改性壳聚糖对多重金属污染土壤酸雨淋溶特征

为研究在酸雨条件下改性壳聚糖对多重金属污染土壤的作用机理及环境影响,文章以环氧氯丙烷改性壳聚糖-生物炭复合材料（ECS-B）和原壳聚糖作为稳定剂,通过土柱淋溶实验探讨在模拟酸雨条件下淋出液pH、电导率（EC）和重金属（Cu、Pb、Zn和Cd）含量及形态变化特征,提出了淋溶条件下重金属的累积释放模型。研究表明,相对于对照组,加入ECS-B稳定剂淋出液pH最大升高了1.32;EC最高可达对照组的1.75倍;Cu、Pb、Zn和Cd累积含量明显降低,相比对照组分别下降了82.35%、71.47%、61.88%、90.44%;淋溶前后,各重金属残渣态最高为对照组的2.59倍。土壤中重金属的释放是受多种扩散机制控制的复杂反应过程,ECS-B稳定剂通过增加土壤盐基离子、表面络合、沉淀和离子交换等作用可以抑制酸雨对土壤中重金属的淋溶,有效减少其生态环境风险。     

雨水入渗淋溶下锌冶炼地块土壤中镉铅的迁移特征

文章以某锌冶炼地块剖面土壤为研究对象,开展了为期30 d的模拟酸雨(pH=4.4)滞水、干湿交替（ADW）和连续淋溶条件下柱淋溶实验,探讨土壤中Cd、Pb的释放迁移及形态转化特征。结果表明,各处理下淋出液Cd和Pb浓度均于淋溶初期第5天达到峰值后下降,Cd浓度峰值范围高达21.7～45.1μg/L,超出《地下水质量标准》(GB/T 14848-2017)Ⅳ类标准限值(10μg/L),且整个淋溶期间滞水处理下淋出液Cd浓度均超标,地下水存在Cd污染风险;Pb浓度峰值范围仅为0.90～2.69μg/L,远低于Pb标准限值(100μg/L)。酸雨淋溶促进表层杂填土层（0～10 cm）土壤Cd和Pb释放迁移,主要累积于下层素填土(15～20 cm),Cd的迁移能力和深度较Pb高。欧共体参比司三步连续提取法结果显示,淋溶后表层土壤Cd和Pb的可交换态占比增加,残渣态占比降低,迁移性增大;浅及深层10～60 cm处土壤中Cd和Pb可交换态含量比例减少,残渣态占比上升,而ADW淋溶处理促进土壤中Cd和Pb向可交换态转化。降雨特别是酸雨淋溶会导致冶炼地块土壤中Cd、Pb的释放和迁移,存在地下水重金属污...     

采用离石黄土原位修复煤矸石渗滤液污染地下水

为以较好的技术手段和较低的经济成本治理煤矸石淋滤液、矿坑废水对地下水的污染,通过土柱淋滤试验、PRB (permeable reactive barrier)模拟试验以及场地修复试验,对煤矸石淋滤液中重金属(Zn、Mn、Pb、Cr、Cu、Cd、Hg)及As的吸附性进行了研究. 土柱淋滤试验结果表明:离石黄土(粒径0.05~0.10mm)、亚砂土(粒径0.05~0.10mm)和细沙(粒径>0.10~0.25mm)对煤矸石淋滤液中的重金属(Zn、Mn、Pb、Cr、Cu、Cd、Hg)及As的吸附能力为离石黄土>亚砂土>细沙,其中离石黄土对As的分配系数为2.26L/kg.模拟槽试验表明,在地下水流速为0.20m/d、m(煤矸石):m(离石黄土)分别为5和7的情况下,淋滤液中的As能够全部被黄土墙吸附;m(煤矸石):m(离石黄土)为10时,部分As透过黄土墙向下游迁移. 5个月的场地修复试验表明,利用离石黄土作为PRB的吸附材料能够较好地去除地下水中的重金属(Zn、Mn、Pb、Cr、Cu、Cd、Hg)和As,厚约0.5m的离石黄土墙对被煤矸石淋滤液污染的地下水中Cr的去除率最高,达到70.97%,对Pb的去除率最低,为43.14%.      

污泥堆肥施用对土壤及地下水影响研究

为探究北京市污泥堆肥产品施用对土壤和地下水的影响,采用原状土柱模拟降雨试验方法,研究了在污泥堆肥产品年施用量为3、6、12kg/m²的条件下,Cu、Cr、Ni、Zn、Pb、Cd、As、Hg 8种重金属元素的迁移和淋溶特征.结果表明,Cd淋溶后残留最少（6.1%~11.9%）,进入淋溶水最多（4.5%~7.3%）;Hg淋溶残留最多（16.0%~22.1%）,进入淋溶水最少（<0.1%）.Hg、Pb、Ni、Cd、Cu在0~20cm土壤层积累最多（52.0%~78.7%）;Cr、Zn、As则在20~40cm层积累最多（42.7%~53.2%）.8种元素在土壤中的含量均符合《土壤环境质量农用地土壤污染风险管控标准（试行）》（GB 15618-2018）限值.淋溶水中测得的6种重金属浓度由大至小依次为Zn > As > Cd > Cu > Pb > Cr,受堆肥施用量及降雨量共同影响.淋溶水中Cu、Cr、Ni、Zn、Pb 5种元素的浓度始终在《地下水质量标准》（GB/T 14848-2017）Ⅰ类水质范围内,Cd、As、Hg在Ⅲ类范围内.     

不同施磷量(KH2PO4)作用对Cu、Zn在红壤中的迁移转化

为了比较不同施磷量对土壤中重金属Cu、Zn迁移转化的影响,采用土壤柱进行室内淋溶实验,研究常见的磷肥磷酸二氢钾在少量5 mg·kg-1,适量15 mg·kg-1以及过量25 mg·kg-1条件下对Cu、Zn在红壤中的淋溶效应.结果表明土壤施用磷酸二氢钾降低了土壤渗滤液的pH,不同施磷量对土壤渗滤液pH影响不大,在整个淋滤过程,渗滤液pH呈现上升的趋势.磷酸盐作用下重金属Cu在土壤中的迁移主要集中表层土壤中,而Zn逐渐向深层土壤中迁移.土壤深层渗滤液中Cu、Zn浓度均比较低,对浅层地下水的危害性不大.淋滤结束后,重金属主要以残渣态存在土壤中,重金属Cu残渣态的比例为60%左右,重金属Zn残渣态比例为40%左右.高浓度磷酸二氢钾作用下有利于重金属Zn从残渣态及有机结合态向交换态转化.     

天津污灌区菜地土壤团聚体中有机碳和重金属含量特征

以天津某污灌菜地土壤为研究对象,分析干筛法所得不同粒径土壤团聚体颗粒中有机碳及重金属含量特征.结果表明,土壤团聚体粗大颗粒(2 mm)含量最大,约为70%.0.25～0.5 mm粒级团聚体中Cu、Zn、Cd和Pb含量最高,Cr含量在5～8 mm粒径团聚体中最高,As在不同颗粒中含量差异较小,不同重金属元素含量随土层深度增加而减小.污灌土壤中重金属富集因子表现为Cd Pb Zn Cu Cr As,在0.25～0.5 mm粒级团聚体颗粒中Cu、Zn、Cd和Pb分布因子最高,而5～8 mm粒径团聚体中重金属负载因子最大.土壤有机碳含量整体上随团聚体粒径增加表现为先增加后降低,不同粒径团聚体中Cu、Cd、Pb和As含量与有机碳含量呈显著正相关(p0.05).     

重金属和有机氯农药在沈阳郊区农田土壤中的吸附和迁移

采用静态吸附和土柱淋溶实验研究了重金属和有机氯农药在沈阳郊区农田土壤中的迁移转化规律.吸附实验结果表明,土壤对Pb和Cd阳离子的吸附大于对Cr(VI)和As(V)阴离子的吸附,对Cr(VI)的吸附大于对有机氯农药六六六(BHC,包括α-BHC、β-BHC、γ-BHC、δ-BHC)和滴滴涕(DDT,包括o,p'-DDT、p,p'-DDT)的吸附能力.土柱淋溶实验结果表明,Cr(VI)和As(V)在耕层土壤中的迁移速度远大于Pb、Cd的迁移速度,α-BHC由于淋溶液初始浓度较低,因而迁移速度较慢.淋溶实验后,具有较高生物可利用性和迁移性的可交换态重金属的相对含量增加了1.2%～5.4%,从而增加了Pb、Cd、Cr和As等重金属对生态系统的威胁.结合吸附和迁移实验结果可知,所研究污染物中,Cr(VI)和As(V)对地下水的威胁较大,Pb和Cd对农业生产的威胁较大,而目前有机氯农药已被国家明令禁止使用,土壤中的部分残留有机氯农药由于土壤的吸附作用,使得其对农业生产的威胁逐渐减小,对地下水的威胁性也较小.     

万庄金矿田土壤重金属的垂直分布及形态研究

利用等离子体发射光谱法、原子荧光光谱法等研究了北京水源涵养区上游万庄金矿田4个土壤剖面样品中的Cu、Zn、Ni、Pb、Cd、Cr、Hg和As共8种重金属元素在剖面上的分布特征,以及Cu、Zn、Pb、Cd、Cr、Ni元素的形态分布特征,并对重金属元素污染现状进行了评价。结果表明部分重金属元素在土壤表层有明显的富集现象,Cd、As、Pb、Zn、Cu、Hg 6种重金属基本都随深度的增加,含量大体呈现逐渐减小的趋势,Cr、Ni有较相似的迁移和富集规律;相关性分析发现Zn、Ni、Cd、Cr、和As的相关性显著可能具有同源性。形态分析可知重金属Zn、Cd的迁移能力相对较高。地累积指数评价结果可见,土壤中Pb、As、Cd环境生态污染较严重。     

模拟酸雨下铅锌冶炼废渣重金属的静态释放特征

以株洲某铅锌冶炼废水中和渣为研究对象,开展不同初始pH值（3.0,4.5,5.6和7.0）模拟酸雨静态浸出实验,研究22d浸泡过程中废渣Cd、Cu、Pb和Zn等重金属的动态释放规律及其化学形态变化和矿物相变特征.结果表明,废渣具有较强的酸缓冲潜力,浸出液pH值稳定在6.20~6.66.Cu和Pb在浸泡初期释放较快,Cd和Zn释放相对较慢.浸出液Cd浓度随浸出时间增加而上升,Zn浓度呈波动变化,Cu和Pb浓度变幅较小.提高雨水酸度促进废渣中重金属的释放,浸出液Cd、Cu、Pb和Zn浓度范围分别为1.38~8.70,0~0.02,1.21~2.26和27.2~135mg/L,其中Cd、Pb和Zn浓度分别超过我国《铅、锌工业污染物排放标准》（GB 25466-2010）限值的26.6~173倍、1.42~3.52倍和17.1~89.0倍..重金属BCR顺序提取表明,浸出液中较高Cd和Zn浓度与其赋存高活性态比例一致,且酸雨促使残渣态Cd和Pb向活性态转化.XRD分析显示,pH=3.0酸雨处理22d后原废渣中Cd和Zn的赋存矿物相消失,PbSO₄谱峰增强,表明废渣重金属的释放受其赋存矿物相及次生矿物形成的影响.重金属释放率呈现出Cd （2.50%~15.8%）> Zn （0.41%~2.13%）> Pb （0.06%~0.10%）> Cu （0.0003%~0.11%）的趋势.自然堆存酸雨作用下废渣中Cd、Pb和Zn具有较大环境风险,需加强降雨淋滤污染防治管控.     

典型铅锌矿流域土壤重金属累积与分布的影响因素分析

以桂北地区阳朔铅锌矿流域为研究对象,对其流域内表层土壤中9种重金属元素(Zn、 Pb、 Cd、 Fe、 Mn、 Cu、 Cr、 Sb和As)的全量和形态,以及5种土壤性质指标(pH、电导率、阳离子交换量、有机质和粒径)进行分析测定.综合运用相关性分析、冗余分析(RDA)和地理探测器揭示土壤重金属累积与分布的主控因素.在土壤样本分析数据中,As、 Cd、 Fe、 Cu、 Mn、 Pb和Zn含量平均值均超过背景值,其中Cd、 Mn、 Pb和Zn分别是背景值的4.01、 3.15、 5.53和9.72倍,表明其在表层土壤中明显富集;在分布上具有较为明显的空间差异,在冲洪积扇堆积区(1～6号)高于其他区域(7～9号). Pb和Mn可利用态占比(K)分别为48.8%和57.2%,生物可利用性较大,潜在迁移能力一般(PMI分别为0.015～0.068和0.036～0.082);Zn和Cu可利用态占比(K)分别为30.9%和16.8%,且中等利用态占比(Z)分别为10.9%和13.6%,有一定生物可利用性,但Zn迁移能力较强(PMI为0.160～0.203),Cu潜在迁移能力一般(PMI为0.017...     

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.