典型污灌区土壤中多环芳烃的垂直分布特征

研究了有污水灌溉历史的沈抚灌区、浑浦灌区和清原对照点3个土壤剖面多环芳烃(PAHs)含量的分布特征.结果表明,在美国EPA优先控制的16种PAHs中,沈抚灌区土壤剖面中检测出10种,浑浦灌区检出12种,清原检出8种.PAHs总含量峰值随着土壤深度的增加呈下降趋势,但最高值均未出现在0～2 cm土层,而是分布在2～5和5～10 cm土层.各剖面单组分分布以4～5环PAHs为主,主要污染物是荧蒽、苯并[a]蒽和苯并[k]荧蒽,低环PAHs含量峰值多集中在0～2 cm土层,中、高环PAHs大部分分布在5～10 cm土层.从单组分比值和母体多环芳烃比值可以看出,3个剖面的PAHs污染源来自于汽油、原油、煤的不完全燃烧,或通过污水灌溉,或以烟尘颗粒为载体通过大气干、湿沉降和风力输送进入到土壤环境中.      

环境污染及其防治 土壤污染及其防治

X53200701690典型污灌区土壤中多环芳烃的垂直分布特征/肖汝(北京科技大学土木与环境工程学院)…∥环境科学研究/中国环科院.-2006,19(6).-49~53环图X-6研究了有污水灌溉历史的沈抚灌区、浑浦灌区和清原对照点3个土壤剖面多环芳烃(PAHs)含量的分布特征.结果表明,在美国EPA优先控制的16种PAHs中,沈抚灌区土壤剖面中检测出10种,浑浦灌区检出12种,清原检出8种.PAHs总含量峰值随着土壤深度的增加呈下降趋势,但最高值均未出现在0~2cm土层,而是分布在2~5和5~10cm土层.各剖面单组分分布以4~5环PAHs为主,主要污染物是荧蒽、苯并[a]蒽和苯并[k…     

南京和宜兴市土壤中多环芳烃(PAHs)的纵向分布

采集了江苏省南京和宜兴市的土壤剖面样品,用高效液相色谱分析了16种PAHs在土壤样品中的含量,研究了PAHs在土壤剖面中的纵向分布特征和影响因素。结果表明,在采样点土壤0～10cm的表土中16种PAHs总量最高,为280.8～717.1μg/kg,随着土壤剖面的加深PAHs总量减少,在70～80cm土层中为8.7～97.5μg/kg。不同PAHs组分在土壤中分布的特点不同,低环的PAHs(≤3环)含量在0～80cm土层中都有分布且随土壤深度加深而减少,而高环的PAHs(≥4环)主要分布在0～30cm土层中,30cm以下土层中含量较少甚至检测不到。相关分析表明,在每个土壤剖面中PAHs总量与其土壤有机碳含量显著相关,PAHs在农田土壤剖面中的纵向分布与土壤有机碳含量、PAHs的理化性质有很大的关系。     

天津地区土壤多环芳烃在剖面中的纵向分布特征

在天津市北部山区、中部农田和东南部油田采油作业区分别采集了土壤样品 ,研究了土壤中多环芳烃 (PAHs)的纵向分布特征 ,并对土壤中多环芳烃的来源进行了分析 .结果表明 ,PAHs含量峰值一般位于土壤表层或次表层 ,并随着土壤剖面的加深而减少 .农田菜地土壤PAHs在 4 0cm深处含量仍然较高 ,而油田仅表层 3cm富集PAHs ,这与耕作土壤表层常受到人为扰动有关 .与高环物质相比 ,低环物质更容易向下迁移 .土壤中有机碳的含量、土壤的性质以及土壤的粒度均是影响PAHs迁移的重要因素 .山区和菜地土壤中PAHs主要来自燃烧源 ,而油田则显示为石油源和燃烧源的混合源 .     

有机碳含量对土壤剖面中多环芳烃纵向迁移的影响

为探索有机碳含量对土壤剖面中多环芳烃(PAHs)纵向迁移的影响,选取北京地区3条有机碳(TOC)含量明显不同的土壤剖面进行了土柱淋滤实验研究.结果表明,通过30 d(相当于北京地区3年的淋滤水量)的淋滤实验后,不同剖面中PAHs均存在不同程度的迁移现象,但剖面中残留的PAHs仍然主要富集在土柱表层0～30 cm土壤中,且中高环数PAHs的残留率明显高于低环数PAHs.TOC含量与PAHs的残留总量之间具有显著的正相关性,TOC含量越高,PAHs残留量越高.此外,TOC对不同环数PAHs迁移的影响程度存在差别,高环数PAHs受TOC变化的影响高于低环数PAHs.     

煤矿区表层土壤中芳香烃组成、分布特征及标志化合物研究

采用GC-MS技术分析了平顶山市石龙区土壤样品中多环芳烃(PAHs)污染物的化学组成及分布特征,共鉴定出78种代表性化合物,包括11种US EPA优控PAHs.结果表明,总体上土壤样品中单体烃菲、荧蒽、芴、芘含量比较高.在不同功能区域芳烃含量差别较大,采矿区及焦化厂区土壤中芳烃含量明显高于污灌区和农业区,而煤矸石山附近土壤中芳烃含量最高.采矿区、焦化厂区和污灌区土壤中低环数PAHs的比例远大于高环数PAHs,农业区反之.通过对(ρ)MP/(ρ)P、MPI1、(ρ)P/(ρ)A、(ρ)FL/(ρ)PY等参数值的分析认为,煤尘、烟灰沉降是石龙区土壤中PAHs积累的主要影响因素.由单体烃与PAHs的相关性分析得知,苊和蒽可作为煤矿区域表层土壤中PAHs的标志性污染物.     

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.     

太原市污灌区有机氯农药垂直分布特征及源解析

采用气相色谱-电子捕获检测器（GC-ECD）方法分析了太原市小店污灌区9个土壤剖面中有机氯农药（OCPs）的垂直分布特征.结果表明,OCPs主要积累在土壤上层0～30 cm,含量最大值为98.56 ng·g-1,其中六六六（HCHs）、滴滴涕（DDTs）、硫丹（endosulfans）和甲氧滴滴涕（methoxychlor）为主要污染物质,占总有机氯农药的85.1%,其它有机氯农药物质相对含量较少.绝大部分剖面土中OCPs含量随着深度增加而明显减少,β-HCH和DDE（o,p＇-DDE＋p,p＇-DDE）在HCH农药和DDT农药中占主要成分.组分分析表明,清灌区和沼泽区中最近可能有新的DDT源输入,其它剖面土中HCH和DDT主要来自历史使用残留.研究区内绝大部分土壤为粉砂壤土;污灌区和清灌区中ΣOCPs含量与总有机碳（TOC）均表现出明显正相关性,但沼泽区和背景点与TOC相关性不显著.     

古水稻土中多环芳烃的分布特征及其来源判定

测定了马家浜文化(距今约6 000a)遗址2个剖面表层土壤、古代水稻土和古代旱地土壤、以及底层土壤中15种多环芳烃的含量,并对其可能来源进行了判定.结果表明,表层土壤中PAHs的含量分别为202.9μg·kg^-1和207.7μg·kg^-1,主要来源于大气沉降;古水稻土中PAHs含量明显降低,仅为56.0μg·kg^-1,但高于古旱地土壤及底层土壤。古旱地土壤及底层土壤PAHs含量在32.0～36.9μg·kg^-1.古水稻土中,2环和3环所占比例较大,达63%,萘和菲含量最高,而4环以上的多环芳烃含量较低.Phe/Ant和BaA/Chr比值和有机质¹³C-NMR图谱显示,古水稻土中的多环芳烃主要来源于水稻秸秆的焚烧,同时还原条件下的生物合成可能是其另一个重要来源.     

典型岩溶槽谷区不同地表覆被土壤中多环芳烃的运移特征和来源解析

为探究岩溶槽谷区土壤中多环芳烃(PAHs)的环境行为,选取典型的竹林地、灌丛地和耕地作为研究对象,运用气相色谱-质谱联用仪定量分析土壤中的PAHs.结果表明,土壤剖面中PAHs污染水平表现为竹林地(204.13 ng·g^-1)>耕地(175.47 ng·g^-1)>灌丛地(106.00 ng·g^-1),土壤质量总体良好.3种土地类型均表现为浅层土壤的PAHs含量显著高于深层土壤(p<0.05),表明岩溶区土壤对防止地下水污染具有重要意义;2~3环PAHs易运移至深层土壤,而4~6环PAHs受TOC含量的影响则主要积聚在浅层土壤,富集能力表现为灌丛地>耕地>竹林地;PAHs运移特征主要受控于有机质的吸附和水的溶解两种机制,PAHs和土壤的理化性质是影响PAHs运移的重要因素.结合同分异构体比值法和主成分分析法的源解析结果,得出研究区土壤中PAHs主要源于当地能源燃烧和交通污染,而大气沉降是重要污染途径.     

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.     

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.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

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.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

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.