A porous biochar supported nanoscale zero-valent iron material highly efficient for the simultaneous remediation of cadmium and lead contaminated soil

Risk associated with heavy metals in soil has been received widespread attention.In this study,a porous biochar supported nanoscale zero-valent iron（BC-nZVI） was applied to immobilize cadmium（Cd） and lead（Pb） in clayey soil.Experiment results indicated that the immobilization of Cd or Pb by BC-nZVI process was better than that of BC or nZVI process,and about 80% of heavy metals immobilization was obtained in BC-nZVI process.Addition of BC-nZVI could increase soil pH and organic matter（SOM）.Cd or...     

白腐菌联合纳米零价铁强化去除水中Cd(II)

采用白腐菌和纳米零价铁(nZVI)联合体系强化去除水中Cd (II),并考察pH值、Cd (II)初始浓度、温度、nZVI投加量对Cd (II)去除的影响,分析nZVI对白腐菌胞内外富集镉的影响特性,同时结合扫描电镜、红外光谱、X射线光电子能谱、三维荧光光谱等手段分析联合体系对Cd (II)的强化去除机制.结果表明,在pH=6,Cd (II)初始浓度为50mg/L,温度为30℃,nZVI投加量为0.1g/L的条件下反应180min后,Cd (II)的去除率可达到99.5%以上.联合体系对Cd (II)的去除过程符合准二级动力学,主要去除机制为白腐菌对Cd (II)的胞外络合吸附,添加nZVI能促进白腐菌对Cd (II)的胞外吸附,FTIR和XPS分析表明,羟基、羧基和氨基参与了Cd (II)的吸附,白腐菌胞外聚合物(EPS)能与铁发生内层配位形成P-O-Fe键,加速富含羟基官能团的纤铁矿、磁铁矿等铁矿物形成,从而促进对溶液中Cd (II)的吸附去除.     

生物炭负载纳米零价铁制备及修复六价铬污染土壤技术研究进展

近年来,纳米零价铁颗粒（nZVI）应用于Cr（Ⅵ）污染修复治理技术研究备受关注。生物炭负载型纳米零价铁（nZVI@BC）作为纳米零价铁改性技术之一,具有低成本、易制备和修复效果优越等优点,但此技术应用于Cr（Ⅵ）污染土壤修复方面研究尚不多。生物炭（BC）主要通过植物秸秆热解生成,生物炭负载纳米零价铁（nZVI@BC）则通过生物炭与纳米零价铁在热解-液相还原法或一步热解法合成。制备的nZVI@BC能够有效解决纳米零价铁团聚和钝化等缺点,显著提高纳米零价铁（nZVI）利用率。综述了生物炭负载纳米零价铁（nZVI@BC）应用于修复Cr（Ⅵ）污染土壤反应机理和研究进展,总结出提升该材料性能的途径有:通过调整BC热解条件和改性BC以提升BC性能;适当的质量比（BC/nZVI）;使用聚乙二醇（PEG）、羧甲基纤维素（CMC）、污泥衍生的BC和茶多酚（TP）提高nZVI稳定性。nZVI@BC材料能够提高土壤中有机质含量,在Cr（Ⅵ）修复治理方面极具应用前景。     

生物炭负载零价纳米铁去除土壤中十溴二苯乙烷

作为十溴联苯醚的替代品,新型溴代阻燃剂十溴二苯乙烷（DBDPE）已经在国内外大量使用.随着DBDPE在各种环境介质中被普遍检测到,其造成的环境污染正引起广泛关注.本论文首先制备生物炭（BC）负载零价纳米铁（nZVI）材料（BC/nZVI）,进而研究了BC/nZVI去除土壤中DBDPE的动力学过程,并探究了作用机制.结果表明：BC加入能促进nZVI均匀分散在生物炭的表面,并改善了其分散程度;BC/nZVI去除效率最高（投加量为0.1 g·g^-1,BC：nZVI为2：1,DBDPE初始浓度为10 mg·kg^-1）,24 h内达到了89.74%,去除过程涉及到吸附和降解的共同作用,实验数据符合准一级动力学方程;采用LC-MS-MS探究了DBDPE的降解产物和途径;ECOSAR毒性评价数据显示BC/nZVI能够降低DBDPE的生态毒性.     

热解温度对生物炭强化镉污染土壤治理的影响

为了探究污泥生物炭对Cd污染土壤的钝化修复效果,采用人工模拟Cd污染土壤进行盆栽实验,并探究了生物炭对Cd污染土壤pH、有机碳、Cd含量及价态、玉米株高、富集系数及生物转化系数的影响。结果表明:热解温度为800℃时制备的生物炭的修复效果优于300℃时制备的生物炭,且生物炭的最佳剂量为9.0 g/kg。施用800℃下制备的生物炭时,土壤中Cd含量也增加至7.9 mg/kg,较热解温度300℃增加约1.0 mg/kg。污泥生物炭显著降低了土壤中酸可提取态及还原态Cd的含量,升高了氧化态及残渣态Cd含量。当热解温度为800℃时,酸可提取态和还原态Cd含量分别降低至0.68,0.45 mg/kg,氧化态及残渣态Cd含量分别升高至0.76,1.72 mg/kg,从而降低了土壤中可生物利用Cd的含量。此外,生物炭能够降低Cd的生物富集系数及转化系数。     

制备工艺对nZVI/污泥基生物炭中Zn、Cu、Pb形态分布及其生态风险的影响

以市政污泥为原料、纳米零价铁（nZVI）为添加剂,采用热解法制备污泥生物炭,考察了nZVI添加量、热解温度和升温速率对生物炭中Zn、Cu、Pb形态分布及其生态风险的影响。结果显示:高nZVI添加量、高热解温度及低升温速率可提高稳定态（BCR法） Zn、Cu和Pb的含量;高nZVI添加量可促使Zn、Cu和Pb向可氧化态转化,而高热解温度和低升温速率有利于残渣态Zn、Cu和Pb的生成;最优nZVI添加量、热解温度和升温速率分别为2000 mg/kg,800℃和4℃/min。此外,当nZVI添加量为800 mg/kg、热解温度为800℃和升温速率为2℃/min时有利于降低Zn、Cu和Pb的生态风险;Zn、Cu和Pb总体生态风险等级分别为低风险、低风险和无风险,与Cu和Pb相比,Zn的生态风险较高;以RI值为评价指标,nZVI/污泥基生物炭的优化制备工艺为:nZVI添加量为200 mg/kg,热解温度为800℃,升温速率为5℃/min。     

生物质炭对磷镉富集土壤中两种元素生物有效性及作物镉积累的影响

以磷镉富集土壤(总Cd 0.94mg·kg~(-1)、全磷0.86g·kg~(-1))和低镉积累基因型红菜薹金秋红三号为供试材料,采用盆栽试验的方法,设置了绝对对照CK0(仅施NK无机肥)、相对对照CKp(施NPK无机肥)、生物质炭BC(BC+NK无机肥)和BC-CKp(BC+NPK)这4个处理,考察了土壤磷素和重金属Cd的生物有效性、植株可食部位生物量及其Cd累积特征和土壤基本性状等指标.结果表明,至作物收获时,添加生物质炭的BC和BC-CKp处理与未添加生物质炭的CK0和CKp处理相比,土壤有效Cd含量分别降低了8.23%和5.68%;同时土壤有效磷含量提高了11.60～16.26mg·kg~(-1).施加外源磷肥的CKp和BC-CKp处理土壤有效Cd含量与未施加磷肥的CK0和BC处理相比分别降低了31.43%和33.29%.除CK0处理外,其它3个处理(CKp、BC及BC-CKp)的红菜薹作物可食部位Cd含量均未超出我国食品安全国家标准(GB 2762-2017)中Cd的限定值0.1mg·kg~(-1).结果表明,将生物质炭输入到磷素富集的中、轻度Cd污染土壤中,能够同时实现土壤中重金属Cd钝化和磷素活化的双重功能;且在不额外使用磷素化肥的条件下,种植弱吸收低积累Cd的蔬菜作物基因型,既可以保证可食部位生物量增加,也可以使其可食部位重金属Cd含量满足食品安全国家标准.     

还原氧化石墨烯支撑纳米零价铁对含Sb(Ⅲ)废水的处理

针对含重金属Sb(III)废水处理问题,采用液相还原法制备出高效的还原氧化石墨烯负载纳米零价铁(nZVI/rGO)复合吸附材料,并采用多种技术手段对所制备的nZVI/rGO复合材料进行表征.同时,复合材料中nZVI的负载量、吸附剂投加量、初始pH值以及反应温度等因素对废水中Sb(Ⅲ)吸附去除效果的影响被全面考察,并进一步对吸附过程进行吸附等温线和吸附动力学拟合.结果表明,在25℃,pH为3.0时,当nZVI负载量为70wt%,nZVI/rGO投加量为0.5g/L时,Sb(Ⅲ)的去除率最高,140min内可达99.7%.该吸附过程符合准二级动力学模型与Langmuir等温吸附模型,因此nZVI/rGO被证实是一种高效的Sb(III)吸附材料.     

牛粪生物炭对磷的吸附特性及其影响因素研究

以牛粪生物炭为吸附剂,采用平衡吸附法研究了牛粪生物炭对磷的吸附特征.研究了pH值、共存离子、反应温度、投加量、热解温度等对牛粪生物炭吸附磷的影响.结果表明,牛粪生物炭吸附磷的最佳初始pH值为7.0;共存离子的存在对生物炭吸附磷的影响有限;反应温度升高不利于磷的吸附;当投加量为0.1g时,对磷的去除率较为理想;热解温度升高不利于对磷的吸附.通过对实验数据进行动力学、吸附等温线及热力学分析,发现牛粪生物炭对磷的吸附动力学数据符合拟二级吸附动力学方程,Langmuir-Freundlich(R2=0.9705)和Temkin(R2=0.9556)方程能很好地描述磷在牛粪生物炭上的吸附行为.热力学分析结果显示25,35,45℃下的吉布斯自由能变化(ΔG0)分别为-17.43,-15.98,-15.89kJ/mol,表明牛粪生物炭对磷的吸附是自发的过程.     

不同热解温度的生物炭在土壤中的矿化作用研究

为探究不同热解温度的生物炭不同组分(易降解和相对难降解碳)对其在土壤中矿化作用的影响及机理,将生物质甘蔗渣和在300、500、800℃下热解生成的生物炭(分别表示为BC300、BC500、BC800)通过水洗法剥离出碳骨架部分,然后加入含有定量土壤菌悬液的石英砂中,设置了50 d的控温培养实验并测定培养过程中不同处理样品的矿化速率.结果表明,随着热解温度从300℃升高至800℃,生物炭的易降解碳含量降低,平均停留时间从2 d增加到38 d,相对难降解碳平均停留时间从14年增加到700多年.环境温度为25℃时,碳骨架中由于缺少微生物可利用的溶解性有机碳,所以在土壤中稳定性强.环境温度升高至35℃时,温度升高提高了微生物活性,增加了碳骨架的微生物可利用部分.800℃热解生成的生物炭(BC800)及其碳骨架(W800)的累积矿化量比空白低,且即使温度升高,W800的相对难降解碳含量仍然保持最高,表明高温生物炭具有更好的固碳效果.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

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.     

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.     

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.     

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.     

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.     

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.     

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.