有关部门需采取措施降低河网水体中PAHs的生态风险.     

安徽中北部河流沉积物的特征与多环芳烃分布

通过对安徽省中北部6条河流沉积物样品的粒径、矿物组分和有机质含量的测试,并应用气相色谱质谱联用仪测定了样品中萘、二氢苊、苊、芴、菲、蒽、荧蒽、芘、苯并[a]蒽、、苯并[a]芘和二苯并[a,h]蒽等12种多环芳烃的含量,分析了研究区河流沉积物的特征和多环芳烃分布。研究结果表明:位于安徽省中北部的淮河南北岸支流沉积物粒径和矿物组分具有不同特征;就PAHs总量来看,北岸支流平均值为313.3ng/g,南岸支流平均为112.8ng/g,差异比较明显,南岸支流沉积物中大多数多环芳烃的平均含量都低于北岸支流(蒽和菲除外,二苯并[a,h]蒽未检出);而有机质的含量,南北岸支流总体无明显差异(含量在0.55%至1.83%之间),但单条河流的分布呈沿水流方向自中上游至下游逐渐降低。     

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.     

我国8种市售蚊香燃烧烟气中多环芳烃的排放特征

利用GC-MS对8种具有代表性的市售蚊香燃烧烟气中16种列入美国环境保护署(US EPA)优先控制的多环芳烃(PAHs)进行分析. 结果表明:有烟蚊香烟气中16种优先控制的PAHs均有检出(6号蚊香除外),排放因子较大的化合物主要有萘、苊、二氢苊、菲和荧蒽;无烟蚊香烟气中仅检出10～11种,排放因子最大的化合物是菲,其次为萘;各种蚊香烟气中PAHs均以2～3环化合物为主,约占排放量的83.3%～98.0%. 同无烟蚊香相比,有烟蚊香烟气中PAHs的排放量较大,毒性也较高. 根据烟气中PAHs排放因子估算出一盘蚊香燃烧后烟气中苯并［a］芘排放量相当于燃烧4支香烟,PAHs排放量相当于燃烧8支香烟;蚊香燃烧后室内空气中ρ(PAHs)高达1 486.60 ng/m3,其中ρ(苯并［a］芘)为8.07 ng/m3,超过其《室内空气质量标准》(GB/T18883─2002)中的日均限值.      

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

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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.