3种复合铁基钝化剂对黔西南高砷土壤的修复效果研究

为研究不同复合铁基钝化剂对黔西南高砷(As)土壤修复效果,筛选出钝化土壤砷和抑制水稻籽粒砷富集效果较好的复合铁基钝化剂,以期为黔西南高砷背景土壤的修复和管理提供科学依据。本文以黔西南某矿区耕地高砷土壤为研究对象进行水稻盆栽实验,分析了3种市售复合铁基钝化剂(复合型铁基生物炭(A)、铁基生物炭(B)和铁基腐殖酸钾(C))在不同用量(0.67g/kg、1.34g/kg、2.68g/kg、5.36g/kg)下土壤有效态砷、土壤中砷的各种结合态以及水稻籽粒砷含量的变化。结果表明,三种复合铁基钝化剂的施加可不同程度的提高土壤pH和钝化土壤砷,其中钝化剂C在5.36g/kg施用量下效果最好,钝化率为26.2%;各处理均使土壤砷的赋存形态发生一定的改变,均不同程度的降低了非专性吸附态、专性吸附态及无定形和弱结晶铁铝氧化物结合态的砷,其中钝化剂A和B主要是向结晶铁铝氧化物结合态砷转变,C处理主要向残渣态砷转变;各处理均显著抑制了水稻精米砷含量,相比对照组,复合钝化剂A在1.34g/kg施用量下大米对As的富集作用最弱,降低率为48.6%;因为土壤砷钝化率不能完全表征水稻对砷的富集能力,其不宜作为土壤砷修复的唯一考察指标,因此土壤修复评估时应综合考虑土壤钝化率及水稻籽粒对砷累积的综合影响。     

镁基膨润土和水泥对砷铅复合污染土壤的钝化效能与机理研究

利用镁基膨润土（MB）和水泥（SN）作为钝化剂修复化工厂砷（As）、铅（Pb）复合污染土壤,探索了两种钝化剂对土壤pH值、有机碳含量（OC）、阳离子交换量（CEC）、浸出毒性及重金属形态分布的影响,结合钝化前后土壤形貌的变化,初步揭示了钝化机理.结果表明,两种钝化剂均可使土壤pH值显著升高,有机碳含量增加,阳离子交换能力增强.钝化30 d后,MB-5对As、Pb的钝化率分别达到67.09%和65.93%;SN-5对As、Pb的钝化率分别达到65.76%和65.04%.经两种钝化剂处理后,Pb的弱酸提取态和可还原态向更加稳定的可氧化态和残渣态转化.MB处理使土壤As由可交换态、可氧化态向无定形铁结合态、结晶性铁结合态转化,SN处理使土壤As向残渣态转化.两种钝化剂均可使土壤的微观形态从片状转变为碎屑状、增加团聚颗粒.与SN相比,MB更能促使土壤As（Ⅲ）向As（V）转化,从而显著降低土壤毒性.     

铁基硅盐对土壤环境镉砷赋存形态及转化影响

为探明铁基硅盐对土壤镉砷赋存形态影响及各形态间转化规律,采用室内长期淹水培养吸附实验,研究不同比例铁硅材料对土壤离子态镉砷活性影响;筛选适宜铁基硅盐(FS)配比同时添加腐殖酸(FSC)和金属氧化物(FSCa),明确复配处理土壤中镉砷分级形态转化程度.结果显示,铁:硅比值增加10%,土壤pH值平均降低0.35;F₂-S₈处理土壤离子态镉降幅71%;F₁₀-S₀处理土壤离子态砷降低59.9%,离子态镉砷含量与硅酸盐-铁盐施用量互呈反比;处理F₄-S₆和F₆-S₄之间镉、砷钝化率产生交点,约为25%~30%.土壤中镉主要以可溶态为主,占比58%;砷主要以铁铝氧化态和钙结合态为主,占比40%和23%.铁硅比例为5:5或5.5:4.5左右复配能有效将铝结合态砷和铁铝氧化态砷转变为钙结合态砷和残渣态砷,可溶态镉转化为碳酸盐结合态镉以及铁锰氧化态镉,同步降低土壤中镉砷的活性.     

稻田镉污染原位钝化修复及磷积累与迁移特征

选择苏南某镉（Cd）污染稻田,研究钙镁磷肥和钙铝水滑石2种钝化修复材料对Cd污染土壤原位钝化修复的效果,并且探讨含磷钝化剂的使用对水土环境磷累积与迁移特征的影响.结果表明：施用2种钝化剂后均能有效降低土壤中有效态Cd的含量,且随着钝化时间的推移,有效态Cd含量均呈现稳定缓慢降低的趋势,在施加钝化剂16周后达到最低,不同处理的钝化效果依次为：1500kg/hm²钙镁磷肥>6000kg/hm²钙铝水滑石>750kg/hm²钙镁磷肥,各处理有效态Cd比施加前分别降低了54.5%、50.3%以及46.9%.各处理在不同阶段的土壤pH值与有效态Cd含量呈显著负相关.施用钙镁磷肥作为钝化剂会加快土壤中磷的累积,且随着施用量的增加60~90cm深度渗漏水中总磷和溶解性磷酸盐含量有明显升高趋势.     

富里酸改性FeMnNi-LDH对砷镉污染土壤的钝化修复

选用腐殖质活性组分富里酸(FA)作为铁锰镍层状双氢氧化物(FeMnNi-LDH)的修饰物,采用共沉淀法制备出稳定层状FA@Fe Mn Ni-LDH复合材料,并运用于As(Ⅲ)和Cd(Ⅱ)复合污染土壤的钝化修复.通过小白菜盆栽实验研究了在不同砷镉复合污染水平及不同初始土壤pH值条件下,复合材料对土壤As(Ⅲ)和Cd(Ⅱ)的钝化效果、各形态含量变化及对小白菜根部和地上部As(Ⅲ)和Cd(Ⅱ)转运、富集系数的影响,并进行相关性分析.结果表明,FA@Fe Mn Ni-LDH复合材料对As和Cd具有显著的同步钝化效果.当复合材料添加量由0%增加到1.0%,促进了土壤非专性吸附态和结晶铁铝氧化物结合态As向专性吸附态、无定型铁铝氧化物结合态和残渣态As转化,土壤可交换态Cd主要向残渣态、碳酸盐结合态、铁锰氧化物结合态和有机结合态Cd转化;土壤初始pH对As和Cd的钝化效果影响明显,酸性和中性土壤的pH分别增加了1.65和0.64个pH单位,土壤有效态As的降低率分别达到69.74%和63.31%,有效态Cd的降低率分别为60.25%和61.78%;小白菜的鲜重和株高随复合材料添加量的增加而提高,并...     

赤泥基纳米零价铁对多金属污染土壤修复效果

为实现重金属复合污染（Pb、Zn、Cu和Cd）土壤同步修复,构建土壤-小白菜体系,探究赤泥（RM）、纳米赤泥（RMn）以及纳米赤泥负载纳米零价铁（RMn-nZVI）这3种不同赤泥基钝化剂对Pb、Zn、Cu和Cd复合污染土壤的修复效果与机制,并考察土壤中Pb、Zn、Cu和Cd形态分布对小白菜积累Pb、Zn、Cu和Cd的控制作用.结果显示,3种钝化剂施用可显著提高土壤pH,降低土壤酸可提取态（F1）Pb、Zn、Cu和Cd含量,增加残渣态（F4）含量,最终钝化效果表现为：RMn-nZVI>RMn>RM.此外,3种钝化剂显著降低了小白菜可食用部分Pb、Zn、Cu和Cd的积累,其中RMn-nZVI处理下降低程度最高,Pb、Zn、Cu和Cd含量分别下降35.11%、45.05%、69.52%和59.63%.结果表明,纳米赤泥负载纳米零价铁新型钝化材料在重金属复合污染土壤修复领域具有一定的应用潜力.     

生物质炭与铁钙材料对镉砷复合污染农田土壤的修复

选取了铁钙材料（FC）和山核桃蒲生物质炭（BC）制备得到复合材料（BF）,用于修复农田土壤中镉砷复合污染,以降低水稻糙米中的镉和砷含量.通过水稻盆栽试验,在植物生长期内,采集了土壤孔隙水、根际土壤、非根际土壤、水稻植株和水稻根表铁膜,探究了铁钙材料、生物质炭及其复合材料对土壤中镉和砷生物有效性和植株中镉和砷含量的影响及机制.结果表明,生物质炭材料能显著（P <0.05）提高非根际土壤（0.55～0.66个单位）和根际土壤（0.28～0.36个单位）pH,且提升土壤DOC含量;铁钙材料能显著（P <0.05）降低非根际土壤（0.14～0.27个单位）和根际土壤（0.38～0.41个单位）pH,同时降低土壤DOC含量.铁钙材料和复合材料能够同时降低土壤孔隙水、根际土壤和非根际土壤有效态Cd和As含量,而生物质炭能降低Cd含量,却提高了As含量,其中复合材料1%添加处理的效果最佳,土壤有效态Cd和As分别降低了41.8%～48.2%和6.1%～10.1%.生物质炭、铁钙材料和复合材料均能提高植株生物量（根、茎、叶和籽粒的干重）,水稻籽粒干重较CK增加了48.5%～184.0%,根...     

高分子聚合物与钝化剂复配对汞污染土壤钝化修复研究

采用盆栽试验方法,研究了添加1种耐酸性较强的高分子聚合物与传统的有机或无机类钝化剂复配来钝化土壤重金属汞,并探讨其对土壤理化特性、植物生长发育、土壤汞形态以及酶活性等的影响。结果表明:与对照（CK）相比,添加不同钝化剂均能有效改善汞污染土壤理化状况和土壤微环境,促进植物生长。不同钝化剂处理均显著降低了土壤有效态汞的比例,土壤水溶态、可交换态汞比例分别较CK降低了106%~315%、12.61%~34.60%;与单一钝化剂相比,添加高分子聚合物的钝化剂能更有效吸附、固定土壤中的汞,并降低土壤重金属汞的生物有效性;生物炭-聚丙烯酰胺（BI-PAM）处理对土壤有机质含量和pH增加最为明显,且对土壤重金属汞的钝化效果最好（水溶态汞、可交换态汞和Fe-Mn氧化物结合态汞占总汞比例最小,分别为1.05%、12.14%、12.72%,而强有机结合态汞和残渣态汞比例最高,分别为15.86%和58.23%）,能促进增产且减少白菜叶片对汞的吸收富集。根据试验结果,针对汞污染酸性土壤,建议施用生物炭与聚丙烯酰胺复配而成的钝化剂。     

钝化材料对镉污染农田原位钝化修复效果研究

原位钝化修复在重金属污染土壤修复中有着不可替代的作用,而修复材料在污染农田中的长期应用效果一直是人们关注的焦点。该文以Cd污染农田酸性土壤为研究对象,选择2种水稻品种(DY:德优4727;CY:川优6203)为供试材料,设置T1(石灰0.15kg/m~2)、T2(海泡石1.12 kg/m~2)、T3(石灰0.15 kg/m~2+海泡石1.12 kg/m~2)、T4(石灰0.15 kg/m~2+偏硅酸钠30 g/m~2+七水硫酸镁7.5 g/m~2)、T5(石灰0.15 kg/m~2+腐殖酸75 g/m~2)、T6(秸秆生物炭1.12 kg/m~2)和T7(灌浆期叶面喷施0.2%螯合铁肥)7个钝化处理。通过田间试验,研究不同钝化剂处理对土壤理化性质、Cd形态、水稻产量及糙米Cd含量的影响。结果表明,与对照相比,施加钝化剂后土壤pH降低了0.09～1.07个单位,有机质增加了2.48%～41.96%,速效钾增加了3.62%～103.91%,碱解氮降低了0.25%～29.71%,其中,T3、T5和T6能有效提高土壤有机质,且对土壤肥力影响较大。T1、T4和T6处理的Cd形态向更稳定的氧化态和残渣态转化。T1和T5处理下,不同品种水稻产量及糙米Cd含量均表现为CYDY。因此,推荐以DY作为水稻品种,选用T5钝化处理作为修复酸性Cd污染农田具有较好的修复效果。     

毛竹遗态Fe/C复合材料对As(Ⅴ)污染土壤的钝化修复性能

选择广西红壤为背景土壤,以自制毛竹遗态Fe/C复合材料（PBGC-Fe/C）为钝化剂,对As（Ⅴ）污染土壤进行钝化修复,结合扫描电镜（SEM）、X射线衍射（XRD）和红外光谱（FT-IR）的表征结果对钝化机制展开分析.结果表明：PBGC-Fe/C能有效钝化修复高浓度As（Ⅴ）污染土壤,在投加比例为5%、含水量为25%和材料粒径为100目的条件下,PBGC-Fe/C对500 mg·kg^-1和1000 mg·kg^-1As（Ⅴ）污染土壤的稳定率分别可达80.95%和73.49%;毛竹炭遗态结构有吸附点位多的优势,酸性条件有利于土壤中As（Ⅴ）的钝化.PBGC-Fe/C不仅可吸附固定砷,同时可促使砷的形态转向稳定化,化学络合和离子交换在钝化修复过程中起主要作用.     

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.     

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.     

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.