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。     

In situ fixation of metals in soils using bauxite residue: chemical assessment

Contamination of soils with heavy metals and metalloids is a widespread problem all over the world. Low cost, non-invasive, in situ technologies are required for remediation processes. We investigated the efficiency of a bauxite residue (red mud) to fix heavy metals in two soils, one contaminated by industrial activities (French soil), and one by sewage sludge applications (UK soil). This Fe-oxide rich material was compared with lime, or beringite, a modified aluminosilicate that has been used for in situ fixation processes. Four different crop species were successively grown in pots. Metal concentrations in the soil pore waters were analyzed during the growing cycles. At the end of the experiment fluxes of heavy metals were measured using a diffusive gradient in thin film technique (DGT). Furthermore, a sequential extraction procedure (SEP) and an acidification test were performed to investigate the mechanisms of metal fixation by different soil amendments. In both soils, the concentrations of metals in the soil pore water and metal fluxes were greatly decreased by the amendments. An application of 2% red mud performed as well as beringite applied at 5%. Increasing soil pH was a common mechanism of action for all the amendments. However, the red mud amendment shifted metals from the exchangeable to the Fe-oxide fraction, and decreased acid extractability of metals. The results suggest that specific chemisorption, and possibly metal diffusion into oxide particles could also be the mechanisms responsible for the fixation of metals by red mud.     

An inter-laboratory study to test the ability of amendments to reduce the availability of Cd, Pb, and Zn in situ

An international inter-laboratory research program investigated the effectiveness of in situ remediation of soils contaminated by cadmium, lead and zinc, measuring changes in soil and soil solution chemistry, plants and soil microbiota. A common soil, from mine wastes in Jasper County MO, was used. The soil was pH 5.9, had low organic matter (1.2 g kg(-1) C) and total Cd, Pb, and Zn concentrations of 92, 5022, and 18 532 mg kg(-1), respectively. Amendments included lime, phosphorus (P), red mud (RM), cyclonic ashes (CA), biosolids (BIO), and water treatment residuals (WTR). Both soil solution and NH4NO3 extractable metals were decreased by all treatments. Phytotoxicity of metals was reduced, with plants grown in P treatments having the highest yields and lowest metal concentration (0.5, 7.2 and 406 mg kg(-1) Cd, Pb, and Zn). Response of soil micro-organisms was similar to plant responses. Phosphorus addition reduced the physiologically based extraction test Pb from 84% of total Pb extracted in the untreated soil to 34.1%.     

In situ fixation of metals in soils using bauxite residue: biological effects

Soils polluted with heavy metals can cause phytotoxicity and exhibit impared microbial activities. In this paper we evaluate the responses of different biological endpoints to in situ remediation processes. Three soil amendments (red mud, beringite and lime) were applied to two soils polluted by heavy metals. Oilseed rape, wheat, pea and lettuce were grown successively in pots on the untreated and amended soils and their yield and metal uptake were determined. A suite of microbial tests (lux-marked biosensors, Biolog and soil microbial biomass) were performed to determine the effect of the soil amendments on the functionality and size of the soil microbial community. In both soils all three amendments reduced phytotoxicity of heavy metals, enhanced plant yields and decreased the metal concentrations in plants. The red mud treatment also increased soil microbial biomass significantly. The microbial biosensors responded positively to the remediation treatments in the industrially-contaminated soil used in the experiment. Red mud applied at 2% of soil weight was as effective as beringite applied at 5%. The results also showed that since the biological systems tested respond differently to the alleviation of metal toxicity, a suite of biological assays should be used to assess soil remediation processes.     

Migration of heavy metals in soil as influenced by compost amendments

Soils contaminated with heavy metals can pose a major risk to freshwaters and food chains. In this study, the success of organic and inorganic intervention strategies to alleviate toxicity in a highly acidic soil heavily contaminated with As, Cu, Pb, and Zn was evaluated over 112 d in a mesocosm trial. Amelioration of metal toxicity was assessed by measuring changes in soil solution chemistry, metal leaching, plant growth, and foliar metal accumulation. Either green waste- or MSW-derived composts increased plant yield and rooting depth, reduced plant metal uptake, and raised the pH and nutrient status of the soil. We conclude that composts are well suited for promoting the re-vegetation of contaminated sites; however, care must be taken to ensure that very short-term leaching pulses of heavy metals induced by compost amendment are not of sufficient magnitude to cause contamination of the wider environment.     

A remediation strategy based on active phytoremediation followed by natural attenuation in a soil contaminated by pyrite waste

Phytoremediation of metal-polluted soils can be promoted by the proper use of soil amendments and agricultural practices. A 4-year phytoremediation programme was applied to a site affected by the toxic spill of pyrite residue at Aznalcóllar (Spain) in 1998, contaminated with heavy metals (Zn, Cu, Pb, Cd) and arsenic. This consisted of active phytoremediation, using organic amendments (cow manure and compost) and lime and growing two successive crops of Brassica juncea (L.) Czern., followed by natural attenuation without further intervention. Changes in soil pH, extractable metal and As concentrations, organic carbon content and microbial biomass was evaluated. The initial oxidation of metal sulphides from pyrite residues released soluble metals and reduced soil pH to extremely acidic values (mean 4.1, range 2.0-7.0). The addition of lime (up to 64 t ha(-1)) increased soil pH to adequate values for plant growth, resulting in a significant decrease in DTPA-extractable metal concentrations in all plots. The natural attenuation phase showed also a decrease in extractable metals. Organic treatments increased the soil total organic carbon, which led to higher values of microbial biomass (11.6, 15.2 and 14.9 g kg(-1) TOC and 123, 170 and 275 microg g(-1) biomass-C in control, compost and manure plots, respectively). Active phytoremediation followed by natural attenuation, was effective for remediation of this pyrite-polluted soil.     

Vegetation establishment on a deposit of zinc mine wastes

Field trials concerning the establishment of plant cover on a deposit of wastes from the Ammeberg zinc mine in central Sweden were carried out during 1976-1985. Different soil conditioners and manures were applied and plant species cultivars were evaluated with regard to plant biomass, vigour, durability and content of zinc, lead and cadmium. Sewage sludge and topsoil led to better establishment of grasses than did municipal waste, straw and hydraulic seeding. After 2 years, Festuca rubra and Poa pratensis dominated the swards. Other species (Dactylis glomerata, Bromus inermis, Lolium perenne, Phleum nodosum, Festuca pratensis and F. arundinacea) constituted only a minor part of the stand. After 10 years, F. rubra was the most dominant species, while native Agrostis tenuis had invaded 20-50% of the area within the plots. Merlin was the clearly dominant red fescue cultivar. The concentration of zinc in shoots (616 mg kg(-1) dw) was about 10% of that in the soil. Zinc concentration decreased with increasing biomass above ground. It increased with age in Scots pine needles and was very high in birch leaves. Grasses survived longer than legumes in the zinc sand waste. Among the surviving grasses was a group with high (3800 mg kg(-1) dw) and a group with low (320 mg kg(-1) dw) zinc concentrations. The low group included Merlin red fescue and Sobel creeping bent. The cultivar Merlin contained a much lower zinc concentration than the other cultivars of red fescue (375 and 624 mg kg(-1) dw, respectively). A large amount of root biomass was present in plots with dominating Merlin red fescue (1715 g m(-2)), 97% of which was concentrated in the top 10 cm of the soil. The concentration of zinc in the roots was very high (13 000-25 000 mg kg(-1) dw). Nitrate fertilizer, especially ammonium nitrate, and acidic water (pH 4.3) increased zinc leaching.     

Effect of Coal Mine Soil Contamination on the Elemental Uptake and Distribution in Two Edible Amaranthus Species,A. dubius and A. hybridus

The impact of coal mine dump contaminated soil on the elemental uptake by two edible plants, namely, Amaranthus dubius (red herbs) and Amaranthus hybridus (green herbs), was studied by investigating their response and ability to tolerate and accumulate varying levels of elements in their roots and shoots. The vegetation was grown on varying amounts of contaminated soil, viz. 0%, 5%, 15%, 25% w/w using coal mine dump soil. The soil was analyzed for soil pH, cation exchange capacity (CEC), soil organic matter (SOM), moisture content, and selected heavy metals. The distribution of six metals, namely, Pb, Cd, Hg, Ni, Mn, and Fe, in roots, stem, and leaves of the plants was determined in two stages of growth after 5 weeks and 10 weeks. All soil and plant samples were microwave digested and subjected to heavy metal analysis using the ICP-OES, GFAAS, and CVAAS. The pH of the coal mine dump contaminated soil decreased with an increase in contamination. Both the SOM and CEC values decreased, which increases the availability of elements, by providing more binding sites in the soil. Relatively, the red herbs had higher elemental concentrations than the green herbs. Both plants recorded high manganese accumulation. No mercury was detected in the soils or plants.     

过磷酸钙与石灰混施对污染农田低累积玉米生长和重金属含量的影响

通过田间实验,研究了过磷酸钙和石灰混施对重金属污染农田上低累积玉米产量以及籽粒、茎叶重金属含量的影响,并分析了施用过磷酸钙和石灰后土壤pH和有效重金属含量的变化。结果表明,与单施过磷酸钙和单施石灰相比,过磷酸钙和石灰混施更能显著提高玉米生物产量,且过磷酸钙和石灰均有一定的后效。单施石灰处理、石灰与过磷酸钙混施处理都均显著降低玉米籽粒Cd、Zn和Cu含量,其中以中量(0.4 kg/m2)、高量石灰(0.6 kg/m2)+中量过磷酸钙(0.2kg/m2)处理效果最佳,其玉米籽粒Cd、Zn和Cu含量降低到了国家食品卫生标准允许的含量水平。石灰处理均不同程度地提高了玉米籽粒Pb含量,配施过磷酸钙也不能明显降低玉米籽粒Pb含量,但仍低于饲料卫生标准允许的含量水平。另外,单施石灰处理和石灰与过磷酸钙混施处理均显著降低了玉米茎叶Cd、Pb、Zn和Cu含量,可以安全用作有机肥。     

汞、铅、铬污染土壤的微生物修复

利用裂褶菌(Schizophyllum commune)GGHN08-116菌株,以棉籽壳、玉米秸等为固体发酵底物修复受汞、铅、铬污染的土壤。通过菌丝穿透重度重金属土壤实验,研究了菌丝在穿透土壤过程对交换态重金属的影响以及该菌株子实体对重金属离子的富集能力,同时,通过盆栽实验研究了在重度重金属污染土壤上,施用不同比例的固体发酵料对污染土壤中汞、铅、铬及其胡萝卜根茎质量、产量的影响,研究结果表明,该菌株能穿透厚度为5 cm的土壤,并有子实体生成,土壤pH值略有下降,与对照差异不显著;与对照相比,土壤中交换态汞、铬含量均显著下降,而交换态铅差异不显著,子实体中除汞含量符合标准外,铅、铬均超出了GB 7096-2003,GB 2762-2005规定标准。在固体发酵料处理下土壤中交换态汞、铅、铬含量均显著下降,胡萝卜根茎中均未检测到汞、铅含量,铬含量也符合GB 2762-2005规定标准。GGHN08-116菌株及其固体发酵产物具有修复受重金属污染土壤的能力。     

Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.     

Agro-industrial wastes as effective amendments for ecotoxicity reduction and soil health improvement in aided phytostabilization

Aided phytostabilization is a technology that uses metal tolerant plants and organic and/or inorganic amendments to reduce soil metal bioavailability, while improving soil health. Our objective was to determine the effects of the application of amendments [sheep manure (SHEEP), poultry litter (POULTRY), cow slurry (COW), and paper mill sludge mixed with poultry litter (PAPER)], together with the growth of a metallicolous Festuca rubra L. population, on (i) chemical and microbial indicators of soil health and (ii) soil ecotoxicity, during the aided phytostabilization of a Zn/Pb contaminated mine soil. Amendment application led to an increase in soil pH, organic matter content, and inorganic salts, resulting in a decrease in Pb and Zn CaCl₂-extractable concentrations in soil, which, in turn, contributed to lower ecotoxicity and a stimulation of plant growth and soil microbial communities. The factor most affecting the metal extractability was probably soil pH. POULTRY was the best amendment in terms of increasing plant growth, chlorophylls content, and soil microbial biomass and activity, but resulted in higher levels of phytoavailable Pb and Zn. SHEEP and PAPER were more effective at reducing metal CaCl₂-extractability and, consequently, led to lower values of metal accumulation in plant tissues, thereby reducing the risk of metals entering into the food chain. When combined with the application of organic amendments, the metallicolous F. rubra population studied here appears an excellent candidate for aided phytostabilization. Our results indicate that the application of organic amendments is essential for the short-term recovery of highly contaminated metalliferous soils during aided phytostabilization.     

Dissolved and colloidal transport of Cd, Pb, and Zn in a silt loam soil affected by atmospheric industrial deposition.

As a result of processing of metal ores, trace metals have contaminated large areas of northern France. Metal migration from the soil to groundwater presents an environmental risk that depends on the physico-chemical properties of each contaminated soil. Soil water samples were obtained over the course of 1 year with zero-tension lysimeters from an acidic, loamy, metal contaminated soil. The average trace metal concentrations in the soil water were high (e.g. for Zn 11 mg l-1 under the surface horizon), but they varied during the sampling period. Zn concentrations were not correlated with pH or total organic carbon in the solutions but were correlated with Cd concentrations. On average, 95% of the Zn and Cd but only 50% of Pb was present in a dissolved form. Analytical transmission electron microscopy was used to identify the Zn or Pb carriers. Colloids containing Pb and Zn were biocolloids, whereas colloids containing only Zn were smectites.     

Uptake of heavy metals and As by Brassica juncea grown in a contaminated soil in Aznalcóllar (Spain): the effect of soil amendments

Two crops of Brassica juncea (L.) Czern. were grown in a field experiment, at the site affected by the toxic spillage of acidic, metal-rich waste in Aznalcóllar (Seville, Spain), to study its metal accumulation and the feasibility of its use for metal phytoextraction. The effects of organic soil amendments (cow manure and mature compost) and lime on biomass production and plant survival were also assessed; plots without organic amendment and without lime were used as controls. Plots, with or without organic amendment, having pH < 5 were limed for the second crop. Soil acidification conditioned plant growth and metal accumulation. The addition of lime and the organic amendments achieved higher plant biomass production, although effects concerning metal bioavailability and accumulation were masked somewhat by pH variability with time and between and within plots. Tissue metal concentrations of B. juncea were elevated for Zn, Cu and Pb, especially in leaves of plants from plots with low pH values (maxima of 2029, 71 and 55 microg g(-1), respectively). The total uptake of heavy metals in the plants was relatively low, emphasising the problems faced when attempting to employ phytoextraction for clean-up of pluri-contaminated sites.     

Chemical methods and phytoremediation of soil contaminated with heavy metals

The effects of chemical amendments (calcium carbonate (CC), steel sludge (SS) and furnace slag (FS)) on the growth and uptake of cadmium (Cd) by wetland rice, Chinese cabbage and wheat grown in a red soil contaminated with Cd were investigated using a pot experiment. The phytoremediation of heavy metal contaminated soil with vetiver grass was also studied in a field plot experiment. Results showed that treatments with CC, SS and FS decreased Cd uptake by wetland rice, Chinese cabbage and wheat by 23-95% compared with the unamended control. Among the three amendments, FS was the most efficient at suppressing Cd uptake by the plants, probably due to its higher content of available silicon (Si). The concentrations of zinc (Zn), lead (Pb) and Cd in the shoots of vetiver grass were 42-67%, 500-1200% and 120-260% higher in contaminated plots than in control, respectively. Cadmium accumulation by vetiver shoots was 218 g Cd/ha at a soil Cd concentration of 0.33 mg Cd/kg. It is suggested that heavy metal-contaminated soil could be remediated with a combination of chemical treatments and plants.     

Effect of coal mine soil contamination on the elemental uptake and distribution in two edible Amaranthus species, A. dubius and A. hybridus

The impact of coal mine dump contaminated soil on the elemental uptake by two edible plants, namely, Amaranthus dubius (red herbs) and Amaranthus hybridus (green herbs), was studied by investigating their response and ability to tolerate and accumulate varying levels of elements in their roots and shoots. The vegetation was grown on varying amounts of contaminated soil, viz. 0%, 5%, 15%, 25% w/w using coal mine dump soil. The soil was analyzed for soil pH, cation exchange capacity (CEC), soil organic matter (SOM), moisture content, and selected heavy metals. The distribution of six metals, namely, Pb, Cd, Hg, Ni, Mn, and Fe, in roots, stem, and leaves of the plants was determined in two stages of growth after 5 weeks and 10 weeks. All soil and plant samples were microwave digested and subjected to heavy metal analysis using the ICP-OES, GFAAS, and CVAAS. The pH of the coal mine dump contaminated soil decreased with an increase in contamination. Both the SOM and CEC values decreased, which increases the availability of elements, by providing more binding sites in the soil. Relatively, the red herbs had higher elemental concentrations than the green herbs. Both plants recorded high manganese accumulation. No mercury was detected in the soils or plants.     

Phosphate-induced metal immobilization in a contaminated site

To assess the efficiency of P-induced metal immobilization in soils, a pilot-scale field experiment was conducted at a metal contaminated site located in central Florida. Phosphate was applied at a P/Pb molar ratio of 4.0 with three treatments: 100% of P from H3PO4, 50% of P from H3PO4+ 50% of P from Ca(H2PO4)2, and 50% of P from H3PO4+5% phosphate rock in the soil. Approximately 1 year after P application, soil and plant samples were collected to determine mobility and bioavailability of selected metals (Pb, Zn, and Cu) using sequential extraction procedure and mineralogical characterization using X-ray diffraction (XRD) and scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis. Phosphorus distribution and soil pH effects were also evaluated. Phosphate was more effective in transforming soil Pb (to 53%) from the non-residual to the residual phase than soil Zn (to 15%) and soil Cu (to 13%). This was because Pb was immobilized by P via formation of an insoluble pyromorphite-like mineral in the surface and subsurface of the soil, whereas no phosphate mineral Zn or Cu was identified. While P amendment enhanced metal uptake in the roots of St. Augustine grass (Stenotaphrum secundatum), it significantly reduced metal translocation from root to shoot, especially Pb via formation of a pyromorphite-like mineral on the membrane surface of the root. A mixture of H3PO4 and phosphate rock was effective in metal immobilization, with less soil pH reduction and less soluble P. Although H3PO4 was effective in immobilizing Pb, its use should be limited to minimize soil pH reduction and potential eutrophication risk.     

Speciation of heavy metals during co-composting of sewage sludge with lime

During composting the humification of organic matter will have a significant effect on the physicochemical form of existence of heavy metals. Therefore the present study was conducted to investigate the effect of co-composting sewage sludge with lime on heavy metal speciation and the changes in DTPA extractable metals. Metal speciation was conducted to evaluate the redistribution of Cu, Mn, Ni, Pb and Zn in sewage sludge composted with lime. Sewage sludge was mixed with sawdust in 2:1 (w/w fresh weight) and then composted with lime at 0%, 0.63%, 1% or 1.63% (dry weight) for 100 days. The lime addition did not cause any changes in the different forms of Cu and Mn, but the composting process caused transformations of residual form of Cu and Mn into oxidizable and reducible form, respectively. For Ni, the reducible form was mainly transformed into residual form and lime addition decreased this transformation. Major transformation of different forms of Pb was not found, however the residual form of Pb increased with lime addition. The predominant residual form of Zn was mainly transformed into oxidizable form and the lime addition reduced this transformation. Addition of lime to sewage sludge during composting resulted in lower DTPA extractable metal contents. Therefore, lime is a suitable material to co-compost with sewage sludge to reduce the availability of heavy metals.     

Stabilization of Pb- and Cu-contaminated soil using coal fly ash and peat

The stabilization of metal contaminated soil is being tested as an alternative remediation method to landfilling. An evaluation of the changes in Cu and Pb mobility and bioavailability in soil induced by the addition of coal fly ash and natural organic matter (peat) revealed that the amount of leached Cu decreased by 98.2% and Pb by 99.9%, as assessed by a batch test. Metal leaching from the treated soil was lower by two orders of magnitude compared to the untreated soil in the field lysimeters. A possible formation of mineral Cu- and Pb-bearing phases and active surface with oxides were identified by chemical equilibrium calculations. Low metal leaching during a two-year observation period, increased seed germination rate, reduced metal accumulation in plant shoots, and decreased toxicity to plants and bacteria, thereby demonstrating this stabilization method to be a promising technique for in situ remediation of Cu and Pb contaminated soil.     

Phytostabilization of a metal contaminated sandy soil. I: Influence of compost and/or inorganic metal immobilizing soil amendments on phytotoxicity and plant availability of metals

In a lysimeter set-up, compost addition to an industrial contaminated soil slightly reduced phytotoxicity to bean seedlings. The "Phytotoxicity Index" (on a scale from 1 to 4) decreased from 3.5 to 2.8. The same treatment also reduced metal accumulation in grasses: mean Zn, Cd and Pb concentrations decreased respectively from 623 to 135, from 6.2 to 1.3 and from 10.7 to <6 mg kg-1 dry weight. When combined with inorganic metal immobilizing amendments, compost had a beneficial effect on plant responses additional to the inorganic amendments alone. Best results were obtained when using compost (C)+cyclonic ashes (CA)+steel shots (SS). The "Phytotoxicity Index" decreased to 1.7, highest diversity of spontaneously colonizing plants occurred, and metal accumulation in grasses reduced to values for uncontaminated soils. Based on the first year evaluation, C+CA+SS showed to be an efficient treatment for amendment assisted phytostabilization of the contaminated Overpelt soil.