硫化铁铜双金属复合材料的制备及除铬机制

以零价铁为原料,利用液相置换法制备铁铜双金属（Fe-Cu）,对其硫化改性后,得到一种除铬效率更高的硫化铁铜双金属铁基复合材料（S-Fe-Cu）.探讨了Cu/Fe质量比、S/Fe摩尔比、pH值和氯离子对S-Fe-Cu去除水体中Cr（Ⅵ）效果的影响.采用扫描电子显微镜与能谱分析仪（SEM-EDX）、比表面积分析仪（BET）和X射线电子能谱（XPS）等表征手段分析了S-Fe-Cu的表面结构及元素组成,并研究了其除铬机制.结果表明,S-Fe-Cu表面成功负载上了FeS_x,理论最佳S/Fe摩尔比为0.056,理论最佳Cu/Fe质量比为0.025.与Fe-Cu相比,S-Fe-Cu的比表面积增大了2.1倍,pH为5时除铬效率提高了6.1倍;pH值增大,S-Fe-Cu除铬效果下降,但其碱性条件下的除铬效果仍是Fe-Cu的两倍.氯离子能够促进材料在反应过程中Fe（Ⅱ）的释放,分析认为氯离子能够渗透表面钝化层,使钝化层产生缺陷,从而促进零价铁的直接氧化,提高S-Fe-Cu除铬性能.XPS与EDX表面元素分析表明,材料除铬机制主要包含还原、吸附或共沉淀.     

湿法解毒还原工艺对铬渣中Cr(Ⅵ)的治理特性

以治理铬渣中的Cr(Ⅵ)污染为目的,提出了硫酸浸出-硫酸亚铁还原的铬渣湿法解毒工艺,在对铬渣处理前后的表面形貌进行表征的基础上,探究了不同处理条件下铬渣中Cr(Ⅵ)的处理效果及其修复机理。结果表明:铬渣湿法球磨时间为20 min时,铬渣颗粒98.68%过200目筛,水溶性Cr(Ⅵ)的浸出率可达40.96%;铬渣硫酸添加量为60%,液固比为4∶1,酸溶时间为2.5 h时,Cr(Ⅵ)浸出趋于饱和,此时浸出终点pH为5.8,水溶性和酸溶性Cr(Ⅵ)总浸出率为95.38%;硫酸亚铁添加量为40%时,铬渣中Cr(Ⅵ)含量下降为1.38 mg/kg。铬渣中Cr(Ⅵ)的去除主要与硫酸对含Cr(Ⅵ)矿物的溶解、SO₄2-和CrO₄2-的离子交换以及Fe(Ⅱ)对溶液中Cr(Ⅵ)的还原作用有关。     

零价铁PRB修复硝酸盐和铬复合污染地下水

通过连续流动试验研究了Fe0(零价铁)-PRB(渗透反应格栅)修复受NO₃--N、Cr(Ⅵ)以及NO₃--N和Cr(Ⅵ)复合污染模拟地下水的反应特性,分析了Fe0对NO₃--N和Cr(Ⅵ)的氧化还原产物,并且对NO₃--N和Cr(Ⅵ)的相互影响进行了研究. 采用粒径为0.15～0.42 mm的Fe0和粒径为0.15 mm的活性炭作为PRB反应介质,二者的质量比为1∶1. 结果表明,Fe0单独与NO₃--N反应情况下,当进水中ρ(NO₃--N)为20 mg/L时,去除率达95%,NO₂-为还原过渡状态,NH₄+是主要产物,出水pH从原水的7.1升至9.0左右,出水中ρ(TFe)<0.60 mg/L. Fe0处理Cr(Ⅵ)情况下,对Cr(Ⅵ)有较高的去除效果,进水中ρ〔Cr(Ⅵ)〕为10 mg/L时,去除率达96%,反应产物Fe3+和Cr(Ⅲ)可以形成沉淀附着在反应介质上,不会迁移到“下游”水体中,出水pH从原水的7.0升至8.0左右,出水中ρ(TFe)<0.30 mg/L. Fe0去除NO₃--N和Cr(Ⅵ)复合污染时,共存的NO₃--N对Cr(Ⅵ)的去除效果没有影响,Cr(Ⅵ)的存在降低了NO₃--N的去除效果.      

某铬盐厂Cr(Ⅵ)污染土壤还原稳定化效果研究

以某铬盐厂铬渣堆存场地内Cr(Ⅵ)污染土壤为研究对象,采用七水硫酸亚铁(Fe SO_4·7H_2O)、多硫化钙(Ca Sx)、Fe SO_4·7H_2O和Ca Sx、Fe SO_4·7H_2O和水泥4种药剂开展Cr(Ⅵ)污染土壤的还原稳定化实验,并利用BCR连续提取法进行铬形态分析。结果表明,Cr(Ⅵ)还原效果:Fe SO_4·7H_2O和Ca Sx复配药剂在4种药剂中对Cr(Ⅵ)的整体还原效果最好。铬稳定效果:Fe SO_4·7H_2O和水泥复配药剂在4种药剂中对土壤铬的稳定性最好,Fe SO_4·7H_2O和水泥复配药剂处理对铬的形态分布的影响是使弱酸提取态、可还原态和可氧化态转化成残渣态,处理后残渣态铬质量分数高达30.98%。污染土壤中铬的形态分布为可氧化态(63.67%)残渣态(23.29%)弱酸提取态(6.80%)可还原态(6.25%),4种药剂处理后土壤中铬的形态分布为可氧化态残渣态可还原态弱酸提取态。     

生物法修复铬污染土壤的研究

用生物修复技术来处理受铬污染的土壤，利用自然界中微生物，通过生物还原反应，将Cr(Ⅵ)还原成三价铬。先是通过土壤与合铬的培养基一起培养，筛选出5种能还原Cr(Ⅵ)的菌种，鉴定其菌属，并试验用这些菌种处理铬污染土壤的效果。同时还考虑了pH值对处理效果的影响。试验结果表明：筛选出5种菌种可以还原Cr(Ⅵ)；混菌处理效果最好，最高可达到100％；混菌处理污染土壤的适宜pH值范围为6．0—8．0。     

旋风炉掺烧铬渣污染物排放特性分析

针对260 t/h旋风燃烧炉机组进行烟气污染物排放测试,并通过旋风炉掺烧铬渣后对其飞灰、底渣进行XRD、XRF分析,考察对重金属Cr(Ⅵ)、Hg的固化效果。结果表明:烟尘、SO_2、CO排放浓度偏高,需进一步改造处理;旋风炉掺烧铬渣飞灰中Hg、Cr(Ⅵ)的浓度分别为6.77,94.7 mg/kg,其中有毒Cr(Ⅵ)浓度显著降低,下降了97.5%;结合XRD分析可知,掺烧铬渣过程中,大部分重金属Hg、Cr(Ⅵ)主要靠挥发和通过铬渣与原煤中矿物质相互反应生成化合物释放到烟气和飞灰中,而底渣中未检测出明显的含Cr矿物质存在。     

难溶态Cr (Ⅵ)对重度铬污染土壤淋洗还原修复效果的影响

通过对某铬渣堆场的重度铬污染土壤进行解吸动力学和难溶态Cr (Ⅵ)还原实验,揭示限制重度铬污染土壤有效修复的关键因素。结果表明:室温下,采用柠檬酸淋洗可显著降低土壤中难溶态Cr (Ⅵ)浓度,将淋洗温度提高至90℃,可进一步显著降低难溶态Cr (Ⅵ)浓度。淋洗后土样中难溶态Cr (Ⅵ)浓度越低,其还原效果越好。供试土样经柠檬酸高温淋洗+FeSO₄高温还原工艺修复后,Cr (Ⅵ)浓度从(1813.2±59.8) mg/kg降至(99.1±8.8) mg/kg。此外,淋洗实验中柠檬酸对难溶态Cr (Ⅵ)的还原可忽略不计;土样中残留的柠檬酸对土壤Cr (Ⅵ)的检测结果无显著影响。研究证明了难溶态Cr (Ⅵ)的还原效果是重度铬污染土壤修复的关键限制因素,结果可为铬污染土壤修复工艺研发提供参考。     

硫化物对电镀厂铬污染土壤的稳定化效果及其机理研究

以某电镀厂旧址内的铬(Cr)污染土壤为研究对象,分别添加多硫化钙(CPS)、硫化钠(Na2S)以及焦亚硫酸钠(Na_2S_2O_5)3种硫化物稳定剂,探究3种稳定剂不同投加摩尔比对土壤中Cr的价态变化、浸出毒性和形态分布的影响.结果表明:CPS对Cr(Ⅵ)还原效果最佳,当CPS投加摩尔比为3时,土壤中Cr(Ⅵ)含量从1587.5 mg·kg-1减少至12.43 mg·kg~(-1),还原效率高达99.2%,然而相同条件下Na_2S和Na_2S_2O_5对Cr(Ⅵ)的还原效率仅分别为55.6%和74.5%.CPS对Cr(Ⅵ)和总Cr稳定效率最高,当CPS投加摩尔比为3时,浸出Cr(Ⅵ)和总Cr浓度分别为0.02mg·L~(-1)和0.32 mg·L~(-1),Cr(Ⅵ)和总Cr稳定效率分别为99.8%和99.1%,此时Cr(Ⅵ)浓度满足GB/T 14848-93《地下水水质标准》规定的限值.相同投加摩尔比下Na2S和Na_2S_2O_5对Cr(Ⅵ)稳定效率分别仅为63.0%和98.9%,对总Cr稳定效率分别为66.5%和77.2%;浸出Cr(Ⅵ)和总Cr浓度随着CPS和Na2S投加摩尔比的增加而降低,然而随着Na_2S_2O_5投加摩尔比的增加,浸出Cr(Ⅵ)浓度持续下降,但总Cr浓度不断升高.CPS和Na2S稳定化后土壤中Cr的有机物结合态变化不大(p0.05)、铁锰氧化物结合态显著增加(p0.05).硫化物稳定剂稳定化后土壤中Cr的可交换态含量的变化是影响浸出总Cr浓度变化的主要原因.基于3种硫化物稳定剂对土壤中Cr(Ⅵ)还原效率、Cr(Ⅵ)和总Cr稳定效率和Cr的可交换态含量的影响,CPS投加摩尔比为3时,对该电镀厂铬污染土壤的稳定化效果最佳.     

铬渣动态淋滤重金属铬溶解释放规律研究

为了全面系统地研究铬渣中Cr(Ⅵ)和Cr(Ⅲ)溶解释放特征,以锦州和沈阳两地铬渣堆场为研究对象,通过动态淋滤试验,测定滤出液中Cr(Ⅵ)和总铬的质量浓度变化,分析铬渣淋滤液中Cr(Ⅵ)和Cr(Ⅲ)溶解释放规律。试验结果表明,锦州新铬渣和沈阳陈铬渣淋滤过程中,Cr(Ⅵ)和总铬浓度都经历先迅速下降再缓慢下降的过程;相较锦州新铬渣,沈阳陈铬渣Cr(Ⅵ)和总铬浓度下降都较慢,且初始浓度也较低;相比Cr(Ⅵ)的溶出,两地铬渣Cr(Ⅲ)的溶出量均较少,Cr(Ⅲ)溶出占比呈波动性上升趋势;锦州新铬渣和沈阳陈铬渣的Cr(Ⅵ)和总铬溶出浓度随淋出液体积分别呈双指数曲线衰减关系和幂函数曲线衰减关系。试验成果将为防治铬渣对地下水污染提供科学理论依据。     

外控电势对Ch-1菌株生长及Cr(Ⅵ)还原的影响

为进一步优化Ch-1菌株对碱性含铬废水的处理及铬渣的解毒效果,以细菌总数和6价铬的还原率为指标,详细考察了外控电位对Ch-1菌株生长及Cr(Ⅵ)还原的影响.结果表明,电极材料对细菌生长及其活性有一定的影响,不锈钢电极和铂电极体系对细菌生长及活性的影响基本相同,而采用石墨电极细菌的培养效果欠佳.静态培养和动态培养Ch-1菌株时,Cr(Ⅵ)的最终还原率与初始Cr(Ⅵ)浓度无关,24h时Cr(Ⅵ)的还原率均达到了100%;但就还原过程而言,动态培养对Cr(Ⅵ)的还原速率明显优于静态培养,外控电势能够增强或抑制Ch-1菌株的生长及活性,0～-900 mV的负电位可以促进细菌的生长,而400 mV以上的正电势对Ch-1菌株的生长有抑制作用.在-800～ 200 mV的电势范围内,Ch-1菌株还原6价铬的能力得到增强,在此范围外其还原能力受到抑制.     

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.     

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.     

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.     

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.