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。     

铬渣污染土壤清洗剂筛选研究

以3种不同质地的铬渣污染土壤(A土,B土和C土)为研究对象,探讨了4种清洗剂对污染土壤中Cr的清洗效果,并采用欧盟BCR三步顺序提取法,研究了不同清洗剂对土壤中各形态Cr的去除效果. 结果表明:同一污染土壤上4种清洗剂对总Cr的去除效果差别不大;低浓度清洗剂对Cr(Ⅵ)和Cr(Ⅲ)的去除效果与去离子水相当;高浓度清洗剂效果优于低浓度清洗剂,且高浓度清洗剂洗出的总Cr主要以Cr(Ⅲ)为主. 同一清洗剂对3种污染土壤的清洗效果为C土>B土>A土. 去离子水主要去除酸可提取态Cr;EDTA-Na₂对酸可提取态和可还原态Cr去除效果较好;柠檬酸去除的是酸可提取态、可还原态和可氧化态Cr;而HCl对各形态Cr都有所去除. 因此,对于酸可提取态和可氧化态Cr含量较高的A土,柠檬酸是最佳清洗剂;而对于酸可提取态Cr占优势的B土和C土,去离子水是最佳清洗剂.      

柱淋洗法修复铬污染土壤的效果研究

以铬渣污染土壤为供试土壤,采用土柱淋洗法研究柠檬酸、草酸和盐酸单一淋洗以及复合淋洗对铬去除动态和修复效果的影响,并对淋洗前后土壤中铬形态进行分析,探讨修复机理。结果表明,各淋洗方案中,以10体积0.5 mol/L草酸溶液为淋洗剂时的修复效果最好,总Cr累计淋出量为2 304 mg/kg,上层、中层和下层土壤总Cr去除率分别为79.6%、78.1%和69.6%,Cr(VI)去除率为87.8%、86.2%和75%,且土壤Cr(VI)和总Cr随着土壤深度的增加而升高,有在底部积累的可能;淋洗后土壤明显酸化,p H值从10.5降至3左右;以酸作为淋洗剂能有效降低土壤可氧化态铬含量,将其转化为移动性较强的酸可提取态,这有助于达到预期修复效果。     

硫酸/硫酸钠复合淋洗剂对铬渣的淋洗效果研究

以湖南长沙某铬盐厂铬渣为研究对象,通过室内模拟实验,采用振荡淋洗方法研究了硫酸-硫酸钠复合淋洗剂对铬渣污染场地Cr的淋洗效果,探讨了淋洗剂浓度、液固比和淋洗时间等对淋洗效果的影响,以及淋洗前后重金属形态的变化,并通过对比试验研究了硫酸钠、柠檬酸、草酸、Na2-EDTA、硫酸、柠檬酸-柠檬酸三钠以及盐酸-氯化钠作为淋洗剂对总铬和六价铬的淋洗效果。结果表明:硫酸/硫酸钠复合淋洗剂在浓度为0.4 mol/L,液固比为20∶1,反应时间为6 h,常温条件下可以达到最佳淋洗效果,总铬和六价铬的浸出效率分别为70.35%和71.56%;另外,重金属形态分析表明,该复合淋洗剂有效减少了铬渣中弱酸可提取态和有机物结合态Cr的百分比,使得残渣态Cr的百分比增加,从而降低了Cr的活性,达到修复目的。淋洗剂对比试验结果表明,与其他淋洗剂相比,硫酸-硫酸钠淋洗效果最好,其中的氢离子能与Cr~(3+)进行离子交换,而硫酸根能够有效地将钙与六价铬分离,对此高钙铬渣的处理更具针对性和有效性。     

有机螯合剂对污染土壤中Pb和Cd淋洗修复研究

以辽宁省某锌厂附近农田耕作层土壤为研究对象,采用酒石酸、柠檬酸和草酸为淋洗剂,在不同实验条件下进行振荡淋洗实验,研究三种有机螯合剂淋洗土壤中Pb和Cd的最佳环境条件以及淋洗机理。结果表明:酒石酸、柠檬酸和草酸在液固比为20,淋洗液浓度为0.2 mol·L~(-1),温度为30℃,pH为3的实验条件下,对Pb和Cd的淋洗效果最好;温度升高,导致重金属离子的扩散速率相应提高,从而提高重金属的淋洗率;pH降低,有机酸中所含质子数越多,对重金属的活化能力越大,提高重金属化合物的可溶性,从而提高重金属淋洗率;酒石酸、柠檬酸和草酸对酸可提取态的Pb和Cd均有很好的去除效果,对可还原态和可氧化态有一定程度的去除效果。     

H2O2氧化联合化学淋洗修复电镀工厂铬污染黏性土壤的试验研究

以合肥某电镀工厂遗留的铬污染黏性土壤为研究对象,采用H₂O₂氧化联合盐酸和柠檬酸进行化学淋洗对土壤中的总铬和Cr(Ⅵ)进行修复去除,并对氧化剂H₂O₂的浓度、淋洗剂盐酸和柠檬酸的浓度对土壤中铬的去除率的影响进行探究。结果表明:单独采用H₂O₂氧化,在浓度为10.0%时,其对土壤中铬的去除效果最佳,Cr(Ⅵ)去除率达到51.5%,总铬去除率达到20.9%;单独H₂O₂氧化、盐酸和柠檬酸淋洗后土壤中Cr(Ⅵ)浓度仍然超过GB 36600—2018《土壤环境质量 建设用地土壤污染风险管控标准(试行)》二类用地标准。而对H₂O₂氧化后土壤继续联合盐酸或柠檬酸淋洗,当盐酸浓度为1.0 mol/L、固液比为1∶4时,H₂O₂氧化联合化学淋洗修复后的土壤中Cr(Ⅵ)浓度为4.4 mg/kg,达到GB 36600—2018二类用地标准,此时土壤中Cr(Ⅵ)去除率为85.5%,总铬去除率为50.6%。Tessier五步提取形态分析表明:修复后土壤中残渣态铬的比例从44.7%提高到93.4%,显著降低了铬二次释放的风险。研究结果可为铬污染土壤的治理修复和铬的回收利用提供参考。     

复合淋洗剂土柱淋洗法修复Cd、Pb污染土壤

选取三氯化铁和有机酸(柠檬酸、苹果酸、酒石酸)复合淋洗,采用土柱淋洗的方法对Cd、Pb污染土壤进行淋洗实验,研究了复合淋洗剂浓度配比、淋洗剂用量和淋洗次数对重金属去除效果的影响,并测定了土壤淋洗前后Cd、Pb形态的变化。结果表明:三氯化铁浓度为10 mmol/L,有机酸浓度为20 mmol/L时,淋洗率Cd为72.15%,Pb为30.26%,与使用单一淋洗剂相比均有大幅提升。复合淋洗剂能有效地去除交换态、碳酸盐结合态和氧化物结合态重金属,而对有机态和残余态部分重金属作用效果不明显;Cd比Pb容易去除是由于污染土壤中Cd的存在形态主要是可交换态、碳酸盐结合态和铁锰氧化物结合态,而Pb的存在形态主要是有机结合态和残渣态。淋洗后土壤中Cd和Pb均达到土壤环境质量标准。     

绿色合成纳米零价铁铜淋洗修复Cr(Ⅵ)污染土壤

采用自制的绿色合成纳米零价铁铜(GT-nZVI/Cu)对Cr(Ⅵ)污染土壤进行淋洗修复。分别测定了土壤浸出液中Cr(Ⅵ)浓度、pH值和电导率,并使用改进的BCR连续提取法分析了淋洗前后污染土壤中铬的形态变化。结果表明:淋洗过程分为2个阶段,Cr(Ⅵ)的释放主要在前3个孔隙体积(PV)内;浸出液中电导率的变化趋势与Cr(Ⅵ)浓度变化一致;浸出液pH值随着淋洗体积的增加而增加,土壤的平衡作用变得稳定;土壤中Cr(Ⅵ)浓度、悬浮液pH值和GT-nZVI/Cu浓度对铬污染土壤的修复效果均有一定影响。铬的形态分析表明:铬污染土壤在淋洗后可还原态铬含量降低,氧化态铬和残渣态铬的含量增加。GT-nZVI/Cu悬浮液对污染土壤淋洗后,土壤中铬形态更加稳定。     

酸化-电动强化修复铬渣场地污染土壤

为解决常规电动修复方法对Cr污染土壤Cr(T)(总Cr)去除效率低的问题,提出了酸化预处理-电动强化修复技术. 以国内某化工厂铬渣堆放场地Cr污染土壤为研究对象,通过改变土壤酸化条件,分析乙酸和柠檬酸的酸化时间、酸浓度(以c计)对电动修复Cr污染土壤中Cr去除率的影响,并对土壤中Cr的形态进行分析. 结果表明:①酸化预处理-电动强化修复技术可以显著提高Cr污染土壤中Cr的去除率,其中0.9 mol/L柠檬酸酸化5 d组Cr(T)和Cr(Ⅵ)的去除率由对照组的6.23%、19.01%分别升至26.97%、77.66%. ②土壤酸化可以将部分Cr由碳酸盐结合态向水溶态转化,进而提高Cr去除率;在适宜的酸浓度范围内,酸浓度越高,土壤释放的Cr越多,Cr去除效果就越好. ③与乙酸组相比,柠檬酸组Cr的去除率较高,因为柠檬酸本身也是一种络合剂,在酸化作用释放碳酸盐结合态Cr的基础上,柠檬酸能与Cr发生络合作用,进一步提升了Cr的去除率. 电动修复过程中迁移出土壤的Cr主要以醋酸可提取态、可还原提取态和可氧化提取态为主,残留Cr的生物可利用性降低.      

皂角苷和柠檬酸联合去除厌氧消化污泥中重金属的研究

以武汉某污水处理厂未厌氧消化与厌氧消化的污泥(分别为S1和S2)为研究对象,通过振荡淋洗实验,研究了皂角苷(质量分数0.1%~2.0%)和柠檬酸(0~1 mol·L~(-1))联合对2种污泥中Ni、Pb、Zn的去除效果,确定皂角苷和柠檬酸联合淋洗的最佳浓度组合,并采用BCR连续提取法分析淋洗前后3种重金属的形态变化.结果表明,皂角苷和柠檬酸联合对污泥中3种重金属均有较好的去除效果,Ni、Pb、Zn的最高总去除率分别为76.02%、59.93%和15.94%.综合分析,1%的皂角苷与0.4 mol·L~(-1)的柠檬酸联合淋洗的去除效果最好,2种污泥中重金属去除率的大小均为未厌氧消化污泥(S1)厌氧消化污泥(S2).与未厌氧消化污泥相比,厌氧消化污泥Ni的残渣态、Pb的可还原态及Zn的可氧化态含量明显增加,而Ni的可还原态含量减少.联合淋洗后S1、S2中约80%的酸溶态和可还原态的Ni、Zn被去除,Pb的可还原态分别去除67.07%和58.06%;且各重金属残渣态所占比例大幅度增加,其中,Pb的增加最为明显,所占比例超过90%.     

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.