Accumulation of heavy metals in oil-contaminated peat soils

X-ray fluorescence and X-ray radiometry represent easy and simple methods to determine concentrations of heavy metals in the ash of peat soils contaminated with oil and can be applied for soil monitoring purposes. Oil spills on peat bogs produce two contamination zones differing in the composition of heavy metals. In the zone of primary contamination, the peat surface is covered by a bitumen crust with V, Ni, Sr, Ba, Ce, and La accumulating there. This zone adjoins the zone of secondary peat contamination, where heavy alkaline-earth metals (Sr, Ba) and lanthanides (Ce and La) are accumulated to a lesser extent. Biological preparations recommended for remediation of oil-contaminated peat soils should be tolerant to high concentrations of heavy metals, particularly, V, Ni, and Ba that are present in the oil contaminated soils in relatively high amounts.     

Einflußgrößen der Schwermetallöslichkeit und -bindung in Böden

Solubility and retention of heavy metals in soils Model experiments were carried out under oxidizing conditions with soil samples from surface and subsurface horizons of different composition in order to investigate the solubility and retention of Cu, Zn, Cd, and Pb in soils. The solubility of heavy metals is mainly determined by ad- and desorption processes and complexation reactions of organic and inorganic ligands. Precipitation and dissolution of definite heavy metal compounds do not seem to govern the solution concentration in soils. An exception may probably be the formation of lead phosphate and zinc silicate under specific reaction conditions. The main factors which determine solubility and retention of heavy metals are total amount (except the proportion incorporated in the silicate structure) of the different metals, soil reaction, content of mobilizing and immobilizing organic substances, content of pedogenic oxides and clay minerals, and kind and concentration of salts and inorganic ligands. The results of the model experiments are used together with the results of other authors and general physico-chemical data to give an interpretation of the solubility behaviour of heavy metals in soils. The relations between heavy metal solubility, availability and mobility and possible procedures for melioration of soils contaminated with heavy metals are discussed.     

印度芥菜(Brassica juncea L.)重金属耐性机理研究进展

印度芥菜可富集/忍耐Cd、Zn 等多种重金属, 是研究植物修复技术的一种模式植物。高浓度的重金属离子会改变植物的基因表达、细胞形态、细胞结构, 最终使植物生长受抑, 甚至死亡。印度芥菜高效的抗氧化系统、损伤修复系统以及对重金属的螯合、区域化可部分解除重金属的毒性, 缓解重金属离子的毒害作用。利用基因工程技术在印度芥菜中导入重金属耐性及运输相关基因可大幅度提高其重金属富集能力, 在重金属污染修复方面具有广阔的应用前景。     

Immobilization of the heavy metals Cd, Cu and Pb in an acid soil amended with gypsum- and lime-rich industrial by-products

In situ stabilization of heavy metals in contaminated soils by the addition of various types of soil amendment is an attractive technique for remediation. We investigated the potential of three industrial by‐products (phosphogypsum, red gypsum and dolomitic residue) for boosting the heavy metal sorption capacity of an acid soil (patents pending, Spanish applications no 200201704 and 200201375) by using sorption isotherm experiments. The three by‐products were found substantially to increase the retention of lead, cadmium and copper on the solid components of the soil. The increase in lead retention of the soil horizons upon the addition of both phosphogypsum and red gypsum was dominated by the formation of anglesite minerals. The dolomitic residue increased the metal retention capacity of the soil horizons through the precipitation of laurionite‐type minerals as well as cadmium and copper hydroxy‐chlorides. In addition to the batch sorption study, we used scanning electron microscopy to investigate the metal sorption processes in the soil by the effect of the treatments. Lead was frequently found to be linked to the edge charges of kaolinite minerals. The three metals were found to be associated with organic matter in the Ap horizon treated with the three by‐products. Finally, the three metals were found to be associated with undissolved dolomitic residue particles.     

南京栖霞重金属污染区植物富集重金属效应及其根际微生物特性分析

以南京栖霞重金属污染区5种植物及其根际土壤为研究对象,对植物富集重金属特征以及重金属含量与根际土壤细菌数量、土壤酶活性等的相关性进行了调查分析。结果发现,植物根际重金属污染物以Zn和Cd为主;重金属污染地区的植物有较强的吸收重金属能力,龙葵和茼草具备了超积累植物的基本特征;植物根际细菌和Pb抗性细菌的数量达到了107CFU g-1土;根际土壤酶活性未受到重金属的毒害或受到的毒害很小;植物体中重金属含量与土壤重金属含量及其存在状态、土壤酶、土壤重金属抗性细菌有显著的正相关性。根际土壤细菌尤其是具有重金属抗性的活性细菌可能会促进土壤重金属的活化,由此促进植物体对重金属的吸收和转运。     

Self-purification of agrosoddy-podzolic sandy loamy soils fertilized with sewage sludge

Sandy loamy agrosoddy-podzolic soils and plants growing on them were studied. The soils had been treated with sewage sludge from the Lyubertsy aeration station applied as organic fertilizer for 5–10 years before 1990. Initially, these soils were used for cultivating vegetables and fodder crops. The content and mobility of heavy metal compounds increased in the plow horizons of studied soils under the influence of sewage sludge. The concentrations of Cd and Zn exceeded the tentative permissible concentrations (TPC) for these elements by 8–16 and 2–4 times, respectively. The contaminated layer was found at the depths within 30–50 cm, which attests to a low migration rate of heavy metals added to the studied soils with sewage sludge (SS) 25 years ago. The concentration of Cd exceeded the maximum permissible concentration (MPC) of this element in all vegetable and fodder crops cultivated on the studied soils. The content of heavy metals in plants differed by three–five times in dependence on the capacity of particular plants to accumulate them. The period of soil self-purification from heavy metals was found to depend on the soil contamination level and element mobility, as well as on the element removal with harvested crops and with soil water flows. The maximal time of achieving the normal level of Cd concentration was estimated as 288 years for maximally contaminated soils; the corresponding values for Cu and Zn were estimated as 74 and 64 years, respectively.     

Accumulation of Zinc and Copper in an Arable Field after Animal Manure Application

An experiment was conducted to examine the accumulation and mobility of heavy metals (Zn and Cu) at different depths in three types of arable soils (Brown Lowland soil, Andosol, and Brown Forest soil) amended with cattle and pig farmyard manures for 5 years. Nitric-perchloric acid digestion was performed for the determination of the total amounts of heavy metals, and 0.1 M hydrochloric acid extraction was performed for the determination of the amounts of soluble heavy metals. Results of the soil analysis indicated that pig farmyard manure application resulted in serious contamination of arable soils with Zn and potentially Cu. Especially, the Brown Forest soil displayed a high ability to accumulate heavy metals on the soil surface. Total-Zn concentration in surface soils was considerably affected by the holding capacity of soluble-Zn traction. Although the Andosol amended with pig farmyard manure showed higher concentrations of heavy metals related to the higher ability of retention on a weight basis, the soil did not contribute to high heavy metal accumulation because of its low bulk density. Heavy metals were easily leached in sandy soils such as Brown Lowland soil, and Cu was potentially stable compared with Zn. We suggest that long-term pig farmyard manure application to the Brown Lowland soil and Andosol with a light soil texture is associated with a higher risk of groundwater pollution than the application to the Brown Forest soil.     

南方几种水稻土重金属污染下的土壤呼吸及微生物学效应

采集南方几种重金属污染下的水稻土,通过室内培养的方法研究土壤CO2排放的动态变化以及微生物学指标的差异。结果表明,在60d的培养期内,前7d土壤呼吸速率较高,占了整个排放量的30．89％～64．37％,并且这一阶段重金属对土壤呼吸速率的影响最大。重金属对土壤微生物生物量的影响表现出增加、抑制与无显著性差异的结果,而重金属对微生物熵及微生物代谢熵（qCO2）的影响却是极显著的,同时表现出增加与降低的不同结果。这说明土壤呼吸以及不同的微生物学指标,在长期的复合重金属污染条件下,其表现并不一致,微生物熵与代谢熵用于基本性质差异较大的土壤时,对重金属的响应更为灵敏。此外,土壤重金属的累积还能提高土壤中有机碳的含量。     

Leaching of soil‐derived major and trace elements in an arable topsoil after the addition of biochar

The addition of biochar to soils appears to be attractive for sequestering carbon and improving soil fertility. Biochar has been shown to alter carbon, nutrient and element cycling, but there is little information on the cycling of trace elements, which will be introduced increasingly into soils because of their use in modern technologies (e.g. rare earth elements) and significant concentrations in phosphate fertilizers. This study investigated, using column experiments, the effect of biochar addition on the leaching of soil‐derived trace metals from a soil contaminated with heavy metals. The biochar used in this study showed a clear potential to reduce soil‐derived trace metals, including transition metals, rare earth elements and heavy metals such as cadmium (Cd) and lead (Pb), while increasing the amounts of essential nutrients such as potassium (K) and molybdenum (Mo). Uranium was mobilized in the presence of biochar, indicating a risk of increased leaching in biochar‐amended soils. During elution under anoxic conditions manganese (Mn) and iron (Fe) oxides were reduced and a release of metals typically bound to these oxides such as Pb, cobalt (Co), zirconium (Zr) and niobium (Nb) was observed. The retention of dissolved organic matter (DOM) in the amended soil led to a retention of DOM‐associated elements such as copper (Cu), zinc (Zn) and nickel (Ni). Analysis by liquid chromatography followed by ICP‐MS indicated an association with UV‐active DOM. In previous studies conducted with inorganic metal species added to soil, an increased retention of metals has often been interpreted as being caused by cation exchange with the biochar. Our results indicate that the decreased mobility of trace elements is at least partly caused by an enhanced retention of metal‐binding DOM after biochar application.     

Iron minerals in urban soils

Technogenically contaminated urban soils contain a substantial amount of magnetite Fe₃O₄, whereas another ferrimagnetic, i.e., maghemite αFe₂O₃, more often prevails in unpolluted soils. The content of magnetite may exceed the content of another iron oxide, hematite, in contaminated soils. In the town of Chusovoi, where emissions from a single enterprise, a metallurgical plant, predominate among pollutants, the upper soil horizons are contaminated with magnetite of one type. In the much larger city of Perm, the polluting sources are diverse, which results in a wide variation of magnetic susceptibility of technogenic magnetite. The difference in magnetite properties may depend on the composition and the content of heavy metals associated with this mineral. A considerable amount of oxalate-soluble magnetite in technogenically contaminated soils produces two important consequences. Schwertmann’s criterion Fe_ox: Fe_dit as a gleying index turns out to be overestimated and, therefore, does not work in technogenically contaminated soils. The second consequence is that Tamm’s reagent is inapplicable to extracting heavy metals bound to amorphous iron compounds from contaminated soils. On the other hand, a high solubility (30–60%) of technogenic magnetite by oxalate favors the use of Tamm’s reagent for the complete extraction of iron (hydr)oxides and heavy metals bound to them.     

Effect of the initial soil water saturation on the behaviour of a mixed LNAPL and heavy metal contaminated glaciofluvial deposit

Soil contamination by mixtures of petroleum hydrocarbons and heavy metals is common in urban and industrial localities. Interactions between these contaminants have an impact on the mobility and the management of contamination. We have characterized the modifications to the transport of heavy metals (Cd, Cu, Pb, Zn) in soil induced by residual light non‐aqueous phase liquid (LNAPL) for two conditions of trapping. Experiments on the elution of tracers and heavy metals in columns of soil were performed with a glaciofluvial material as the soil. Tracer experiments were modelled with the mobile–immobile (MIM) system of partial differential equations. The experiments were designed to compare water flow and metal transport in LNAPL‐contaminated soil with a control set. Residual LNAPL was trapped in water‐saturated and dry soil to ensure preferential wettability of soil surfaces, namely either water‐wet or LNAPL‐wet. In water‐wet soil columns, LNAPL decreased water flow by two orders of magnitude and increased the fraction of immobile water. Solute residence times (SRTs) suggested that heavy metals resided mainly in mobile water where the reaction time was sufficient to reach steady‐state retention. The SRTs also indicated that a fraction of the heavy metal flux diffused to the immobile water where its retention was limited by diffusion. Retention of heavy metals was significantly greater than in the control columns. In LNAPL‐wet soil columns, the obstruction of small pores and surface coating by residual LNAPL significantly decreased the attenuation capacity of the soil by decreasing the diffusion of heavy metals to immobile water and surface sites. Evidently, the individual behaviour of heavy metals can be significantly modified by non‐miscible organic contaminants. These modifications can have important implications for risk evaluation, contamination management and in situ remediation of soil that is contaminated by mixtures of petroleum hydrocarbons and heavy metals.     

The Influence of Heavy Metals and Mineral Nutrient Supply on Bituminaria bituminosa

With a view to the selection of plants for the re-vegetation of contaminated, semi-arid land, two populations of the perennial species Bituminaria bituminosa (Fabaceae) from the south of Spain were studied: one (“LA”) from a non-contaminated soil and the other (“C2”) from a similar soil having elevated total levels of Pb and Zn (1,112 and 4,249 μg g^?1, respectively). For sand-cultured plants receiving nutrient solution, flow cytometry showed that heavy metals, at the concentrations measured in aqueous extracts from contaminated soils, had only slight genotoxic effects on root tip cell nuclei. Both populations were also grown in both soils, in two pot experiments. In the first, shoot biomass of LA and C2 in the contaminated soil was decreased to similar extents, with respect to the “clean” soil. Tissue heavy metal concentrations were unlikely to have been phytotoxic, except in the case of shoot Zn for population LA, but there were tissue deficiencies of P and K for populations LA and C2, respectively. In the second pot assay, the stimulation of growth by NPK fertiliser confirmed that even though this soil had high total heavy metal levels, nutrient availability was the principal factor limiting growth. The lesser transport of heavy metals (Cd, Mn and Zn) to the shoot by the population from the contaminated site is a factor that should be considered when selecting B. bituminosa lines for the phytostabilisation of such sites.     

Limited downward migration of pollutant metals (Cu,Zn, Ni,and Pb) in acidic virgin peat soils near a smelter

The distribution of pollutant heavy metals (Cu, Zn, Ni, Cd, and Pb) was determined in 11 acidic virgin peat profiles located along two transects moving away from a smelter plant in the Noranda region of Quebec. The levels of all five metals were found highest in the 0 to 15 cm layer at site near the smelter, and decreased progressively with the distance from the smelter, up to 42 km. Copper had the highest concentrations (5525 μg g^?1) followed by Pb and Zn. The maximum levels of total metals built up in the peat surface near the smelter were high, approximately reaching the threshold limits for phytotoxicity in peat soils. The amounts of heavy metals moving down and accumulating in the anaerobic zone of the peat profiles were limited. The distribution and enrichment ratios in the profiles showed that Cu, Zn, and Cd would have relatively higher mobility than Pb.     

杭州市城市土壤重金属的潜在可淋洗性研究

研究了杭州市城市土壤 8个重金属元素 (Cd、Co、Cr、Cu、Ni、Pb、Zn、Mn)的含量、形态和潜在可淋洗性。结果表明 ,该城市土壤中Cd、Cr、Cu、Ni、Pb、Zn和Mn均有明显的积累 ,其中Cd、Co、Cr和Ni主要以稳定的残余态为主 ,而Cu、Pb、Zn和Mn则以可提取态为主 ,因此在强还原、强酸性或有利于有机质分解条件下Cu、Pb、Zn、Mn的释放潜力较高。用荷兰能源研究中心的淋洗方法 (pH4 0 )测试表明 ,该市城市土壤的重金属可淋洗性较低 ,在一般条件下该城市土壤重金属不会有较大的释放 ,这与该城市土壤中酸可提取态重金属比例较低并含有较高的有机质及粘粒含量有关     

Laboratory Investigation of the Geochemical Behavior of Metals in Paddy Soils Contaminated with Mine Tailings

The geochemical behavior of metals, including Fe, Mn, Pb and Zn, in contaminated paddy soils was investigated during the cultivation of rice crops through laboratory microcosm experiments. From the two paddy fields contaminated by mine tailings, Siheung and Deokeum in Korea, paddy soils were collected and analyzed for their geochemical characteristics. The Siheung paddy soil showed higher levels of heavy metals, whereas the higher potential for the release of metals was anticipated due to the extremely acidic conditions at Deokeum. In microcosm experiments of flooded paddy soils over 18 weeks, Fe and Mn were released in subsurface pore waters by reductive dissolution, and Pb and Zn were dissolved in high amounts at the surface by oxidation of sulfides. Although amorphous Fe oxide-rich layers were formed at the surface of both paddy soils, the release of Pb and Zn were controlled at the surface by these layers only under slightly alkaline conditions at Siheung. Lead and Zn were associated with the reducible and carbonate fractions at the surface paddy soil of Siheung from the sequential extraction on core samples collected during the flooded period. In the acidic conditions at Deokeum, Pb and Zn were continuously released until the late stage of flooding. A great increase in the exchangeable fraction of metals was observed after the soils had drained. The bioavailability of metals for rice crops would be high under acidic conditions at Deokeum, despite the lower levels of heavy metal contamination.     

Lysosomal Fragility in Earthworms (Eisenia Veneta) Exposed to Heavy Metal Contaminated Soils from Two Abandoned Pyrite Ore Mines in Southern Norway

In this study we have investigated the toxicity of soils from thetwo abandoned pyrite mines Ertelien and Konnerud in the southernpart of Norway. Soil samples were collected close to the pitheadof the mines, and earthworms were exposed to different concentrations of the contaminated mine soil mixed with commercial plant soil for a period of 14 days. Life-cycle responses such as growth and survival, as well as the biomarkerresponse lysosomal fragility were measured. The body burdens ofthe four heavy metals Cu, Cd, Zn and Pb were detected in the worms, and the body concentration of the metals generally increased with increasing heavy metal concentration in the soil.The growth and mortality of the earthworms were not influenced when exposed to any of the mine soil concentrations used. The lysosomal fragility of the earthworm coelomocytes measured by the neutral red retention time (NRR-time) was found to be markedly reduced in all the exposed earthworms. This assay seemsto be a sensitive and dose dependent endpoint for the toxicity assessment of heavy metal mixtures in pyrite mine soils.     

二乙三胺五醋酸萃取后污染土壤中重金属Pb、Cu的形态分布

以硫铜矿尾矿区域土壤和库区周边受污染的农田土壤为研究对象,采用Tessier连续提取法研究了二乙三胺五醋酸(DTPA)萃取前后受污染土壤中的重金属Pb、Cu的形态变化。结果表明,两类污染土壤中的重金属Pb、Cu的形态分布各有差异,矿区土壤Pb、Cu主要以残渣态为主,农田土壤以有机结合态为主。在0.01molL-1浓度的条件下,DTPA对供试土壤Pb的萃取能力较其对Cu萃取能力强;经DTPA萃取后土壤中Pb、Cu的残渣态、碳酸盐结合态、铁锰氧化物结合态、交换态的含量分别有所下降。两种类型土壤中Pb、Cu残渣态、碳酸盐结合态、铁锰氧化物结合态、交换态变幅表现各异;矿区土壤和农田土壤中Cu的有机结合态含量有所增加,矿区土壤和农田土壤中Pb的有机结合态含量却表现各异,矿区土壤其含量有所增加,而农田土壤其含量却明显减少。     

复垦沉积池土壤中镍、铅、锌的吸附

The wastes used to amend soils sometimes have high concentrations of metals such as nickel (Ni), lead (Pb) and zinc (Zn). To determine the capacity of soils to retain these metals, the sorption capacities of different mine soils with and without reclamation treatments (tree vegetation and waste amendment) for Ni, Pb and Zn in individual and competitive situations were evaluated using the batch sorption technique. The untreated settling pond soil had low capacity for Ni, Pb and Zn retention. The site amended with wastes (sewage sludges and paper mill residues) increased the sorption capacity most, probably because of the higher concentrations of soil components with high retention capacity such as carbon and clay fraction. No significant competition was observed between metals in the competitive sorption experiment, indicating that the maximum of sorption was not achieved by adding 0.5 mmol L^-1 of metal. We can conclude that, despite the possible additions of Ni, Pb and Zn from wastes to degraded soils, sewage sludges and paper mill residues have a high sorption capacity that would prevent the metals from being in a mobile form.     

The Diversity of Bacterial Communities in Urban Soils

Urbanozems (Urbic Technosols) contaminated by heavy metals and polychlorbiphenyls (Urbic Technosols Toxic) and intruzems (Urbic Technosols Toxic) were studied in Moscow; additionally, we studied recreazems (Urbic Technosols Thaptohumic) and culturozems (Urbic Technosols Pantohumic) on the territory of the Botanical Garden of Moscow State University (Aptekarskii Ogorod, the Apothecaries’ Garden). In the soils contaminated with heavy metals and oil products, the number of viable cells of bacteria decreased, whereas the content of filterable forms of bacteria increased. The taxonomic structure of saprotrophic bacterial complexes in contaminated urban soils was transformed towards an increase in the diversity of bacterial taxa atypical of natural undisturbed soils. Rhodococci (Rhodococcus genus) predominated in the soils contaminated with oil and polychlorbiphenyls, enterobacteria (Escherichia, Enterobacter, and Klebsiella genera) predominated in the soils contaminated with municipal wastes, and Arthrobacter genus was dominant in the soils contaminated with cement dust. Soils of both Botanical Gardens of Moscow State University were characterized by the high population density and specific distribution of bacteria in the profile; the structure of their saprotrophic bacterial complex had some similarity with that in the soils of more southern regions. The obtained data on the bacterial diversity of urban soils attest to considerable transformation of bacterial communities both in the contaminated urban soils and in the soils of botanical gardens.     

用突变点检测方法预测木生境下污染土壤中的可提性镉、铅和锌

Accumulation of heavy metals in soils poses a potential risk to plant production, which is related to availability of the metals in soil. The phytoavailability of metals is usually evaluated using extracting solutions such as salts, acids or chelates. The purpose of this study was to identify the most significant soil parameters that can be used to predict the concentrations of acetic and citric acid-extractable cadmium (Cd), lead (Pb) and zinc (Zn) in contaminated woody habitat topsoils. Multiple linear regression models were established using two analysis strategies and three sets of variables based on a dataset of 260 soil samples. The performance of these models was evaluated using statistical parameters. Cation exchange capacity, CaCO3, organic matter, assimilated P, free Al oxide, sand and the total metal concentrations appeared to be the main soil parameters governing the solubility of Cd, Pb and Zn in acetic and citric acid solutions. The results strongly suggest that the metal solubility in extracting solutions is extractable concentration-dependent since models were overall improved by incorporating a change point. This change point detection method was a powerful tool for predicting extractable Cd, Pb and Zn. Suitable predictions of extractable Cd, Pb and Zn concentrations were obtained, with correlation coefficient (adjusted r) ranging from 0.80 to 0.99, given the high complexity of the woody habitat soils studied. Therefore, the predictive models can constitute a decision-making support tool for managing phytoremediation of contaminated soils, making recommendations to control the potential bioavailability of metals. The relationships between acetic and/or citric acid-extractable concentrations and the concentrations of metals into the aboveground parts of plants need to be predicted, in order to make their temporal monitoring easier.