污染土壤的微波辐照技术研究进展

简要介绍了土壤污染的状况,总结了国外学者对重金属和有机物两大类污染土壤所进行的微波修复工作,探讨了修复机理及影响因素,最后展望了微波修复污染土壤的研究重点.     

Remediation of toxic metal contaminated soil by washing with biodegradable aminopolycarboxylate chelants

Ex situ soil washing with synthetic extractants such as, aminopolycarboxylate chelants (APCs) is a viable treatment alternative for metal-contaminated site remediation. EDTA and its homologs are widely used among the APCs in the ex situ soil washing processes. These APCs are merely biodegradable and highly persistent in the aquatic environments leading to the post-use toxic effects. Therefore, an increasing interest is focused on the development and use of the eco-friendly APCs having better biodegradability and less environmental toxicity. The paper deals with the results from the lab-scale washing treatments of a real sample of metal-contaminated soil for the removal of the ecotoxic metal ions (Cd, Cu, Ni, Pb, and Zn) using five biodegradable APCs, namely [S,S]-ethylenediaminedisuccinic acid, imminodisuccinic acid, methylglycinediacetic acid, DL-2-(2-carboxymethyl) nitrilotriacetic acid (GLDA), and 3-hydroxy-2,2′-iminodisuccinic acid. The performance of those biodegradable APCs was evaluated for their interaction with the soil mineral constituents in terms of the solution pH and metal-chelant stability constants, and compared with that of EDTA. Speciation calculations were performed to identify the optimal conditions for the washing process in terms of the metal-chelant interactions as well as to understand the selectivity in the separation ability of the biodegradable chelants towards the metal ions. A linear relationship between the metal extraction capacity of the individual chelants towards each of the metal ions from the soil matrix and metal-chelant conditional stability constants for a solution pH greater than 6 was observed. Additional considerations were derived from the behavior of the major potentially interfering cations (Al, Ca, Fe, Mg, and Mn), and it was hypothesized that use of an excess of chelant may minimize the possible competition effects during the single-step washing treatments. Sequential extraction procedure was used to determine the metal distribution in the soil before and after the extractive decontamination using biodegradable APCs, and the capability of the APCs in removing the metal ions even from the theoretically immobilized fraction of the contaminated soil was observed. GLDA appeared to possess the greatest potential to decontaminate the soil through ex situ washing treatment compared to the other biodegradable chelants used in the study.     

Comparison of EDTA-enhanced phytoextraction and phytostabilisation strategies with Lolium perenne on a heavy metal contaminated soil

Phytoremediation is a promising and cost-effective strategy to manage heavy metal polluted sites. In this experiment, we compared simultaneously phytoextraction and phytostabilisation techniques on a Cd and Zn contaminated soil, through monitoring of plant accumulation and leaching. Lolium perenne plants were cultivated for 2 months under controlled environmental conditions in a 27.6 dm³-pot experiment allowing the collect of leachates. The heavy metal phytoextraction was promoted by adding Na-EDTA (0.5 g kg⁻¹ of soil) in watering solution. Phytostabilisation was assessed by mixing soil with steel shots (1%) before L. perenne sowing. Presence of plants exacerbated heavy metal leaching, by improving soil hydraulic conductivity. Use of EDTA for phytoextraction led to higher concentration of heavy metal in shoots. However, this higher heavy metal extraction was insufficient to satisfactory reduce the heavy metal content in soil, and led to important heavy metal leaching induced by EDTA. On the other hand, addition of steel shots efficiently decreased both Cd and Zn mobility, according to 0.01 M CaCl₂ extraction, and leaching. However, improvement of growth conditions by steel shots led to higher heavy metal mass in shoot tissues. Therefore, soil heavy metal mobility and plant metal uptake are not systematically positively correlated.     

Measurements of Cd, Cu, Pb and Zn in the lower reaches of major Eurasian arctic rivers using trace metal clean techniques

Concentrations of dissolved and particulate Cd, Cu, Pb and Zn were determined in samples collected in summer 1998 from the lower reaches of six major Eurasian arctic rivers: the Onega, Severnaya Dvina, Mezen, Pechora, Ob and Yenisey. These data comprise some of the earliest measurements of trace metals in Eurasian arctic rivers above the estuaries using recognized clean techniques. Significant (α = 0.05) differences were observed among mean concentrations of particulate metals in the individual rivers (F ≤ 0.006), with highest levels overall observed in the Severnaya Dvina and Yenisey. No significant differences were observed among mean concentrations of dissolved metals in the individual rivers (F = 0.10-0.84). Contributions from anthropogenic sources are suggested by comparison of trace metal ratios in the samples to crustal abundances. These results establish a baseline for assessing future responses of Eurasian arctic river systems to climate-related environmental changes and shifting patterns of pollutant discharge.     

Monitoring heavy metal concentrations in leachates from a forest soil subjected to repeated applications of sewage sludge

The aim of the study was to establish whether the repeated application of sewage sludge to an acid forest soil (Dystric Cambisol) would lead to short-term groundwater contamination. Sludge was applied at four loading rates (0, 2.4, 17 and 60 Mg ha⁻¹) in two consecutive years and leachates were analysed. Heavy metal inputs to soils at the lowest dose were below EC regulations but, at higher doses, limits for Zn, Cd, Cr and Ni were exceeded. Repeated application of sludge at 60 Mg ha⁻¹ resulted in significantly (P < 0.05) higher concentrations of Zn, Cd, Cr and Ni in the leachates than with other treatments. The drinking water standards for Cd and Ni were surpassed in all treatments. Control plots were contaminated by groundwater flow despite the existence of buffer zones between plots. This complicated interpretation of the results, highlighting the importance of careful design of this type of experiment.     

环境友好型淋洗剂对重金属污染土壤的修复效果

以广西某废弃铅锌冶炼企业重金属复合污染土壤为对象,采用土柱淋洗的方法,分别将自制的茶皂素、柠檬酸和EDTA 3种淋洗剂进行复合淋洗,并对复合淋洗的最佳配比、淋洗剂添加方式和淋洗时间进行研究,得到对环境友好且淋洗效果好的复合淋洗剂。最后,对淋洗前后土壤中Cu、Pb和Zn的赋存形态进行研究,探讨淋洗机理。研究结果表明,茶皂素和柠檬酸复合时对重金属Cu、Pb、Zn的去除率分别达到了77.00%、52.09%和58.66%,综合考虑淋洗效率以及经济环保等因素,选择将茶皂素和柠檬酸复合进行淋洗。复合淋洗实验结果表明,柠檬酸和茶皂素体积比为3：1复合方式淋洗30 h,淋洗效果最佳,对重金属Cu、Pb和Zn的去除率分别达到82.77%、65.49%和78.12%。茶皂素和柠檬酸复合淋洗能有效的去除土壤中酸可提取态和有机结合态的重金属,氧化物结合态的Pb和Zn也有较大程度的降低,同时还发现,茶皂素和柠檬酸共同作用对残余态的Pb去除效果也较好,可达到50%以上。从茶籽饼中提取茶皂素与天然有机酸柠檬酸复合淋洗,用于修复污染面积小、污染浓度高且污染比较集中的重金属污染土壤,效果好且对环境友好。     

超声强化EDDS/EGTA淋洗修复重金属污染土壤

采用响应面法中的Box-Behnken实验设计,研究了超声强化N,N'-乙二胺二琥珀酸(EDDS)和乙二醇双(2-氨基乙基醚)四乙酸(EGTA)复合淋洗对土壤中Cu、Zn、Pb 和Cd 等4种重金属的去除效果,拟合了各重金属去除率、潜在生态风险指数削减率与EDDS投加量、EGTA投加量、超声功率和初始pH等淋洗条件之间的关系,模拟值与观测值相关性高,模拟精度较高。EGTA在较广pH范围对高生理毒性的Cd具有较强的洗脱效果,酸性条件下可有效洗脱Zn;Cu去除率在酸性条件下随着EDDS投加量的增加而显著提高,Pb去除率则在碱性条件随着EDDS投加量的增加而显著提高。基于模型优化结果的验证实验显示,当EDDS/重金属摩尔质量比为0.81、EGTA/重金属摩尔质量比为3.92、超声功率为569.85 W、pH为3.95时,潜在生态风险指数削减率最大,达到86.05%,Cu、Zn、Pb和Cd去除率分别为72.48%、62.40%、59.25%和87.45%,与模型拟合结果偏差较小,表明模型具有较好的拟合和预测能力。     

观赏植物与驯化污泥联合修复垃圾渗滤液污染土壤

垃圾填埋场渗滤液污染土壤具有重金属-有机物复合污染的特性。研究了观赏植物广东万年青、白掌、孔雀竹芋和经垃圾渗滤液驯化的污泥对该污染土壤的修复效果,结果表明：采用单一植物修复时,广东万年青较白掌和孔雀竹芋对土壤污染物具有更强耐性,能在污染土壤中生长良好,对重金属Cd和Pb的富集能力也更强;驯化污泥能明显提高污染土壤中有机污染物的降解率,并使重金属Cd和Pb稳定态比例分别提高了34.7%和36.6%,降低了重金属的生物有效性。当采用广东万年青和驯化污泥联合修复时,污泥能促进植物的生长,且当污泥添加量为480 mg·kg-1时,联合修复对土壤中Cd、Pb及有机污染物的去除率分别较不加污泥的对照提高了51.7%、25.5%和40.2%。     

Metal fractionation in a contaminated soil after reforestation: Temporal changes versus spatial variability

In a lysimeter experiment, topsoils were polluted with filter dust from a non-ferrous metal smelter and then planted with trees. Sequential extractions were used to follow the changes in metal fractionation of Cu, Zn, Cd, and Pb over 42 months. Plant-free and uncontaminated soils served as reference. In the contaminated and planted soils, the largest changes in speciation occurred within the first 6 months. The relative amounts of certain metal fractions were linearly related to each other, indicating systematic redistribution between fractions. The results indicate that under natural conditions with high heterogeneity in total metal contents spatial differences are more important than temporal variations in determining the fractionation and solubility of metals in contaminated soils. In the absence of plants soils exhibited a completely different fractionation 30 months after pollution, with much higher proportions in the more refractory phases. This suggests that plant activity kept the metals in a more soluble form.     

Trace element mobility in a contaminated soil two years after field-amendment with a greenwaste compost mulch

Application of greenwaste compost to brownfield land is increasingly common in soil and landscape restoration. Previous studies have demonstrated both beneficial and detrimental effects of this material on trace element mobility. A pot experiment with homogenised soil/compost investigated distribution and mobility of trace elements, two years after application of greenwaste compost mulch to shallow soils overlying a former alkali-works contaminated with Pb, Cu and As (∼900, 200 and 500 mg kg⁻¹, respectively). Compost mulch increased organic carbon and Fe in soil pore water, which in turn increased As and Sb mobilization; this enhanced uptake by lettuce and sunflower. A very small proportion of the total soil trace element pool was in readily-exchangeable form (<0.01% As, <0.001% other trace elements), but the effect of compost on behaviour of metals was variable and ambiguous. It is concluded that greenwaste compost should be applied with caution to multi-element contaminated soils.     

Study of the chemistry of an acid soil column and of the corresponding leachates after the addition of an anaerobic municipal sludge

A column leaching study was carried out over a period of 77 days to determine the changes in the chemistry of an acid soil and of the corresponding leachates after the addition of an anaerobic sludge (equivalent to 69 Mg DW ha⁻¹). By the end of the experiment, the addition of the sludge to the soil had induced an increase in soil pH (from pH 3.6–4.0 to pH 4.1–4.8), in spite of the pronounced decrease in pH detected in the leachates by day 18 of the experiment. The decrease in pH (down to pH 3.3) occurred at the same time as leachate SO₄ and Fe peaked. Once the acidification attributed to sulphide oxidation ceased, the “liming effect” of the sludge became evident and counteracted further proton production – such as that associated with oxidation of NH₄ – at least for the duration of the study. Concentrations of Zn, Cd, Ni, and to a lesser extent, Pb in leachates displayed pulses at the beginning of the experiment (first 12 days), whereas the concentration of Cu followed a more irregular pattern; the concentrations of these metals never surpassed the European threshold values for drinking water. In contrast, concentrations of NO₃, Mn, and Cr in leachates had increased by the end of the experiment – in parallel with an increase in dissolved organic C (DOC) – and surpassed the European threshold for drinking water. Mineralisation of native soil organic C (SOC) was enhanced by the addition of this N-rich residue, and the organic C mass balance at the end of the experiment was negative. Nitrogen mass balance, although positive, exhibited a loss of 77% of the N added to the system. The results obtained indicate that application of this sewage sludge to a soil with a pH < 5, at the loading rate used here, and without liming (i.e., non fulfilment of the requirements of the present European Directive) may pose a risk in terms of groundwater contamination.     

Body metal concentrations and glycogen reserves in earthworms (Dendrobaena octaedra) from contaminated and uncontaminated forest soil

Stress originating from toxicants such as heavy metals can induce compensatory changes in the energy metabolism of organisms due to increased energy expenses associated with detoxification and excretion processes. These energy expenses may be reflected in the available energy reserves such as glycogen. In a field study the earthworm, Dendrobaena octaedra, was collected from polluted areas, and from unpolluted reference areas. If present in the environment, cadmium, lead and copper accumulated to high concentrations in D. octaedra. In contrast, other toxic metals such as aluminium, nickel and zinc appeared to be regulated and kept at low internal concentrations compared to soil concentrations. Lead, cadmium and copper accumulation did not correlate with glycogen reserves of individual worms. In contrast, aluminium, nickel and zinc were negatively correlated with glycogen reserves. These results suggest that coping with different metals in earthworms is associated with differential energy demands depending on the associated detoxification strategy.     

Remediation of metal polluted mine soil with compost: co-composting versus incorporation

Trace element contamination of post-industrial sites represents a major environmental problem and sustainable management options for remediating them are required. This study compared two strategies for immobilizing trace elements (Cu, Pb, Zn, and As) in mine spoil: (1) co-composting contaminated soil with organic wastes and (2) conventional incorporation of mature compost into contaminated soil. Sequential chemical extraction of the soil was performed to determine temporal changes in trace element fractionation and bioavailability during composting and plant growth. We show that mine spoil can be co-composted successfully and this action causes significant shifts in metal availability. However, co-composting did not lead to significant differences in metal partitioning in soil or in plant metal uptake compared with simply mixing mine spoil with mature compost. Both treatments promoted plant growth and reduced metal accumulation in plants. We conclude that co-composting provides little additional benefit for remediating trace-element-polluted soil compared with incorporation of compost.     

The effect of environmental conditions on the stability of heavy metal-filter material complex as assessed by the leaching of adsorbed metal ions

In this study the influence of environmental conditions, most likely prevailing in filter beds used for intermittently discharged pollutant streams such as landfill leachate and storm water, on the stability of the heavy metal-filter complex was investigated for 2 filter materials; non-treated and urea treated pine bark, using leaching experiments. The metal-filter complex stability was higher for urea treated than for non-treated pine bark and dependent on the metal adsorbed. The type of environmental condition applied was of less importance for the extent of leaching.     

Mitigation effects of silicon rich amendments on heavy metal accumulation in rice (Oryza sativa L.) planted on multi-metal contaminated acidic soil

The mechanisms of stabilization by silicon-rich amendments of cadmium, zinc, copper and lead in a multi-metal contaminated acidic soil and the mitigation of metal accumulation in rice were investigated in this study. The results from a pot experiment indicated that the application of fly ash (20 and 40 g kg⁻¹) and steel slag (3 and 6 g kg⁻¹) increased soil pH from 4.0 to 5.0-6.4, decreased the phytoavailability of heavy metals by at least 60%, and further suppressed metal uptake by rice. Diffusion gradient in thin-film measurement showed the heavy metal diffusion fluxes from soil to solution decreased by greater than 84% after remediation. X-ray diffraction analysis indicated the mobile metals were mainly deposited as their silicates, phosphates and hydroxides in amended treatments. Moreover, it was found metal translocation from stem to leaf was dramatically restrained by adding amendments, which might be due to the increase of silicon concentration and co-precipitation with heavy metals in stem. Finally, a field experiment showed the trace element concentrations in polished rice treated with amendments complied with the food safety standards of China. These results demonstrated fly ash and steel slag could be effective in mitigating heavy metal accumulation in rice grown on multi-metal contaminated acidic soils.     

Exposure of an anoxic and contaminated canal sediment: Mobility of metal(loid)s

A derelict canal contains an estimated 9800 tonnes of anoxic sediment with highly elevated concentrations of trace elements. Lack of maintenance, reduced water levels and vegetation colonization threaten the stability of pollutants by removing existing waterlogged reduced conditions. A column leaching study of the sediment under increasingly oxidized conditions showed reductions in As mobility but increased heavy metal concentrations. In a reduced state, As mobility was higher (as a consequence of enhanced Fe and organic carbon solubility) whilst heavy metal concentrations in leachates were lower (due to markedly higher pH). Over 10 contiguous wetting and drying cycles, the consequences were profound; all trace elements were continuously leached with enhanced flushing of Fe, As, Zn and Cu. This raises concern over possible mobilization of pollutants to the wider environment, including groundwater. Options for management to stabilize contaminants are discussed that point to the importance of limiting water flow through the sediment.     

不同化学淋洗剂对复合重金属污染土壤的修复机理

化学淋洗技术是一种常用的重金属污染土壤修复技术,化学淋洗剂的选择尤为重要。以乙二胺四乙酸二钠（EDTA）、柠檬酸（CA）和三氯化铁（FeCl3）为化学淋洗剂,采用振荡淋洗法研究淋洗时间与淋洗剂浓度对Cu、Zn、Pb和Cd去除效果的影响,分析重金属污染土壤淋洗前后重金属形态与基本理化性质的变化。结果表明：3种化学淋洗剂对重金属的快速反应阶段基本在60 min内,在240 min达到淋洗平衡,对Pb和Cd的淋洗主要是非均相扩散过程;EDTA、柠檬酸和FeCl3对重金属的去除能力依次为Pb>Cd>Cu>Zn,Cd>Zn>Cu>Pb与Pb≈Cd>Cu>Zn,EDTA的淋洗效率最高,Cd的解吸能力最强;EDTA和FeCl3可有效去除弱酸可溶态与可还原态重金属,柠檬酸能有效去除弱酸可溶态重金属,修复后的土壤仍有环境风险;3种淋洗剂修复后的土壤中总有机碳与粒径分布无明显变化,FeCl3会酸化土壤。综合考虑,EDTA、柠檬酸和FeCl3均为淋洗效果好的环境友好型化学淋洗剂,该研究成果可用于现场淋洗去除土壤中重金属的小试。     

Concentration of trace elements in feathers of three Antarctic penguins: Geographical and interspecific differences

Antarctica is often considered as one of the last pristine regions, but it could be affected by pollution at global and local scale. Concentrations of Al, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Cd and Pb were determinated by ICP-MS in feathers (n = 207 individuals) of gentoo, chinstrap and Adélie penguin collected in 8 locations throughout the Antarctic Peninsula (2006-2007). The highest levels of several elements were found in samples from King George Island (8.08, 20.29 and 1.76 μg g⁻¹ dw for Cr, Cu and Pb, respectively) and Deception Island (203.13, 3.26 and 164.26 μg g⁻¹ dw for Al, Mn and Fe, respectively), where probably human activities and large-scale transport of pollutants contribute to increase metal levels. Concentrations of Cr, Mn, Cu, Se or Pb, which are similar to others found in different regions of the world, show that some areas in Antarctica are not utterly pristine.     

Electro-migration of heavy metals in an aged electroplating contaminated soil affected by the coexisting hexavalent chromium

Cr(VI) was often reported to oxidize soil organic matter at acidic environments due to its high ORP, probably thus changing cationic metal species bound to soil organic matter, and influencing their electro-migration patterns. However, such an effect on the electro-migration was not confirmed in most previous studies. Therefore, this study applied a fixed voltage direct current field on an aged electroplating contaminated clayed soil, with a special interest in the direct or indirect influence of Cr(VI) on the electro-migration of other coexisting metals. After 353 h electrokinetic process, 81% of Zn, 53% of Ni and 22% of Cu in the original soil were electro-migrated into the electrolyte, and most of the remaining concentrated near the cathode. The Cr(VI) oxidized some soil organic matter along its migration pathway, with a pronounced reaction occurred near the anode at low pHs. The resulting Cr(III) reversed its original movement, and migrated towards the cathode, leading to the occurrence of a second Cr concentration peak in the soil. Metal species analyses showed that the amount of metals bound to soil organic matter significantly decreased, while a substantial increase in the Cr species bound to Fe/Mn (hydro-)oxides was observed, suggesting an enhancement of cationic metal electro-migration by the reduction of Cr(VI) into Cr(III). However, the Cr(VI) may form some stable lead chromate precipitates, and in turn demobilize Pb in the soil, as the results showed a low Pb removal and an increase in its acid-extractable and residual fractions after electrokinetic remediation.     

Remediation of soil contaminated with dioxins by subcritical water extraction

The effectiveness of subcritical water extraction (SCWE) was examined for removing dioxins from contaminated soil. Most dioxins in the soil sample were reduced at 300 degrees C or more, but decreased dioxin concentrations were also observed at 150 degrees C. After 4 h of extraction, 99.4%, 94.5% and 60% of PCDDs were removed from samples at 350, 300 and 150 degrees C, respectively. It was also determined that degradation of dioxins had occurred, since the sum of dioxins in the soil plus water extracts after the experiments had considerably decreased. This study revealed that pressurizing is not essential for the removal of dioxins. Reduction was complete within 30 min at 350 degrees C; however, it took a much longer time at lower temperatures. The results of addition experiments in which OCDDs were added to different types of soil samples have shown that dechlorination is one of the major reaction pathways. After addition of OCDD to soil samples, experiments were carried out to examine in detail the degradation pathways of PCDDs. The removal rates and congener profiles varied among soil types. Although it was previously assumed that removal rates and congener profiles depended on the chemical components in soil, nonparametric statistical analysis revealed no significant relationship between the rate of reduction and elements present in the soil. It was confirmed from isomer patterns that dechlorination of the 2,3,7,8-positions in PCDDs takes place somewhat faster than for the 1,4,6,9-positions.