改性蓝藻生物炭促进微生物电合成系统产乙酸的机制研究

微生物电合成系统(MES)是一种以微生物作为催化剂,在阴极电驱动下还原CO₂产生简单化学品的新型碳捕获利用技术.为探究蓝藻生物炭在MES中的添加强化乙酸合成的潜力,本研究通过不同蓝藻生物炭的投加,检测乙酸合成性能及电子回收率,观察阴极微生物分布及形态特征,分析微生物群落结构特征,探究蓝藻生物炭添加对乙酸合成的影响及机制.结果表明,添加蓝藻生物炭(ABC)和过氧化氢改性蓝藻生物炭(ABC-H₂O₂),使MES乙酸产量分别增加了33.8%和77.0%,电子回收率均有所上升,且ABC-H₂O₂组电子回收率高于ABC组.分析蓝藻生物炭电子传递性能和氧化还原活性表明,经过氧化氢改性后的蓝藻生物炭表面含氧官能团数量增加,增强了电子传递能力及氧化活性,有利于微生物通过蓝藻生物炭介导进行间接电子传递.在微生物群落结构方面,蓝藻生物炭的添加降低了产乙酸菌丰度,但提高了微生物群落中电活性微生物和产氢微生物的丰度,使得产乙酸微生物获得更多的电子,实现乙酸合成性能增强.本研究揭示了蓝藻生物炭,特别是改...     

厌氧发酵对废弃钙基生物炭制备温度的影响及对水体中除磷研究

水体中磷的高效去除是降低水体富营养化的有效手段.以废弃蛋壳为碳酸钙源，以厨余垃圾为生物质，采用厨余垃圾和蛋壳混合厌氧发酵进行预处理，制备钙改性生物炭(ES-BC)，并用于水体中磷的去除.结果表明，当m(厨余垃圾)∶m(蛋壳)=3∶1，发酵温度为55℃，发酵7 d天后，在600℃条件下煅烧可制得除磷性能优异的ES-BC；发酵过程产生的有机酸可促进碳酸钙的预分解，进而降低后续材料的煅烧温度，保持生物炭良好的孔隙结构，有利于钙的分散和磷的去除；在较优条件下制得的ES-BC复合材料对不同浓度(1～100 mg·L^-1)的磷污染液均具有较好的去除效果，反应产物主要包括Ca₅(PO₄)₃OH、Ca₁₀(PO₄)₆OH₂(HAP)和Ca₈H₂(PO₄)₆·H₂O(OCP)等.     

CO2气氛热解与硝酸改性的生物炭Pb2+吸附性能对比

酸改性处理常被用于生物炭的改性过程,但也存在酸消耗量大、废液处理难和成本高等问题.利用热解过程直接改性提高生物炭重金属的去除效果、降低改性成本,是未来实现改性生物炭广泛使用的重要前提.为评估CO₂气氛热解法在生物炭制备和应用方面的优势和潜力,对CO₂气氛热解与HNO₃改性生物炭对Pb²⁺的去除性能进行对比分析.采用元素分析、傅里叶红外光谱(FTIR)和X射线光电子能谱(XPS)对生物炭的元素组成和结构特性进行表征.结果表明,500℃热解条件下,HNO₃改性的生物炭产生了较多的C=O和O=C—O—等羧基类官能团,并引入了—NO₍2(asy))和—NO₍2(sym))基团,提高了生物炭的表面活性和络合能力.CO₂气氛制备生物炭中含有较多的金属碳酸盐,可通过离子交换和共沉淀作用吸附去除Pb²⁺.此外,CO₂改性生物炭具有较大的比表面积和更优的微孔结构,有利于Pb^2+...     

不同气氛热解生物炭可溶性有机碳的光谱特征

为探明不同气氛热解生物炭可溶性有机碳(BDOC)的性质特征,在不同热解气氛(CO₂、N₂和空气限制)和热解温度(300～750℃)下制备了一系列小麦秸秆生物炭,通过提取其BDOC并结合紫外-可见光谱和荧光光谱-平行因子分析方法对BDOC性质进行分析.热解温度为300℃时,CO₂和N₂热解生物炭释放的DOC含量高(CO₂:10.55mg/g,N₂:10.17mg/g);而热解温度为450～750℃时,空气限制热解生物炭释放的DOC含量高(0.31～2.88mg/g).生物炭释放DOC含量与生物炭的挥发性物质含量、H/C和(O+N)/C呈正相关关系.空气限制热解BDOC具有更低的分子量,更高的芳香性(SUVA₂₅₄范围:7.66～16.86),腐殖化程度(HIX范围:10.77～52.21)和类腐殖酸物质含量,而CO₂和N₂热解BDOC含有更多的类蛋白物质.此外,CO₂和N...     

混合嗜酸菌浸出污泥中重金属机制判定方法

为判断混合菌种的生物沥浸机制,采用添加沥浸混合菌种+作用底物（硫酸亚铁铵、硫粉）、只添加作用底物和仅加硫酸3组实验,估算直接氧化作用（F₁₁）,化学氧化作用（F₁₂）和酸性浸出作用（F₁₃）的贡献率,从而获得混合菌种的重金属浸出机制.针对某污水处理厂剩余污泥的生物沥滤实验结果表明,Cu的浸出过程中F₁₁、F₁₂、F₁₃贡献率分别为92.55%、7.45%、0%,说明混合菌种作用下Cu的浸出机制主要为直接机制;Zn的沥浸作用中F₁₁、F₁₂、F₁₃贡献率分别为18.86%、44.35%、36.79%,判定Zn在混合菌种的作用下为间接机制.该法可在实际环境条件下判定重金属的生物沥浸机制,对相关研究和实际应用提供理论依据.     

改性稻壳生物炭对水中反硝化过程和N2O排放的影响

为探究H₂O₂改性和NaBH₄改性稻壳生物炭(BC-H₂O₂和BC-NaBH₄)对反硝化过程和N₂O排放的影响及机理,在制备并测定BC-H₂O₂和BC-NaBH₄理化性质及其表面含氧官能团含量基础上,将未改性生物炭(BC)、BC-H₂O₂和BC-NaBH₄以1%(w/V)的比例分别加入含有厌氧反硝化细菌(DB)的培养体系,开展DB去除模拟废水中低浓度硝酸盐(约10mg/L,以N计)的室内培养实验.结果表明,H₂O₂改性增加了生物炭表面的羧基含量,而NaBH₄改性增加了生物炭表面的内酯基和酚羟基含量.另外,傅立叶变换红外光谱分析表明,与BC相比,BC-H₂O₂的C=O含量明显增加.DB+BC-H     

太湖蓝藻对Sb(Ⅴ)的生物吸附作用

利用富营养化湖泊的藻类——太湖蓝藻,对Sb(Ⅴ)的生物吸附特征进行了研究. 结果表明:藻类经0.1 mol/L盐酸处理后,对Sb(Ⅴ)的生物吸附效率大大提高. 原藻和经盐酸处理的蓝藻在1 h左右对Sb(Ⅴ)的吸附量达到平衡;Sb(Ⅴ)在原藻和经盐酸处理的蓝藻表面的吸附能力均随着pH升高逐渐减弱;原藻与经盐酸处理的蓝藻对Sb(Ⅴ)的吸附等温线符合Freundlich方程;不同离子强度的Cl-、NO₃-、SO₄2-、PO₄3-对Sb(Ⅴ)在原藻表面的吸附影响较弱,而对Sb(Ⅴ)在经盐酸处理的蓝藻表面的吸附影响显著.      

酸碱改性对生物炭吸附Cr(Ⅵ)性能的影响

生物炭因具有原料来源广泛、表面活性官能团含量丰富、性质稳定等特点,近年来,在环保领域作为重金属处理吸附剂受到越来越多的重视。使用松木屑在碳化温度为400 ℃条件下制备生物炭(简称AB400),并使用HNO₃、H₃PO₄、NH₃·H₂O、Ca(OH)₂对生物炭进行改性。借助SEM、FTIR、BET、Boehm滴定法和Zeta电位测定等方法对改性前后AB400表征,并进行Cr(Ⅵ)吸附实验。改性后生物炭结构呈半穿透至穿透状圆形塌陷,存在微孔。酸性改性条件下,HNO₃改性生物炭(简称AB400HNO₃)、H₃PO₄改性生物炭(简称AB400H₃PO₄)中酸性官能团含量均有所升高,且生物炭pH均减小,其对应pH_pzc增大,而碱改性的生物炭则反之。对于Cr(Ⅵ)的吸附,酸性改性生物炭在整体上的吸附效果优于碱性改性生物炭,其中AB400H₃PO₄吸附效果最佳,吸附容量从58.48 mg/g提高至101.82 mg/g。这是因为碱性改性生物炭表面为负电荷,与Cr(Ⅵ)的含氧阴离子相斥;而AB400HNO₃微孔容积较小,圆形塌陷数量甚微,表面虽正电荷,但吸附性能不及AB400H₃PO₄。     

两种铁改性生物炭对微碱性砷镉污染土壤的修复效果

改性生物炭作为良好的重金属钝化剂,已被广泛应用于环境修复.为探究不同改性方法对生物炭钝化土壤砷-镉(As-Cd)的影响,采用共沉淀法和浸渍热解法制备铁改性生物炭,通过吸附试验和土壤培养试验,对生物炭性质、吸附As-Cd以及钝化土壤As-Cd的能力进行分析.结果表明,两种改性方法均可提高生物炭铁含量和零电荷点,且共沉淀法制备的铁改性生物炭(FeBC-1)负载的铁矿物主要为Fe₃O₄、 FeO(OH)和γ-Fe₂O₃等,而浸渍热解法制备的铁改性生物炭(FeBC-2)主要为α-Fe₂O₃和γ-Fe₂O₃等铁氧化物.FeBC-1对As和Cd均展现出很强的吸附去除能力,去除率达21.40%～34.14%,可显著促进土壤中非专性吸附态As向残渣态As转化,而FeBC-2仅对As具有较好的吸附效果.BC、 FeBC-1和FeBC-2对Cd的吸附能力与自身的阳离子交换量(CEC)呈正比,其中,BC对Cd的吸附去除效果优于FeBC...     

玉米秸秆生物炭改善污泥脱水性能

本实验以玉米秸秆为原料,制备了生物炭和AlCl₃改性生物炭,研究了2种生物炭分别调理污泥后的脱水效果,并探讨了污泥脱水性能的改善机理.结果表明,经过2种生物炭调理后,污泥比阻（SRF）、泥饼含水率（MC）、污泥沉降体积指数（SV₃₀）、毛细抽吸时间（CST）均下降,污泥净产率（Y_N）升高,说明污泥脱水性能得到了改善,且AlCl₃改性生物炭对污泥脱水性能的改善效果明显优于生物炭.当AlCl₃（溶液浓度3mol/L）改性生物炭的用量为3g/L时,调理后的污泥SRF,MC,SV₃₀,CST分别降低至1.3×10¹²m/kg,81.9%,78.6%,35s,Y_N增加至17.8kg/（m²·h）.分析原因：一方面,经过生物炭调理后,泥饼中会形成一定的骨架结构,使得污泥中的水和EPS能够更容易地释放;另一方面,经过AlCl₃改性后,改性生物炭携带的正电荷（Al³⁺）能够与污泥颗粒所带的负电荷发生电中和作用,使得污泥颗粒更容易聚集,从而提高污泥的脱水效果.     

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.     

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.     

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.     

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.     

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.     

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.     

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.