有机酸与表面活性剂联合作用对土壤重金属的浸提效果研究

重金属污染土壤的原位淋洗修复既要实现对重金属的高效去除,还要尽量减少对土壤性质的破坏,这一点在农业污染土壤修复中尤为重要。以张士污灌区农田土壤为研究对象,利用振荡浸提技术筛选有机酸和表面活性剂组合,并确定了两者联合淋洗修复污染土壤的最佳配比。结果表明:有机酸(酒石酸、乙酸、柠檬酸和苹果酸)中的酒石酸浓度为0.5 mol.L-1和表面活性剂(SDBS、鼠李糖和皂素)中的皂素质量分数为0.7%时对土壤Cd、Pb、Zn的浸提效果较好;在酒石酸与皂素体积配比为1∶1时,对重金属Cd、Pb、Zn浸提效果最好,浸提率分别为87.62%、36.30%、20.67%;单一有机酸、表面活性剂或者有机酸与表面活性剂的混合溶液,对土壤重金属的浸提效果均为Cd>Pb>Zn。虽然有机酸与表面活性剂联合浸提效果略低于酒石酸浸提,但其弱酸性对土壤性质影响较小,在原位淋洗修复工程中有较好的应用前景。     

表面活性剂对土壤中重金属清洗及有效态的影响

采用两种常用的表面活性剂-十二烷基苯磺酸钠(阴离子型)、Tween-80(非离子型),对锦州铁合金厂周边Zn、Cd及Pb重金属污染土壤进行化学修复试验,研究两种表面活性剂对重金属Zn、Cd及Pb的去除率及化学形态影响.结果表明,随着表面活性剂浓度的提高,两种表面活性剂对Pb、Cd及Zn的去除作用增强,Tween-80溶液的浓度越高,对重金属的萃取效果越好,对重金属的去除能力大小顺序为Cd>Zn>Pb,最大去除率分别为83.07%、56.78%及42.57%;十二烷基苯磺酸钠在低浓度时对Cd和Pb的去除效果不明显,而对金属Zn的去除效果较好,在0.09 mol.L-1时达到最大值83.86%;与淋溶前土壤中重金属有效态含量相比较,经不同浓度十二烷基苯磺酸钠淋洗后土壤中Cd有效态含量随LAS浓度的升高而先增加后下降,而Pb的有效态含量随十二烷基苯磺酸钠升高而增加;经不同浓度Tween-80淋洗后土壤中Zn及Cd有效态含量都是随Tween-80浓度的升高而先增加后下降,Pb有效态含量随Tween-80升高而下降.     

螯合剂和表面活性剂辅助金福菇修复重金属污染土壤

通过温室大棚盆栽试验,研究螯合剂和表面活性剂单独或复合处理辅助金福菇修复重金属污染土壤的效果.结果表明,单独添加EDTA(乙二胺四乙酸)时,高浓度的EDTA(E2,5 mmol kg-1)使金福菇的生物量比对照降低26%,子实体Pb、Cu和Cd的浓度分别比对照提高15～88倍、0.8～3.3倍和0.5～0.6倍.单独添加表面活性剂时,各处理生物量与对照没有显著差异,且重金属浓度变化幅度没有单独添加EDTA的处理大.低浓度的表面活性剂对金福菇吸收各种重金属的影响较小,而高浓度则影响较大,但与表面活性剂及重金属种类有关.共同添加EDTA和表面活性剂时,只有当EDTA和CTAB(溴化十六烷基三甲铵)共同添加时,EC2(EDTA:CTAB=1:1)和EC3(EDTA:CTAB=2:1)的生物量显著降低,其余处理与对照差异不明显.EC3的子实体Pb和Cu浓度达到所有处理中的最大值,分别为(1 533.61±131.34)、(1 786.11±328.33)mg kg-1.EDTA和SDS(十二烷基磺酸钠)浓度比为2:1(ES3)时,子实体Cd浓度达到最大值,为(50.56±11.55)mg kg-1.此外,还分析了不同处理的重金属总积累量和富集系数.结果显示,在螯合剂和表面活性剂辅助下,金福菇修复复合重金属污染土壤具有很大的潜能.     

三种表面活性剂对高浓度DDTs污染土壤的洗脱作用

以高浓度滴滴涕(DDTs)污染场地土壤为研究对象,采用表面活性剂洗脱试验,比较研究了聚氧乙烯山梨糖醇酐单硬脂酸酯(Tween60)、辛基酚聚氧乙烯醚(TritonX 100)、十二烷基硫酸钠(SDS)对污染土壤中DDTs的洗脱效率.试验结果表明,三种表面活性剂对污染土壤中DDTs均具有一定的洗脱作用,去离子水对DDTs几乎没有洗脱效果.随着洗脱液中Tween60和SDS质量浓度的逐渐升高,土壤中DDTs的总洗脱效率逐渐增大,一次性洗脱时最大洗脱效率分别为43.60%和34.62%.随着洗脱液中TritonX 100质量浓度的逐渐升高,土壤中DDTs的总洗脱效率出现先增大后降低再升高的变化现象,最大为15.46%.土壤中六种DDT组分的洗脱效率不完全一样,其中Tween60对2,4'-DDD的洗脱效率可达55.12%,对4,4'-DDD的洗脱效率为54.09%;SDS对2,4'-DDD的洗脱效率为59.99%,对4,4'-DDD的洗脱效率为57.10%.试验结果可为筛选适宜的表面活性剂及质量浓度,研发高浓度DDTs污染场地土壤表面活性剂洗脱修复技术的工程应用提供理论依据.     

表面活性剂强化重金属污染植物修复的可行性

表面活性剂因具有亲水亲脂的两亲性，已被广泛用来治理环境污染。利用表面活性剂强化植物萃取土壤重金属的可行性，是建立在表面活性剂、重金属、土壤、植物等四者之问的关系基础上的。文章根据乳化液膜分离、胶团强化超滤、金属液泡吸收等技术探讨了表面活性剂与重金属的关系。表面活性剂在其浓度超过临界胶束浓度时，在溶液中形成胶团，通过静电吸附与超滤，去除溶液中的重金属。超滤技术与ξ电位的试验结果确定了表面活性剂与土壤的关系，即土壤界面的吸附和金属缔合后，通过降低表面张力和增流作用解吸被吸附的金属。细胞膜透性学说揭示了表面活性剂与植物的关系．即表面活性剂改变生物膜的结构和透性，促使植物对重金属的吸收。开发环境友好性的生物表面活性剂是该研究领域的前沿方向。     

一株黑曲霉的分离鉴定及其对土壤重金属的生物浸出效果

某些真菌可产生小分子有机酸,既具有酸化环境介质的功能,又具有络合重金属能力,因此可有效浸出环境介质(如土壤、底泥等)中的重金属.本研究从土壤中分离得到一株产酸能力较高的真菌,经形态学及ITS rDNA基因序列分析鉴定为黑曲霉,命名为Aspergillus niger Y9.测定了其生长特性,并采用摇瓶培养法探究其同步、分步培养法去除污染土壤中重金属的效果.结果显示,该菌适宜生长pH范围较广(3.0-8.0),对Zn2+、Cd2+、Pb2+的80%抑制浓度分别为250、130、2 700 mg/L.培养20 d后pH降至2.1,柠檬酸、葡萄糖酸、草酸和苹果酸的产量分别为54.8、20.1、15.9、6.3mmol/L.分步培养法污染土壤中重金属的浸出率最高为Zn 75%,Cd 100%,Pb 43%,略优于同步培养法(Zn 64%,Cd86%,Pb 19%).上述结果表明,Aspergillus niger Y9具有较强的重金属耐受性,能有效浸出土壤中的Zn、Cd、Pb,为后期采用该菌处理重金属污染土壤提供了技术参考.     

土壤有效Cd浸提剂对Cd的浸提机制

研究比较了六种浸提剂(1mol/l NH_4OAc,1mol/l NH_4NO_3,0.005mol/l DTPA-TEA,0.1mol/l HCl,0.1mol/l CaCl_2,0.1mol/l NaNO_3)在不同土壤条件下对土壤Cd的浸提规律。从浸提剂的特性及pH缓冲能力等角度讨论了其对土壤Cd的浸提机制。结合盆栽试验中植株吸Cd量的相关分析表明,不同浸提剂均有其适合的土壤条件反映Cd的生物有效性,但相对地,0.1mol/l CaCl_2可能是适应性最广的土壤有效Cd浸提剂。     

生物表面活性剂及其在重金属污染生态修复中的应用

介绍了不同污染体系中重金属的存在形态,生物表面活性剂的种类、优点及生产方法。综述了几种典型的生物表面活性剂(鼠李糖脂、槐糖脂s、urfactin和皂角苷)及其在重金属污染生态修复中的应用。分析了生物表面活性剂去除重金属的作用机制,阐述了生物表面活性剂修复重金属污染的研究方向。     

非离子表面活性剂淋洗萘污染土壤的修复研究

采用土柱实验研究了非离子表面活性剂对焦化厂萘污染砂土的淋洗效果,同时研究了超声预处理对非离子表面活性剂土壤淋洗的增强效果及粉土和粘土对非离子表面活性剂土壤淋洗的不利影响.研究表明,1)1g·L-1的TritonX-100、AEO-9和Tween80对同一萘浓度(192.4mg·kg-1)的土壤洗脱效率分别为73.0%、81.5%和59.0%,2g·L-1的表面活性剂的洗脱效率要高于1g·L-1的洗脱率,分别为96.5%、95.1%和88.2%.2)对土壤进行短时超声处理(80Hz)促进了洗脱率的提高,超声10min的淋洗效果要高于超声5min的淋洗效果;土壤分别经5min和10min超声处理后,2g·L-1浓度的TritonX-100对萘的洗脱率从94%分别提高到98.8%和99.6%,洗脱时间从255min分别减少到172min和160min.3)砂土中含有粉土和粘土对洗脱效果有不利影响,且粘土的影响要更严重,当萘污染的砂土混入5%的粘土时,2g·L-1浓度的TritonX-100对萘的洗脱率从94.7%下降至73.8%,洗脱时间从255min增加至605min,而混入20%的粉土洗脱率仅下降到88.4%,洗脱时间增加至512min.     

3种表面活性剂对有机氯农药污染场地土壤的增效洗脱修复效应

以有机氯农药生产企业工业场地污染土壤为对象,研究Tween80、TritonX-100和SDS这3种表面活性剂对土壤中氯丹(α-氯丹和γ-氯丹)、灭蚁灵、七氯、硫丹(α-硫丹和β-硫丹)的增溶洗脱效应.结果表明,3种表面活性剂对土壤中的有机氯农药均具有一定的增效洗脱作用,且洗脱去除率随表面活性剂添加量升高而逐渐增加.3种表面活性剂对土壤中氯丹、硫丹和七氯的去除率明显高于灭蚁灵,TritonX-100对灭蚁灵的去除率明显高于SDS和Tween80.Tween80和TritonX-100添加量为10g·L-1、SDS添加量为8.50g·L-1时,对土壤中4类有机氯农药的总去除率最高,分别为32.8％、59.7％和60.1％.对于该类污染场地土壤,选择10g·L-1 TritonX-100溶液在50℃条件下振荡5min时洗脱效果最好.     

重金属污染土壤的微生物生态效应及其修复研究进展

污染土壤微生物生物修复技术是一项非常有应用前景的环保新技术。本文综述了近年来重金属对土壤微生物生物量、种群及生化过程的影响以及微生物对重金属污染土壤的修复机理和修复研究进展,较全面的分析了重金属对土壤微生物的生态效应。     

Sorption of heavy metals on organic and inorganic soil constituents

Sorption of heavy metals to organic matter and mineral soil constituents can hardly be separated experimentally. Here we studied the retention capacity of organic matter and minerals from soils in a long-term field experiment in which the organic carbon content had been altered, but the mineral phase had remained constant over time. The sorption of Cu, Cd and Zn showed a non-additive contribution of soil organic matter and minerals to the sorption capacity of soil. Sorption on organic matter exceeded mineral sorption from 6 to 13 times. This is the first time that sorption to soil organic matter is quantified in bulk soils.     

Effects of organic matter on the specific adsorption of heavy metals by soil

The adsorption of heavy metals on soil from the Neihu Landfill Site in Taipei City was investigated in order to assess the groundwater pollution problems. The effects of soil organic matter and the behaviors of organic complexing ligands like EDTA and humic acid to the overall adsorption process were studied and discussed. For explaining the results, the pH value of soil system and the properties of the soil/aqueous interface were chosen as two significant and interacted factors for discussion. The concept of the specific adsorption mechanism was also demonstrated and discussed. The results showed that the complexing ligands existing in soil liquid phase have more influences than natural organic matter does. The competitive sequences of different organic matter contents indicated that organic functional sites preferentially bind with Cu and Cd. The presence of EDTA and humic acid which formed ligandlike complexes will reduce Cd adsorption efficiency. These effects will induce mobility and the fate of heavy metals in soils, such as bioavailability.     

Response of roselle (Hibiscus sabdariffa) to heavy metals contamination in soils with different organic fertilisations

The response of green roselle (Hibiscus sabdariffa) to Cu/Pb contamination and manure application in soil was investigated using pot experiments. Subsamples of a mineral soil were treated with increasing doses (0–500 mg kg^?1) of Cu/Pb only and/or amended (at 10% w/w) with poultry or swine manure. Roselle plants were grown, monitored for changes in growth rate and post-harvest aboveground dry biomass and tissue Cu/Pb concentrations were determined. The plants were typically greenish with linear growth profiles at all metal doses, indicating some level of tolerance. Dry biomass yields decreased as metal dose increased. Poultry manure enhanced roselle biomass yields better than swine manure. Tissue Cu/Pb concentrations increased linearly as metal doses increased in unamended soils; whereas nonlinear responses were observed in manure-amended soils. Soil-to-plant transfer factors, T _f (%) indicated that Cu (13≤T _f (% )≤60) was more phytoavailable to roselle than Pb (11≤T _f (% )≤20). Tissue metal concentrations were modelled from soil pH, organic matter, plant available and pseudototal metal; but the models appeared more reliable with plant available metal as a covariate than with pseudototal metal content. These observations may become useful whenever phytoextraction is the remedial option for soils moderately contaminated by toxic metals.     

杨树、落叶松对土壤重金属的吸收及修复研究

在沈阳生态实验站开展了木本植物对土壤重金属的吸收积累及修复效应的研究,实验结果表明,重金属污染物已影响了杨树(Populus canadensis)的正常生长,Cd、Cu、Zn复合污染处理杨树总生物量比对照下降了26%。Cd、Cu、Zn处理杨树和落叶松重金属吸收量多于对照,杨树叶Cd、根Cu重金属吸收量分别比对照增加了2.09倍、2.2倍。落叶松(Larix koreana)根Cd、Cu、Zn的吸收量比对照分别增加了2.17、1.95和1.42倍。树木体内重金属元素迁移能力的大小分别为Cd>Zn>Cu,重金属吸收系数大小依次为杨树>落叶松,重金属在杨树体内的迁移能力及地上部吸收能力要大于落叶松。土壤一旦遭受重金属污染(Cd、Cu、Zn),通过木本植物杨树、落叶松修复净化的时间相当漫长。     

上海化学工业区土壤重金属元素形态分析

选取上海化学工业区土壤背景值样品，采用Tessier A连续提取法研究土壤中6种重金属元素的形态分布。研究结果表明，在该化工区土壤中，Cd主要以可交换态和铁锰氧化物结合态为主，分别占总量的41．5％和36．7％，说明元素Cd较活泼，具有潜在的环境影响能力，应该给予更多的关注；Cr、Cu、Ni和Zn等4种元素主要以有机结合态和残余态为主，两者分别占总量的41．4％、58．9％、31．4、32．5％和45．9％、31．5％、57．4％、52．3％；而Pb则主要以有机结合态形式存在，其占总量的87．8％；元素形态分析表明Cr、Cu、Ni、Zn和Pb这5种元素相对比较稳定。     

矿区周围土壤中重金属危害性评估研究

分别用总量法和连续萃取法对广东大宝山矿周围土壤、植物和沉积物中重金属的总量和化学形态进行了详细分析。结果发现，矿山废水流入的横石河沉积物中Pb、Zn、Cu和Cd的质量分数分别为1841．02、2326．28、1522．61和10.33mg／kg；经此河水灌溉的稻田中重金属(Cu、Cd、Pb和Zn)的质量分数也远远超出了土壤环境二级标准值，其中Cu、Cd超标倍数分别为14．01和4．17倍。结果还表明，生长在矿区周围的植物也受到不同程度重金属的污染且不同植物吸收和积累重金属的能力相差很大。用Tessier连续法对土壤中重金属进行萃取发现，虽然重金属主要存在于残余态中，但在Fe-Mn氧化态、有机结合态中的质量分数也很高．说明这些土壤确实受到了有毒有害重金属元素的严重污染。     

Chelator-induced bioextraction of heavy metals from artificially contaminated soil by mushroom (Coprinus comatus)

This study investigated the potential use of chelator-induced bioextraction of heavy metals from soil by Coprinus comatus in a pot experiment. Two production waves of the mushroom were obtained to determine biomass and metal concentration. The application of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetate (NTA) slightly inhibited the growth of C. comatus, but significantly enhanced the accumulation of heavy metals in fruiting bodies compared with the control. The highest concentrations of Pb, Cu and Cd reached 900.60, 783.61 and 23.64 mg·kg^?1 in a single pot, respectively. However, application of citric acid (CA) had no effect on metal uptake. Moreover, chelators applied to soil after fructification increased the dry biomass and metal concentration in fruiting bodies compared with those applied before sowing mycelia. EDTA was more efficient for inducing metal uptake by C. comatus than NTA or CA, and split applications of EDTA after fructification resulted in the highest total metal uptake by mushroom, i.e. 19.08±2.84, 17.57±0.69 and 0.55±0.06 mg for Pb, Cu and Cd, respectively, which were 130, 12 and 5 times values obtained with the control. Interestingly, many mushrooms turned blue after soil had been treated with chelator, indicating that these mushrooms are rich in Cu.