废旧印刷线路板中溴代阻燃剂对微生物浸提金属铜效率的影响

研究废旧印刷线路板中溴代阻燃剂的多寡对氧化亚铁硫杆菌(Thiobacillus ferrooxidans)浸提废旧印刷线路板金属铜的浸出效率的影响。将废旧印刷线路板剪切破碎后过筛,得到不同粒度段的颗粒样品,分别测定不同颗粒样品中溴代阻燃剂的含量,以含溴量最高的40~100目的颗粒作为试验材料,探讨不同样品浓度(5g/L、15g/L和25g/L),萃取部分溴代阻燃剂与未萃取两种条件下T.ferrooxidans浸提金属铜的效率。在500mL三角瓶中接入活化后的T.ferrooxidans,待菌株培养到对数生长期后加入相应样品,摇床培养120h,每隔一定时间取上清液,分别测定上清液中Cu2+、氧化还原电位(ORP)和pH值。结果为,浸提120h后,未萃取溴代阻燃剂的5g/L、15g/L和25g/L浓度时T.ferrooxidans对铜浸出分别是79.59%、90.53%和66.37%;萃取溴代阻燃剂的5g/L、15g/L和25g/L浓度时T.ferrooxidans对铜的浸出浓度分别是90.98%、97.88%和69.05%。表明溴代阻燃剂是影响微生物浸铜效率的重要因素之一,利用CCl4作为萃取剂萃取废旧印刷线路板中溴代阻燃剂后,T.ferrooxidans对废旧印刷线路板金属铜的浸提率提高,废旧印刷线路板加入量为15g/L时浸提金属铜的效率最高。     

优化混合菌培养及废电路板添加促进铜的浸提

以嗜酸氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)和氧化硫硫杆菌(Acidithiobacillus thiooxidans)为出发菌株,优化混合菌培养及废弃印刷线路板(PCBs)粉末添加方式提高铜浸提效率。首先考察2种菌接种量对混合菌生长的影响;其次响应面优化混合菌培养液pH,硫酸亚铁(FeSO_4·7H_2O)和单质硫(S)浓度;最后采取多点添加策略提高PCBs添加量和铜浸取率。结果表明,混合菌培养最佳条件:嗜酸氧化亚铁硫杆菌与氧化硫硫杆菌接种量之比为1∶2,pH 1.56,FeSO_4·7H_2O和S为16.88和5.44 g/L;多点添加PCBs策略为:48 h添加量6.4 g/L,96 h添加量9.6 g/L,144 h添加量12.8 g/L。混合菌在此工艺条件下培养240 h后,铜浸取率高达92.6%。     

废旧线路板中主要有价金属的生物反应器浸出研究

为探讨可供实际生物浸出应用的反应器规模废旧线路板中有价金属浸出特性和工艺条件,通过设计序批式生物浸出反应器,采用分离到的氧化亚铁硫杆菌Z1作为菌种资源,在考察废旧线路板中有价金属的浸出特性的基础上,确定了反应器运行的最佳工艺条件.结果表明,反应器运行的最佳工艺条件为曝气量1L/min、停留时间30h、搅拌速率300r/min以及粉末投加量12g/L.在此条件下,经过101h可以浸出90.24%的铜.同时,经197h的浸出,可以溶出93.06%的镁、92.00%的锌、85.59%的铝和64.51%的镍.因此,生物浸出反应器能有效回收废旧线路板中的有价金属,为该技术的实际应用提供了实验证据.     

废旧线路板中主要有价金属的生物反应器浸出研究

为探讨可供实际生物浸出应用的反应器规模废旧线路板中有价金属浸出特性和工艺条件,通过设计序批式生物浸出反应器,采用分离到的氧化亚铁硫杆菌Z1作为菌种资源,在考察废旧线路板中有价金属的浸出特性的基础上,确定了反应器运行的最佳工艺条件.结果表明,反应器运行的最佳工艺条件为曝气量1L/min、停留时间30h、搅拌速率300r/min以及粉末投加量12g/L.在此条件下,经过101h可以浸出90.24%的铜.同时,经197h的浸出,可以溶出93.06%的镁、92.00%的锌、85.59%的铝和64.51%的镍.因此,生物浸出反应器能有效回收废旧线路板中的有价金属,为该技术的实际应用提供了实验证据.     

物理诱变处理氧化亚铁硫杆菌的育种研究

以氧化亚铁硫杆菌作为出发菌,采用物理诱变进行处理。研究结果表明,经过微波和超声波诱变均能加快氧化亚铁硫杆菌氧化Fe2+和转化SO32-的速度。尤其是经过90 s微波处理的氧化亚铁硫杆菌进入对数期的时间比未经诱变前缩短12 h,48 h时Fe2+的氧化率达到99%,4小时后SO32-基本全部转化为SO42-。     

嗜酸菌对废旧印刷线路板金属铜的浸出研究

选用嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans,简称T.f)、氧化硫硫杆菌(Thiobacillus thiooxidans,简称T.t)作为实验菌种研究其对线路板(Printed circuit board)粉金属铜的浸出;试验以单一菌种、混合菌种、无菌培养基及酸性蒸馏水进行浸出实验研究,通过对比不同条件下的浸出效果,得出单一氧化亚铁硫杆菌(T.f)的浸出效果最好,浸出率达到92.1%。通过对浸出过程中pH、ORP及Fe2+、Fe3+变化分析,发现Fe3+的氧化作用在铜的浸出过程中起主导作用,酸浸也有一定的贡献;对浸出后残余的PCB进行XRD及SEM观察分析发现,PCB组成成分中含有大量的酚烃、苯酚及邻、对位取代酚以及少量的长链烷烃及其脂肪烃,此类有机物在浸出过程中均与细菌或其代谢物发生了作用。     

嗜酸性细菌对废旧线路板浸出的吸附行为及动力学

探究嗜酸性细菌对废旧线路板浸出的吸附行为及其动力学模型是生物浸出机制研究的重要基础.本研究通过考察接种不同浓度氧化亚铁硫杆菌(A.ferrooxidans)浸出线路板中铜的吸附行为,探索了菌体在线路板粉末表面的吸附过程,分析了其吸附行为的动力学特性.结果表明,A.ferrooxidans在线路板粉末表面的吸附均于5 h内达到平衡.随着初始菌浓度的增大,吸附速率和吸附的微生物量也随之增大.初始菌体浓度为2.4×105、2.4×107和2.4×109cells·m L-1时对应的最大吸附量分别为1.8701、2.3552和2.9833 mg·g-1,吸附的微生物量占总生物量的比例分别为43.75%、53.97%和55.94%,铜的浸出率分别达到71.20%、88.33%和95.05%.进一步的非线性拟合结果显示,一级动力学模型适用于A.ferrooxidans与线路板粉末的吸附行为,模型拟合度(R2)分别达到0.9321、0.9134和0.9193.     

氧化亚铁硫杆菌对河口底泥中重金属的淋滤效果

从天津某铁厂附近排污河的酸性底泥中成功分离出氧化亚铁硫杆菌菌株,对其形态特征和DNA序列进行了鉴定。运用生物淋滤技术对河口底泥中重金属进行了淋滤实验研究。结果表明,氧化亚铁硫杆菌能够较快速启动生物淋滤,且接种该菌株进行底泥生物淋滤可有效溶出底泥中重金属。最佳淋滤条件为:Fe SO4·7H2O添加量为7 g/L,氧化亚铁硫杆菌的接种量为15%,硫粉添加量为3 g/L,污泥浓度为10%,温度为30℃和硫粉为3 g/L。在最佳淋滤条件下,底泥中Cu、Zn和Hg的去除率分别达到80.6%、63.9%和82.5%。     

嗜酸氧化亚铁硫杆菌处理线路板行业污泥的无害化

研究了一株用于浸出线路板中Cu的嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans简称:A.f菌)在高固液比下无害化处理线路板污泥的影响.实验以A.f菌为原始菌种,通过周期性的驯化培养,在不同的浸出条件下探究了生物浸出时间、培养基pH值、菌种驯化周期、固液比和硫酸亚铁浓度等因素对A.f菌浸出线路板行业污泥中有价金属的影响.结果表明:当固液比高于1:20时,溶液中高浓度的重金属对微生物浸出有抑制作用,但通过连续的驯化培养可以提高菌种的耐受性,在FeSO4·7H2O投加量为60g/L、9k培养基初始pH为0.5、浸出时间为6d、固液比为1:10的条件下, Cu、Ni和Zn的浸出率可达:78%、53%和74%.     

嗜酸氧化亚铁硫杆菌对龙门挂架表面铜的浸出效果

龙门挂架(下称挂架)是线路板生产过程必用的固定支架,生产线路板时挂架表面会附着大量铜,使得挂架需经酸法处理后才能回用,造成大量废液和恶劣的工作环境. 为此,采用环境友好的微生物技术回收挂架表面的Cu,分析了A.f菌(Acidithiobacillus ferrooxidans,嗜酸氧化亚铁硫杆菌)脱除挂架表面Cu的效果及9K培养基不同配比(以w计,分别为100%、50%、25%)的影响,并初步解析其浸出过程. 结果表明:①添加100%的9K培养基时,A.f菌浸出挂架及其配件的溶液中ρ(Cu2+)均最高,分别达2.31和1.06 g/L,挂架及其配件表面Cu均已脱除. ②结合浸出液中ρ(Cu2+)、ρ(Fe2+)和pH随时间的变化及三者之间的相互影响关系可知,浸铜过程为A.f菌先将溶液中的Fe2+氧化为Fe3+,Fe3+再将挂架表面的Cu氧化为Cu2+. ③利用一级动力学和二级动力学模型,对3种配比培养基下配件浸出液中的ρ(Cu2+)进行曲线拟合,二级动力学模型的R2(相关系数)分别为0.888 4、0.900 8、0.844 4,均高于一级动力学的R2,表明二级动力学模型更适用于Cu的浸取行为. 该生物浸出方法有望在线路板行业中进行应用.      

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.     

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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