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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

基于地统计条件模拟的土壤重金属污染范围预测方法研究

常用的空间插值模型在土壤污染范围预测时存在平滑效应,导致高值区被平滑和低值区被高估,在划定污染区范围时也往往忽视了插值结果存在的偏差。以某土壤重金属污染区域为例,利用地统计条件模拟方法预测土壤中Cu、Pb的空间分布,在多次模拟结果的基础上估算污染概率,基于概率阈值确定污染区范围。研究结果表明,地统计条件模拟方法获得的土壤Cu、Pb模拟结果统计特征与调查样点的统计特征基本一致,且空间分布格局也相似。基于污染概率的污染区范围确定方法可以定量评估污染区范围预测的不确定性,对提高土壤污染治理效果与科学制定环境管理决策具有重要意义。     

Effects of sewage sludge biochar on plant metal availability after application to a Mediterranean soil

Pyrolytic conversion of sewage sludge into biochar could be a sustainable management option for Mediterranean agricultural soils. The aim of this work is to evaluate the effects of biochar from sewage sludge pyrolysis on soil properties; heavy metals solubility and bioavailability in a Mediterranean agricultural soil and compared with those of raw sewage sludge. Biochar (B) was prepared by pyrolysis of selected sewage sludge (SL) at 500 °C. The pyrolysis process decreased the plant-available of Cu, Ni, Zn and Pb, the mobile forms of Cu, Ni, Zn, Cd and Pb and also the risk of leaching of Cu, Ni, Zn and Cd. A selected Mediterranean soil was amended with SL and B at two different rates in mass: 4% and 8%. The incubation experiment (200 d) was conducted in order to study carbon mineralization and trace metal solubility and bioavailability of these treatments. Both types of amendments increased soil respiration with respect to the control soil. The increase was lower in the case of B than when SL was directly added. Metals mobility was studied in soil after the incubation and it can be established that the risk of leaching of Cu, Ni and Zn were lower in the soil treated with biochar that in sewage sludge treatment. Biochar amended samples also reduced plant availability of Ni, Zn, Cd and Pb when compared to sewage sludge amended samples.     

Remediation of soil contaminated with pyrene using ground nanoscale zero-valent iron

The sites contaminated with recalcitrant polycyclic aromatic hydrocarbons (PAHs) are serious environmental problems ubiquitously. Some PAHs have proven to be carcinogenic and hazardous. Therefore, the innovative PAH in situ remediation technologies have to be developed instantaneously. Recently, the nanoscale zero-valent iron (ZVI) particles have been successfully applied for dechlorination of organic pollutants in water, yet little research has investigated for the soil remediation so far. The objective in this work was to take advantage of nanoscale ZVI particles to remove PAHs in soil. The experimental factors such as reaction time, particle diameter and iron dosage and surface area were considered and optimized. From the results, both microscale and nanoscale ZVI were capable to remove the target compound. The higher removal efficiencies of nanoscale ZVI particles were obtained because the specific surface areas were about several dozens larger than that of commercially microscale ZVI particles. The optimal parameters were observed as 0.2 g iron/2 mL water in 60 min and 150 rpm by nanoscale ZVI. Additionally, the results proved that nanoscale ZVI particles are a promising technology for soil remediation and are encouraged in the near future environmental applications. Additionally, the empirical equation developed for pyrene removal efficiency provided the good explanation of reaction behavior. Ultimately, the calculated values by this equation were in a good agreement with the experimental data.     

Mobility of arsenic, cadmium and zinc in a multi-element contaminated soil profile assessed by in-situ soil pore water sampling, column leaching and sequential extraction

Three methods for predicting element mobility in soils have been applied to an iron-rich soil, contaminated with arsenic, cadmium and zinc. Soils were collected from 0 to 30 cm, 30 to 70 cm and 70 to 100 cm depths in the field and soil pore water was collected at different depths from an adjacent 100 cm deep trench. Sequential extraction and a column leaching test in the laboratory were compared to element concentrations in pore water sampled directly from the field. Arsenic showed low extractability, low leachability and occurred at low concentrations in pore water samples. Cadmium and zinc were more labile and present in higher concentrations in pore water, increasing with soil depth. Pore water sampling gave the best indication of short term element mobility when field conditions were taken into account, but further extraction and leaching procedures produced a fuller picture of element dynamics, revealing highly labile Cd deep in the soil profile.