应用红外方法探讨耐镉菌株高积累Cd2+的机理

从安徽某冶炼厂污染土壤中分离出一株能耐高浓度镉的菌株(J5),经初步鉴定为假单胞菌属(Pseudomonas sp.).该菌株在液体培养基中耐受40 mmol·L-1 CdSO4,在固体培养基上耐受75mmol·L-1 CdSO4.培养基中Cd2+、Zn2+、Pb2+、Cu2+浓度分别为100 mg·L-1和Mn2+浓度为275mg·L-1时,菌株生长正常.在重金属Cu2+、Pb2+、Zn2+、Mn2+存在时,采用红外光谱与原子吸收光谱分析菌株对Cd2+的积累,结果表明,在低浓度Cd2+溶液中菌株细胞对Cd2+的积累,主要靠细胞壁上-NH2与Cd2+配位结合;在高浓度Cd2+溶液中,细胞壁上-NH2、-OH、-COOH、-PO43-、-M-O(O-M-O)基团吸附Cd2+的能力显著.Mn2+可以增加细胞壁上有效官能团活性,提高Cd2+积累率;但当有Zn2+、Pb2+、Cu2+重金属离子共存时,即使有Mn2+存在,菌体对Cd2+吸附积累能力未见提高.     

Pb（Ⅱ）胁迫培养下Pseudomonas putida EPS组分变化及其对铅的吸附性能

近年来,由微生物产生的胞外聚合物（Extracellular Polymeric Substances,EPS）对重金属废水的处理技术引起了人们的关注.本研究采用Pb（Ⅱ）胁迫培养恶臭假单胞菌（Pseudomonas putida,P. putida）,定向调控EPS的化学组成,增加EPS产量,并提高EPS对Pb（Ⅱ）的吸附性能.结果表明,Pb（Ⅱ）胁迫浓度为10 mg·L-1时,P. putida EPS产量最高,达到131.55 mg·g-1（以VSS计,下同）,较胁迫前增加25.35%;其中,蛋白质含量显著增加,达到87.01 mg·g-1,较胁迫前增加35.15%.在此条件下,EPS对Pb（Ⅱ）的吸附量也达到最大,为1372.95 mg·g-1.3D-EEM、FTIR结果表明,胁迫后EPS中氨基酸和蛋白质类物质及C=O、N—H、—COO—、C—N、—OH等负电性官能团增加.进一步实验结果表明,吸附实验最佳pH为6.0,吸附过程符合拟二级动力学和Freundlich等温模型.胁迫后P. putida EPS对Pb（Ⅱ）的理论吸附容量为1452.59 mg·g-1,较胁迫前提高74...     

微生物胞外聚合物对水中As(Ⅴ)的吸附性能研究

以菌株Bacillus lincheniformis W6产生的胞外聚合物EPS-W6作为吸附剂,以傅里叶变换红外光谱(FTIR)对其进行表征,系统地研究了胞外聚合物EPS-W6对水中As(V)的吸附行为。研究结果表明:当水中As(V)的质量浓度为50 mg/L,p H值为2,吸附剂投加量为0.5 g/L,吸附反应温度为30℃的条件下,吸附反应7 h后达到平衡,吸附容量为56.3 mg/g。吸附等温线能较好地用Langmuir模型来描述,吸附动力学符合准二级动力学模型。胞外聚合物EPS-W6的FTIR分析结果表明,胞外聚合物EPS-W6中的C—H、C—N、C—O—C和C—S等的基团与As(V)发生络合作用。     

生物氧化锰矿物对几种重金属的吸附作用

从土壤铁锰结核及其附近土壤中分离、培养并筛选到3株锰氧化细菌:芽孢杆菌(Bacillus sp.)WH4和GY16,假单胞菌(Pseudomonas sp.)WHS26,应用这3个菌株大量合成了生物氧化锰.在此基础上,比较研究了这3个菌株催化合成的生物氧化锰与一种化学合成锰氧化物矿物(S-MnOx:Synthesized Mn oxide)对重金属Cu2+、Zn2+、Cd2+的吸附特征.结果表明,3种生物氧化锰对重金属的吸附具有明显优势,其对Cu2+、Zn2+、Cd2+的最大吸附量约为S-MnO2的10～100倍;各种氧化锰对Cu2+、Zn2+、Cd2+的吸附过程均符合Langmuir等温吸附模型,且是一个快速吸附的过程;3种锰氧化物对Cu2+、Zn2+、Cd2+3种重金属的最大吸附量与其比表面积呈正相关,吸附过程受pH影响,最适的pH范围为3～6.     

产脲酶细菌矿化修复Cd和Pb污染土壤效应和机制

为了修复重金属污染土壤,保障蔬菜品质安全,利用产脲酶筛选培养基从重金属污染生菜根际土壤中筛选产脲酶细菌.通过溶液吸附和土壤静置培养试验研究功能菌株对Cd和Pb的固定钝化机制;利用水培试验研究功能菌株对不同品种蔬菜生长及吸收Cd和Pb的影响.结果显示,从生菜根际土壤中共分离到10株产脲酶细菌,其中菌株Microbacterium foliorum CH6和Bacillus thuringiensis N3的产脲酶能力（分别为62.6,59.6mS/（cm·min））和吸附钝化Cd和Pb （84.6%~91.3%）的能力最高.扫描电镜-能谱、傅里叶红外光谱和X衍射分析表明,菌株CH6和N3能够通过细胞壁吸附和诱导重金属成矿反应,降低溶液中的Cd和Pb含量.土壤静置试验表明,与不接种菌株对照相比,菌株CH6和N3均能降低土壤中可交态Cd和Pb （46.3%~66.7%）的含量,增加碳酸盐结合态及残渣态Cd和Pb （40%~95.4%）的含量.砂培试验表明,菌株CH6和N3均能显著降低生菜、上海青和空心菜可食用部分中Cd （39.2%~81.4%）和Pb （27.4%~82.3%）的含量.产脲酶细菌CH6和N3能够矿化土壤中的Cd和Pb,降低土壤中重金属有效态含量,阻控生菜、上海青和空心菜对Cd和Pb的吸收.     

产脲酶细菌矿化修复Cd和Pb污染土壤效应和机制

为了修复重金属污染土壤,保障蔬菜品质安全,利用产脲酶筛选培养基从重金属污染生菜根际土壤中筛选产脲酶细菌.通过溶液吸附和土壤静置培养试验研究功能菌株对Cd和Pb的固定钝化机制;利用水培试验研究功能菌株对不同品种蔬菜生长及吸收Cd和Pb的影响.结果显示,从生菜根际土壤中共分离到10株产脲酶细菌,其中菌株Microbacterium foliorum CH6和Bacillus thuringiensis N3的产脲酶能力（分别为62.6,59.6mS/（cm·min））和吸附钝化Cd和Pb （84.6%~91.3%）的能力最高.扫描电镜-能谱、傅里叶红外光谱和X衍射分析表明,菌株CH6和N3能够通过细胞壁吸附和诱导重金属成矿反应,降低溶液中的Cd和Pb含量.土壤静置试验表明,与不接种菌株对照相比,菌株CH6和N3均能降低土壤中可交态Cd和Pb （46.3%~66.7%）的含量,增加碳酸盐结合态及残渣态Cd和Pb （40%~95.4%）的含量.砂培试验表明,菌株CH6和N3均能显著降低生菜、上海青和空心菜可食用部分中Cd （39.2%~81.4%）和Pb （27.4%~82.3%）的含量.产脲酶细菌CH6和N3能够矿化土壤中的Cd和Pb,降低土壤中重金属有效态含量,阻控生菜、上海青和空心菜对Cd和Pb的吸收.     

柠檬酸-施氏矿物复合体对Cd和Pb的吸附研究

施氏矿物(Schwertmannite)是酸性矿区废水污染环境中典型的铁硫酸盐次生矿物,由于其较好的吸附能力成为矿区多种重金属的沉积库.环境中同时广泛存在着各种有机质,易与矿物结合形成有机质矿物复合体,从而影响矿物对重金属的吸附行为.目前关于有机质与施氏矿物形成的复合体对重金属的吸附研究相对较少.因此,本研究选取柠檬酸作为天然有机质的代表,研究不同环境条件下柠檬酸施氏矿物复合体对重金属Cd、Pb的吸附.结果表明,复合体保持着施氏矿物基本的矿物学特征,对重金属Cd和Pb的吸附行为表现出不同的趋势:复合体对Cd的吸附量整体上随着Cd浓度和pH值的升高而上升;相反,复合体对Pb的吸附量均比纯施氏矿物要低,并且随着柠檬酸含量的升高吸附量下降越明显;体系中共存的硫酸根离子(SO₄^2-)抑制了复合体对Cd的吸附,而对Pb的吸附则起到促进作用.XRD分析表明柠檬酸抑制了高pH下Pb在矿物表面形成PbSO₄沉淀.FTIR红外谱图进一步证明结合在复合体上的柠檬酸参与了对Cd和Pb的吸附过程.本研究结果有助于更好地预测Cd和Pb在矿区的迁移和归宿.     

木霉(Trichoderma sp.)HR-1活细胞吸附Pb(Ⅱ)的机理

从重金属废水中筛选得到一株能够吸附Pb(II)的丝状真菌,编号为HR-1,初步鉴定其为木霉属(Trichodermasp.).研究了pH值对活细胞吸附铅离子能力的影响及其对铅的耐受性,结果表明,该细胞对铅离子的最大吸附量为597mg/g;扫描电镜(SEM)显示细胞吸附Pb(II)后发生明显的萎缩现象,在细胞表面存在大量的沉积物;X射线光散射能谱(EDX)验证了铅的吸附,同时吸附过程中存在离子交换作用.对比细胞吸附Pb(II)前后的傅立叶红外光谱(FTIR)图谱表明,葡聚糖或几丁质中的羟基和C-O-C、蛋白质的羧基是铅的主要吸附位点,与含氮官能团无关.XPS证实细胞吸附铅离子后生成PbO,XRD图谱得出其处于无定形和晶体之间.     

改性水凝胶的制备及其对Pb2+、Cd2+吸附性能研究

采用60Co-γ射线低温辐射技术,以丙烯酸羟乙酯(HEA)和N-乙烯基甲酰胺(NVF)为共聚单体,合成了一种新型共聚物水凝胶:聚(丙烯酸羟乙酯/N-乙烯基甲酰胺)[p(HEA/NVF)],并采用三乙烯四胺(TETA)对其进行胺化改性,制得一改性水凝胶:聚(丙烯酸羟乙酯/N-乙烯基甲酰胺)-三乙烯四胺[p(H/V)-T].对制备的p(HEA/NVF)凝胶进行了SEM分析和FTIR分析,并对改性后的p(H/V)-T进行XPS分析及FTIR分析.研究了改性前后水凝胶对重金属Pb2+、Cd2+的吸附性能,改性后水凝胶对Pb2+、Cd2+的吸附动力学,以及重金属离子初始浓度、pH值等对改性凝胶吸附性能的影响,并对吸附重金属前后的水凝胶进行电子能谱分析.SEM分析表明,p(HEA/NVF)水凝胶是一种具有多孔结构的高分子材料;吸附实验结果表明,相比较p(HEA/NVF),p(H/V)-T对Pb2+的吸附量增加了700%,对Cd2+的吸附量增加了600%;p(H/V)-T对Pb2+、Cd2+的吸附量随着pH的升高而增加,吸附过程满足准二级动力学方程,并均能较好地符合Freundlich和Langmuir等温吸附模型(R2>0.95);红外分析证实,HEA和NVF已成功聚合为一新型共聚物水凝胶,且多胺基团已被成功地接于共聚物水凝胶表面;XPS分析得出,改性后水凝胶p(H/V)-T对重金属Pb2+、Cd2+的吸附机制为两者之间的螯合作用.     

锌铜胁迫对Bacillus vallismortis EPS组分变化特征及其吸附性能的影响

近年来,微生物胞外聚合物(EPS)在吸附重金属方面的潜能引起了人们的广泛关注,但关于重金属对微生物及其EPS特性的影响鲜有报道.Bacillus vallismortis对锌铜矿捕收剂苯胺黑药具有良好的降解能力.为了解重金属对菌株的胁迫影响,探讨二者之间的相互作用,研究了Zn(Ⅱ)、Cu(Ⅱ)胁迫对菌株EPS产量、组分变化特征及其吸附性能的影响.结果表明,在Zn(Ⅱ)胁迫下,菌株培养至稳定期产生的EPS最多,当Zn(Ⅱ)为12 mg·L~(-1)时EPS产量翻倍,达到100.84 mg·g~(-1)(以VSS计),Zn(Ⅱ)能刺激菌株产生更多富含—COOH和—OH的胞外多糖;菌株在Cu(Ⅱ)胁迫下需培养至对数期产生的EPS最多,在Cu(Ⅱ)为6 mg·L~(-1)情况下EPS产量最高为60.65 mg·g-1(以VSS计),Cu(Ⅱ)的胁迫作用提高了菌株EPS中富含N—H和C—N的蛋白质含量;吸附实验结果表明,2种金属能通过胁迫菌株产生特异性EPS,为金属离子提供大量适用性结合点位,显著提高对重金属的去除能力.研究结果对应用生物法处理同时含有重金属和有机物的复合型选矿废水具有一定的指导意义.     

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.     

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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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.     

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.     

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.     

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.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.