改良剂对土壤中Cu形态变化的影响

采用恒温连续培养的方法,以褐煤、腐殖酸、鸡粪为改良剂,探讨其对土壤中Cu形态变化的影响。结果表明,改良剂的加入均不同程度地改变了土壤pH值及有机质的含量。添加改良剂后土壤中Cu-WAE的含量降低,Cu-RES的含量升高,且Cu各种形态的分配比例发生了变化。相关性分析表明,各种Cu形态之间存在一定的相互关系,土壤中Cu-RED、Cu-RES受pH值影响较大,Cu-WAE、Cu-OXI受有机质影响较大。由再分配系数U可知,经褐煤、鸡粪处理后土壤中各种形态的Cu之间相互稳定,而经腐殖酸处理后各种形态的Cu之间不稳定,将会有较多的Cu-WAE进入到更稳定的形态中。添加改良剂的土壤中Cu的IR值大于CK中Cu的IR值,表明经过改良剂处理后的土壤中有较大比例的Cu结合在较稳定的形态中。3种改良剂对土壤都有较好的改良效果,有利于Cu的固定,降低了Cu的生物毒性。     

赤泥对污染土壤Pb、Zn化学形态和生物可给性的影响

通过土壤培养实验,研究添加赤泥对污染土壤中Pb、Zn化学形态和生物可给性的影响。结果表明,不同赤泥用量处理均可显著降低土壤中HOAc提取态Pb、Zn含量。当赤泥用量为5%时,培养1、2和3个月后,HOAc提取态Pb含量分别比对照下降62.5%、65.3%和73.5%;HOAc提取态Zn含量分别比对照下降56.7%、65.8%和67.4%。培养3个月后,只有1%赤泥用量处理显著降低了土壤中生物可给性Pb含量,而不同用量赤泥处理均显著降低了土壤中生物可给性Zn含量。研究表明赤泥是一种钝化污染土壤中Pb、Zn的潜力添加剂。     

淋洗对污染土壤重金属形态分布及生物可利用性影响研究

淋洗是一种快速高效的土壤重金属修复技术,淋洗条件的选择对不同土地利用类型的重金属污染修复具有重要意义。以Ni、Cu、Cd复合污染土壤为研究对象,在不同淋洗条件(液固比和pH)下考察6种淋洗剂(去离子水、模拟酸雨、柠檬酸、草酸、乙二胺四乙酸二钠(Na2EDTA)和氨三乙酸(NTA))对Ni、Cu、Cd的淋洗效果、形态分布及生物可利用性影响。结果表明:(1)当液固比5∶1mL/g时,柠檬酸、Na2EDTA、NTA表现出良好的淋洗效果,对建设用地土壤Ni、Cu、Cd的去除率分别达到84.53%、92.30%、56.00%以上。(2)淋洗后土壤中可交换态、可还原态Ni、Cu、Cd浓度均明显降低。(3)总体上,淋洗使残余指数升高、迁移系数降低,重金属离子在液固比20∶1 mL/g时生物可利用性最低。(4)根据实际污染土壤效果,pH 5.2的柠檬酸或pH 7.5的Na2EDTA在液固比20∶1mL/g时可降低农业土壤的风险;建设用地土壤使用液固比5∶1mL/g、pH 7.5的Na2EDTA或pH 7.5的NTA对3种重金属的去除率达80.43%以上。     

人工纳米颗粒输入对稻田土壤Cd形态转化及生物有效性的影响

进入农田土壤的人工纳米颗粒对土壤中重金属迁移转化及毒性的影响仍不明确。通过模拟稻田淹水-落干过程,研究了二氧化钛（TiO2-NPs）、氧化锌（ZnO-NPs）和多壁碳纳米管（MWCNTs）3种典型人工纳米颗粒对水稻土中重金属Cd赋存形态及生物有效性的影响。结果表明,3种纳米颗粒的添加均引起了土壤pH的增加;TiO2-NPs和ZnO-NPs添加能够显著降低土壤中酸可提取态Cd含量;ZnO-NPs的添加对土壤中铁锰氧化物结合态和有机结合态Cd的含量也有明显降低,但不同浓度处理间Cd含量并无显著差异;MWCNTs对土壤Cd形态转化无显著影响。与对照处理相比,添加TiO2-NPs的处理土壤中,CaCl2和DTPA提取态Cd含量分别降低了13.9%~17.5%和5.4%~8.9%,降幅均与TiO2-NPs添加浓度成正比。添加ZnO-NPs的土壤中,DTPA提取态Cd的含量降幅在8.4%~18.7%之间,降低幅度与ZnO-NPs添加浓度成反比。     

土壤中无机钠盐对不同形态Cu含量的影响

采用TESSIER连续提取法研究了不同种类、不同加入量的无机钠盐对土壤中不同形态Cu含量的影响。结果表明,对于可交换态Cu,3种无机钠盐的加入均使其含量减少,其中NaCl的影响最大,4、8g/kg的NaCl分别使其减少了28.13%(质量分数,下同)和50.59%;对于碳酸盐结合态Cu,3种无机钠盐的加入均使其含量增加,其中Na2CO3(8g/kg)对其影响最大;对于铁锰氧化态Cu,Na2SO4和Na2CO3的加入使其含量先升高后降低,NaCl则使其含量降低;有机结合态Cu受Na2SO4和Na2CO3的影响较大,在它们的影响下含量均增加;残渣态Cu在3种无机钠盐的影响下变化幅度均很大,其中4、8g/kg的Na2SO4分别使其含量减少了47.47%和62.21%。     

生物沥滤过程中城市污泥Zn、Cu的形态转化

利用80 L SBR进行了生物沥滤城市污泥实验,探讨了污泥胞外聚合物中重金属的含量变化,并对重金属Zn、Cu各化学形态之间的转化情况进行了分析。结果表明,整个生物沥滤过程中,污泥胞外聚合物中Zn和Cu含量先上升后下降,反应结束后,分布于胞外聚合物结合态中的Zn和Cu占其污泥胞外聚合物内总量的比例最高可达39.95%、58.77%。污泥胞外聚合物中松散结合态对Zn、Cu的吸附能力均强于紧密结合态;原污泥中Zn、Cu分别主要以铁锰氧化物结合态和硫化物及有机结合态存在,沥滤结束后,污泥中Zn和Cu均以残渣态存在。     

添加天然沸石和石灰对土壤镉形态转化的影响

采用土壤培养实验,研究镉污染土壤中添加沸石、石灰及两者配施对土壤pH值和土壤镉形态变化的影响。结果表明,土壤pH值随沸石用量的增加而增加,随培养时间呈现先增加后下降并逐渐趋于稳定的趋势,但均高于对照。高剂量石灰的处理对土壤pH的影响最大,与对照相比土壤pH提高了3.33个单位。在土壤5~50 d培养过程中,石灰处理的土壤交换态镉含量呈现先逐渐降低而后略有升高的趋势,其余处理均呈下降趋势。培养50 d后,高剂量的沸石、石灰及高剂量沸石与石灰配施处理的土壤交换态镉含量从5 d时的67.54、61.95和55.56 mg/kg降低至54.65、49.93和45.96mg/kg。相关分析表明,不同培养时期交换态镉含量与土壤pH值呈负相关关系。在10个处理中,L2Z3(石灰2 g/kg土和沸石60 g/kg土)组合处理效果最好,使土壤交换态镉含量下降了34.68%,碳酸盐结合态镉含量上升了4.30%,铁锰氧化结合态镉含量上升了16.97%,有机结合态镉含量上升了1.31%,残渣态镉含量上升了12.11%。     

含磷材料对矿区铅镉污染土壤重金属形态转化的影响

以湖南郴州东江湖风景区矿区遗留地重金属污染土壤为研究对象,研究了3种含P材料,及其与蒙脱石的组合材料,对矿区土壤铅镉污染的修复效果。实验设6组处理,分别为P1组、P2组、P3组、P1+M组、P2+M组、P3+M组,通过添加5%的稳定剂,稳定2d后,分析土壤中铅镉的形态变化。实验结果表明:添加含P材料,及组合材料后,土壤中铅镉的离子交换态、铁锰结合态、有机结合态大幅度降低,残渣态显著升高。对Pb离子转化效果均在90.00%以上, Cd离子的转化效率相对较差,最优P1处理效果为74.20%。离子交换态的减少,有效地降低了重金属的生物有效性,有效地降低了环境风险。同时,含P材料均增加了土壤有效磷的含量,对矿区土壤的肥力也有一定提升。     

南淝河沉积物可转化态氮赋存形态及其对上覆水水质的影响

为了探讨黑臭河道沉积物可转化态氮（TF-N）的赋存对上覆水的影响,以典型黑臭水体——南淝河为研究对象,采用连续提取的方法将沉积物中可转化态氮分为离子交换态氮（IEF-N）、弱酸浸提态氮（WAEF-N）、强碱浸提态氮（SAEF-N）和强氧化剂浸提态氮（SOEF-N）,研究南淝河沉积物中可转化态氮形态受排口类型和沉积物理化性质的影响规律,及其与上覆水氮素含量之间的关系。结果表明：南淝河沉积物可转化态氮以TF-NO3--N为主,占TF-N的88.57%±6.13%,而TF-NH4+-N仅占TF-N的11.43%±6.13%;从赋存形态的角度看,南淝河沉积物中SOEF-N相对含量最高（57.48%±3.67%）,WAEF-N次之（26.16%±3.10%）,SAEF-N和IEF-N较少,其相对含量分别为10.30%±4.85%和6.05%±1.73%;沉积物中TF-NH4+-N含量受排口类型的影响较为敏感,且4种赋存形态氮含量受排口类型影响的规律各不相同。另外,pH值和有机质含量对IEF-N影响较大,而CEC影响着WAEF-N含量。上覆水中溶解有机氮（dissolved organic nitrogen,DON）含量与沉积物IEF-N含量之间的显著相关（P4+-N赋存含量越多,释放到上覆水体的可能性越大。研究结果表明黑臭水体是一个复杂的生态系统,调控沉积物可转化态氮形态给黑臭水体内源污染控制提供新思路。     

改良剂对Cd污染土壤中小白菜品质的影响

通过小白菜盆栽试验,以啤酒污泥、草木灰及其混合物作为土壤改良剂,以生物量、可溶性糖、维生素C和叶绿素含量为指标,研究了改良剂对小白菜品质的影响,并分析了土壤中Cd赋存形态的变化。结果表明,不同改良剂在性质和改良机制上存在差异,因此改良效果各不相同,其中啤酒污泥和草木灰的混合物的改良效果最好,其次是啤酒污泥,最后是草木灰。虽然3种改良剂均能降低小白菜茎叶中Cd含量和土壤中有效态(水溶态和可交换态)Cd含量,提高小白菜品质,但小白菜茎叶中Cd含量仍超过《食品中污染物限量》(GB 2762—2005)规定的蔬菜中Cd限量值。     

Effect of compost and manure amendments on zinc soil speciation, plant content, and translocation in an artificially contaminated soil

The addition of organic matter in soil can modify the bioavailability of heavy metals. A greenhouse pot experiment was carried out using an edible plant species Eruca vesicaria L. Cavalieri grown on an artificially contaminated soil with Zn (665 mg?kg^?1). In this study, the effect of compost at 20 t?ha^?1 (C20) and at 60 t?ha^?1 (C60), manure at 10 t?ha^?1 (M10) and at 30 t?ha^?1 (M30), and chemical fertilizers (NPK) on Zn fate in a soil–plant system was evaluated. At the end of the experiment, the main growth parameters and Zn content in plants were determined. In addition, Zn speciation in the soil was assessed using the original Community Bureau of Reference sequential extraction and diethylene triamine pentaacetic acid extraction. Zinc, though an essential element for plant growth, caused toxicity effects in plants grown on control and manure treatments, while in the compost treatments, plants showed no visual toxicity symptoms. The concentrations of Zn in roots were similar for all treatments, while significant differences were observed for shoots. In fact, in the compost treatments, plants showed the lowest Zn concentration in shoots. Zinc speciation seems not to be affected by the applied treatments. Indeed, Zn plant content and translocation to shoots seems to be affected. Compost amendments significantly reduced Zn content and translocation in comparison to other treatments.     

改良剂对重金属复合污染土壤的修复效果

为揭示不同改良剂及其联合施用对重金属复合污染土壤的修复效果,采用室内土壤培养实验和室外盆栽实验相结合,研究不同施用量（10和20 g·kg-1）的蛭石（A）、泥炭（B）和骨粉（C）以及两两组合施用下,改良剂对土壤重金属DTPA有效态、植物（以空心菜为例）生物量、株高以及植物可食部重金属含量的影响。结果表明：不同处理条件下的土壤pH值的提升与空白对照相比变化不显著;单施2%泥炭对土壤重金属Cu、Zn的钝化效果优于其他处理组,相对空白对照组,在第42天2种金属有效态含量分别降低了57.65%和65.55%,而1%蛭石和1%骨粉的混合添加能有效降低土壤中有效态Cd含量,相对空白对照组在第42天有效态Cd含量降低了40.52%;3种改良剂单施和混施对空心菜均具有增产增收的显著效果,且混施改良剂对空心菜增产效果较好;各处理组中空心菜体内Cu、Zn和Cd含量均有显著的降低,其中2%泥炭、1%蛭石+1%泥炭和1%蛭石+1%骨粉处理组分别对空心菜体内Cu、Zn和Cd含量降低效果最好,相对空白对照组分别降低了75.39%、70.75%和75.42%。因此,在该污染类型土壤泥炭、蛭石+泥炭和蛭石+骨粉分别对空心菜吸收土壤中的Cu、Zn和Cd具有较好的阻控效果。     

还原稳定剂配伍对铬污染土壤的稳定化效果

以某铬盐生产场地内的铬(Cr)污染土壤为研究对象,探讨了多硫化钙(CPS)、硫酸亚铁(FeSO4)、零价铁粉(Fe0)、葡萄糖和淀粉单用或复配对土壤中六价铬(CrⅥ))含量和浸出毒性的影响。结果表明：添加质量比3%的CPS和FeSO4对土壤Cr（Ⅵ）的还原率分别为81.5%和46.4%,而Fe0无显著还原作用,但FeSO4和Fe0对Cr（Ⅵ）的稳定效率分别为95.2%和90.9%,明显高于CPS(83.0%);养护5 d时,CPS+FeSO4对土壤Cr（Ⅵ）的还原率和稳定效率分别为99.8%和97.0%,但养护30 d时,其还原率和稳定效率分别显著降低1.3和8.0个百分点;与CPS+FeSO4类似,CPS+Fe0对土壤Cr（Ⅵ）的还原率随养护时间增加而显著降低,但其稳定效率并未随养护时间增加而显著降低;此外,与CPS-6相比,Fe0参与的复配处理对土壤总Cr和Cr（Ⅵ）的稳定效率显著增加,均达到99.8%以上,浸出浓度均小于0.05 mg·L-1;有机碳源参与的复配处理的还原率和稳定效率均随养护时间的增加而增加,其中CPS+Fe0+葡萄糖处理养护30 d时土壤Cr（Ⅵ）为0.24 mg·kg-1,总Cr和Cr（Ⅵ） 浸出浓度均小于0.05 mg·L-1,满足《重金属污染场地土壤修复标准》（DB 43 1165-2016-T）要求。同等药剂添加比例下,还原稳定剂复配可以取长补短,提高药剂对土壤Cr（Ⅵ）的还原率和稳定效率。     

Arsenic and chromium speciation in an urban contaminated soil

The distribution and speciation of As and Cr in a contaminated soil were studied by synchrotron-based X-ray microfluorescence (μ-XRF), microfocused X-ray absorption spectroscopy (μ-XAS), and bulk extended X-ray absorption fine structure spectroscopy (EXAFS). The soil was taken from a park in Wilmington, DE, which had been an important center for the leather tanning industry along the Atlantic seaboard of the United States, until the early 20th century. Soil concentrations of As, Cr, and Pb measured at certain locations in the park greatly exceeded the background levels of these heavy metals in the State of Delaware. Results show that Cr(III) and As(V) species are mainly present in the soil, with insignificant amounts of Cr(VI) and As(III). Micro-XRF maps show that Cr and Fe are distributed together in regions where their concentrations are diffuse, and at local spots where their concentrations are high. Iron oxides, which can reduce Cr(VI) to Cr(III), are present at some of these hot spots where Cr and Fe are highly concentrated. Arsenic is mainly associated with Al in the soil, and to a minor extent with Fe. Arsenate may be sorbed to aluminum oxides, which might have transformed after a long period of time into an As-Al precipitate phase, having a structure and chemical composition similar to mansfieldite (AlAsO(4)?2H(2)O). The latter hypothesis is supported by the fact that only a small amount of As present in the soil was desorbed using the characteristic toxicity leaching procedure tests. This suggests that As is immobilized in the soil.     

Solid/solution Cu fractionations/speciation of a Cu contaminated soil after pilot-scale electrokinetic remediation and their relationships with soil microbial and enzyme activities

The aim of this study was to investigate the detailed metal speciation/fractionations of a Cu contaminated soil before and after electrokinetic remediation as well as their relationships with the soil microbial and enzyme activities. Significant changes in the exchangeable and adsorbed-Cu fractionations occurred after electrokinetic treatment, while labile soil Cu in the solution had a tendency to decrease from the anode to the cathode, and the soil free Cu²⁺ ions were mainly accumulated in the sections close to the cathode. The results of regression analyses revealed that both the soil Cu speciation in solution phase and the Cu fractionations in solid phase could play important roles in the changes of the soil microbial and enzyme activities. Our findings suggest that the bioavailability of soil heavy metals and their ecotoxicological effects on the soil biota before and after electroremediation can be better understood in terms of their chemical speciation and fractionations.     

The effects of soil amendments on heavy metal bioavailability in two contaminated Mediterranean soils

Two heavy metal contaminated calcareous soils from the Mediterranean region of Spain were studied. One soil, from the province of Murcia, was characterised by very high total levels of Pb (1572 mg kg(-1)) and Zn (2602 mg kg(-1)), whilst the second, from Valencia, had elevated concentrations of Cu (72 mg kg(-1)) and Pb (190 mg kg(-1)). The effects of two contrasting organic amendments (fresh manure and mature compost) and the chelate ethylenediaminetetraacetic acid (EDTA) on soil fractionation of Cu, Fe, Mn, Pb and Zn, their uptake by plants and plant growth were determined. For Murcia soil, Brassica juncea (L.) Czern. was grown first, followed by radish (Raphanus sativus L.). For Valencia soil, Beta maritima L. was followed by radish. Bioavailability of metals was expressed in terms of concentrations extractable with 0.1 M CaCl2 or diethylenetriaminepentaacetic acid (DTPA). In the Murcia soil, heavy metal bioavailability was decreased more greatly by manure than by the highly-humified compost. EDTA (2 mmol kg(-1) soil) had only a limited effect on metal uptake by plants. The metal-solubilising effect of EDTA was shorter-lived in the less contaminated, more highly calcareous Valencia soil. When correlation coefficients were calculated for plant tissue and bioavailable metals, the clearest relationships were for Beta maritima and radish.     

电动修复过程中电极逼近对土壤砷迁移与形态转化的影响

以高浓度砷污染土壤为修复对象,探究电极逼近法耦合捕集室对砷污染土壤的修复效果。实验设置4个处理,分别为固定电极 (FE-EK) 、阴极逼近 (AC-EK) 、阳极逼近 (AA-EK) 和两极逼近 (AAC-EK) 。结果表明,AC-EK、AA-EK以及AAC-EK对总砷[As(T)]的迁移具有促进作用,表现为捕集室中As(T)质量分数与初始值相比显著升高 (p<0.05) ,而FE-EK捕集室中As(T)质量分数与初始值相比无显著性差异 (p>0.05) ,As(T)整体迁移率以AAC-EK最高 (31.50%) ,FE-EK最低 (15.38%) 。由于土壤整体氧化还原电位升高,使得FE-EK、AC-EK、AA-EK、AAC-EK处理组三价砷平均质量分数较初始值分别降低9.78%、7.81%、13.65%、4.09%。砷的生物有效性在Fe₂O₃和电动效应的联合作用下不断降低,表现为可交换态砷、铝结合态砷、钙结合态砷向铁结合态砷、残渣态砷转化。本研究结果表明,AAC-EK促进As(T)迁移的效果最好,可交换态砷占比最低,且单位修复能耗最低,具有良好的砷污染土壤修复潜力。     

工业污染场地土壤中汞的化学形态及其环境限值探讨

汞是中国工业污染场地土壤中常见的重金属污染物,汞的常见形态包括单质汞、无机汞和甲基汞。比较了不同形态的汞及其化合物在物化性质、环境行为、毒性效应及致毒机制上的差异,还以美国、英国为例,探讨了针对不同形态的汞分别制定土壤环境限值的方法。最后指出,中国现有的土壤环境质量相关标准以及污染场地风险评估导则中均尚未区分汞的形态,仅给出总汞含量的限值。因此,在未来的相关标准制定中,应考虑按汞的各种形态制定不同的标准,这将更有利于客观准确评价工业污染场地土壤中汞的污染程度和环境风险。