不同种类有机物对污染农田土壤重金属活性的影响

为了解施用不同种类有机物对污染农田土壤重金属行为的影响,布设了田间小区试验,观察研究施用6种不同类型有机物对土壤水溶性重金属和农作物对重金属吸收等的影响。试验设7个处理,分别为对照(不施有机肥)、施新鲜水稻秸秆、新鲜鸡粪、鸡粪堆肥、新鲜猪粪、猪粪堆肥和商品有机肥,动态检测土壤中水溶性重金属含量、田面水中重金属浓度及收获水稻籽粒中重金属含量的变化。结果表明,与不施有机物的对照处理比较,施用各类有机物在试验前期均可明显提高土壤中水溶性重金属和田面水中重金属的含量,总体上以施用新鲜猪粪的最高,其次为新鲜鸡粪,施用商品有机肥的最低。土壤中水溶性重金属含量随试验时间增长逐渐下降。施用各类有机物对水稻籽粒中重金属的积累影响不明显。土壤中水溶性重金属及田面水中重金属含量均与相应的水溶性碳(DOC)浓度呈显著相关性,表明因有机物施用增加土壤中DOC浓度可能是土壤中水溶性重金属含量增加的主要原因;而不同有机物对土壤重金属活性影响的差异可能与有机物本身的分解程度及可释放DOC大小有关。但施用有机物引起的农田土壤水溶性重金属含量的增加是暂时的,对水稻生长后期籽粒中重金属积累的影响不明显。     

Mobilisation of Heavy Metals in Contaminated Sediments in the River Meuse,The Netherlands

Due to seasonal variation in bottom-water temperature and degradation of organic matter, the depths of the redox boundaries fluctuate in sediments of the river Meuse. This is reflected by a non-steady state behaviour of heavy metals in the surface sediments. Levels of acid-volatile sulphides suggest that dissolved concentrations of heavy metals in the anoxic pore waters are determined by their respective sulphide phases. However, complexation with dissolved organic ligands may significantly increase dissolved concentrations of heavy metals. In most sediments studied, a distinct peak in dissolved concentrations of heavy metals is measured immediately below the sediment-water interface. This concentration peak may be attributed to degradation of organic matter and oxidation of sulphides. Dissolved concentration gradients indicate that upward diffusion of heavy metals from the sediment can contribute to concentrations in the surface water, although significant effects may be confined to specific locations. In addition, it is shown that release of heavy metals as dissolved species to the surface water is negligible compared to particulate-bound fluxes of heavy metals to the sediment.     

Biogeochemistry of heavy metals in contaminated excessively moistened soils (Analytical review)

The biogeochemical behavior of heavy metals in contaminated excessively moistened soils depends on the development of reducing conditions (either moderate or strong). Upon the moderate biogenic reduction, Cr as the metal with variable valence forms low-soluble compounds, which decreases its availability to plants and prevents its penetration into surface- and groundwater. Creation of artificial barriers for Cr fixation on contaminated sites is based on the stimulation of natural metal-reducing bacteria. Arsenic, being a metalloid with a variable valence, is mobilized upon the moderate biogenic reduction. The mobility of siderophilic heavy metals with a constant valence grows under the moderate reducing conditions at the expense of dissolution of iron (hydr)oxides as carriers of these metals. Zinc, which can enter the newly formed goethite lattice, is an exception. Strong reduction processes in organic excessively moist and flooded soils (usually enriched in S) lead to the formation of low-soluble sulfides of heavy elements with both variable (As) and constant (Cu, Ni, Zn, and Pb) valence. On changing aquatic regime in overmoistened soils and their drying, sulfides of heavy metals are oxidized, and previously fixed metals are mobilized.     

Zinc forms in soils (Review of publications)

Zinc has no particular bearing phases in soils, and it forms very diverse compounds; this complicates zinc’s identification by chemical fractionation. However, Zn-containing particles may be identified using synchrotron X-ray analysis. Franklinite, willemite, hemimorphite, and Zn-containing magnetite are found to be the main technogenic Zn-containing pollutants in the heavy fraction of the contaminated surface soil horizon. Among the secondary zinc compounds, Zn-containing trioctahedral structures and clay minerals (unidentifiable by chemical extraction), as well as zinc fixed by manganese oxides and iron hydroxides, predominate in the soil clay fraction. Being a chalcophile element, zinc precipitates in the form of sulfides and forms complexes with organic substances in organic soils and peats. The degree of affinity to chalcophile metals increases in the following sequence: O-, P-, N-, and S-containing functional groups of organic substances.     

水稻子实对不同形态重金属的累积差异及其影响因素分析

在分析成都平原核心区土壤重金属(Cd、Cr、Pb、Cu、Zn)全量、各形态含量及相应点位种植的水稻子实重金属含量的基础上,通过统计分析、空间插值及线性回归方程的模拟,研究了土壤Cd、Cr、Pb、Cu、Zn全量的空间分布状况、各形态重金属含量统计特征,以及水稻子实对重金属各形态的累积差异及其影响因素。结果表明,成都平原水稻土重金属污染较轻,除Cd外,均低于国家土壤环境质量二级标准。土壤中重金属的可交换态含量均较低,Cd主要以铁锰氧化态存在,Cr、Cu、Zn、Pb主要以残渣态存在。水稻子实对5种重金属的累积效应顺序为:Cd>Zn>Cu>Pb>Cr。与水稻重金属累积关系密切的重金属活性形态(可交换态、碳酸盐结合态、铁锰氧化物结合态和有机物结合态)主要有:Cd的碳酸盐结合态、Cr的可交换态、Pb的有机物结合态和Cu的碳酸盐结合态含量;Zn各活性形态对水稻子实含量的影响不明显。土壤理化性质对不同活性形态重金属元素的影响效应各不相同。活性态Cd主要受有机质、pH和容重的影响;活性态Cr与pH、有机质、CEC和容重密切相关;活性态Pb与有机质、容重、中细粉粒、砂粒等均有密切的关系;Cu的活性主要受粘粒、有机质含量的影响;Zn的有效性主要受pH、有机质、砂粒、容重的影响。总的看来,对土壤Cd、Cr、Pb、Cu、Zn各活性形态含量影响效应较强的是有机质、pH、容重,而与土壤吸附性能密切相关的颗粒组成、CEC的影响不甚明显。     

污灌时间对土壤肥力及土壤酶活性的影响

通过时空互代、野外调查和采样分析的方法,研究了石家庄栾城县不同污水灌溉时间下（0~52 a）耕地土壤肥力及土壤酶活性特征。结果表明：与对照点相比,污水灌溉区土壤有机质、全氮、全磷含量,蔗糖酶、脲酶和磷酸酶活性均相对较高,而土壤阳离子交换量、过氧化氢酶和脱氢酶活性无明显的变化规律;污水灌溉区土壤全氮、蔗糖酶、磷酸酶与污灌时间之间表现出显著正相关性（P〈0.05）,其他指标与污灌时间之间均无显著相关性;土壤肥力（有机质和全氮）、重金属（总Cr和总Cd）与水解酶（脲酶和磷酸酶）之间表现出显著正相关性,交换态Cr与脱氢酶活性之间呈现出显著负相关性。上述特征反映了污水灌溉时间对土壤肥力及土壤酶活性具有复杂的影响效应,而这些效应是决定污水灌溉区土地生产力能否高产的重要因素。     

Decalcification of soils subject to periodic waterlogging

Intense decalcification of fine‐grained organic‐rich soils subject to periodic oxidation and reduction takes place in the Biesbosch, a freshwater, tidally influenced wetland area in the Rhine–Meuse delta in The Netherlands. Soil chemical (sulphide concentration and pore‐water characteristics) and hydrological variables (drainage) were measured in three representative Fluvisols differing in hydrology to identify processes inducing calcium carbonate dissolution. Both oxidation of previously formed iron sulphides during periods of low ground water and infrequent inundation, and increased carbon dioxide pressure in the soil during periods of waterlogging combined with drainage of pore‐water solutes, contribute significantly to decalcification of the hydric soils. The effects of these individual processes on decalcification are in the same order of magnitude in the studied soils. Depending on site‐specific hydrological conditions, approximately 0.1–0.3% calcium carbonate may be dissolved per year by a combination of these two processes, which is comparable to actual decalcification rates at these sites. Estimates of long‐term decalcification rates, based on knowledge of the hydrogeochemistry, may be used to assess the risks accompanying the conversion of agricultural soils into wetlands.     

Bodenentwicklung und Schwermetallgehalte einer Straßenkehrichtdeponie

Soil development and heavy metal contents of a street sweepings dump Soils from an unsealed street sweepings dump of the city of Kiel are inhomogeneous in their properties and in their distribution pattern. The deposited material is contaminated with copper, zinc, lead, and at lower concentrations with cadmium. The high pH-values lead to predominating immobility of heavy metals. However, heavy metals bonded in organic complexes are liable to be leached into the underground because of a high portion of large pores in these soils. Since there are only few other possible bonding mechanisms than organics, after the leaching of lime, pH decline, and mineralization of organic matter mobilization of heavy metals may be predicted. Thus, in the unsealed dump a danger of groundwater pollution with heavy metals remains. The site should be treated accordingly permanently after closing.     

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.     

Effects of acidification on the concentrations of heavy metals in running waters in Sweden

Heavy metals in running water are analysed within the Swedish Surface Water Monitoring Programme at about 80 stations. Data for selected rivers and brooks has been used to assess the effect of soil acidification on the concentrations of metals in waters. In southern Sweden, acidification shows a significant effect on Zn and Cd. In the upper parts of the drainage areas, there is an marked increased leakage of these metals from soils to waters indicated by elevated concentrations of Zn and Cd in brooks and also by high maxima during periods of low pH values. The increased leaching from forest soils also influences the concentrations in rivers in southern Sweden. During periods of high water flow, the pH values of the rivers decreases and the concentrations of Zn and Cd increases. At pH levels of 6.2–6.5 the concentrations of these metals are mostly 2–5 times higher as compared to pH levels of about 7.0. Since high concentrations of Zn and Cd coincides with high water flow, the transport of these metals has most certainly increased several times compared to the pre-industrial period. Hence, the by far most important human impact on the loading of Zn and Cd on the marine areas, surrounding southern Sweden is the increased leakage of these metals due to acidification. In northern Sweden the effects of acidification on Zn and Cd are less evident. In general, the concentrations of these metals are lower and the connection between pH and these metals are much less significant in the rivers. The links between acidification and the concentrations of Pb and Cu in the watercourses are comparatively much weaker. These two metals are more related to the content of organic matter in the waters and a possible effect of acidification is overshadowed by natural transport processes in soils and waters.     

Cu and Ni Mobility and Bioavailability in Sequentially Conditioned Soils

The potential ecological hazard of metals in soils may be measured directly using a combination of chemical and biological techniques or estimated using appropriate ecological models. Terrestrial ecotoxicity testing has gained scientific credibility and growing regulatory interest; however, toxicity of metals has often been tested in freshly amended soils. Such an approach may lead to derivation of erroneous toxicity values (EC₅₀) and thresholds. In this study, the impact of metal amendments on soil ecotoxicity testing within a context of ion competition was investigated. Four coarse-textured soils were amended with copper (Cu) and nickel (Ni), incubated for 16 weeks and conditioned by a series of total pore water replacements. Rhizon^TM extracted pore water Cu, Ni, pH and dissolved organic carbon (DOC) concentrations were measured after each replacement. Changes in ecotoxicity of soil solutions were also monitored using a lux-based biosensor (Escherichia coli HB101 pUCD607) and linked to variations in soil solution metal and DOC concentrations, pH and selected characteristics of the experimental soils (exchangeable calcium (Ca) and magnesium (Mg)). Prior to conditioning of soils, strong proton competition produced relatively high EC₅₀ values (low toxicity) for both, Cu and Ni. The successive replacement of pore waters lead to a decline of labile pools of metals, DOC and alleviated the ecotoxicological protective effect of amendment impacted soil solution chemistry. Consequently, derived ecotoxicity values and toxicity thresholds were more reflective of genuine environmental conditions and the relationships observed more consistent with trends reported in historically contaminated soils.     

Determination of High Resolution Pore Water Profiles of Trace Metals in Sediments of the Rupel River (Belgium) using Det (Diffusive Equilibrium in Thin Films) and DGT (Diffusive Gradients in Thin Films) Techniques

The techniques of diffusional equilibrium in thin films (DET) and diffusional gradients in thin films (DGT) were used to obtain high resolution pore water profiles of total dissolved and labile trace (mobilizable) metals in the sediments of the Rupel River, Belgium. DGT measures labile metal species in situ by immobilizing them on a resin gel after diffusion through a diffusive gel whereas for DET an equilibrium is established between the DET gel and the pore water. Concentrations of Pb and Zn obtained by DGT were in good agreement with the results obtained by centrifugation, and thus were well buffered by rapid equilibrium with the solid phase, whereas Fe, Mn and Cd were very tightly bound to the sediment phase and large differences were observed between the labile and the total metal concentrations. Cu, Zn, Co and Ni show intermediated behavior. Good correlations were found between the profiles of As and Fe and Mn and Co for DET as well as DGT showing a close link between the geochemical behavior of these elements. Cu, Zn, Pb and Cd are also influenced by the reductive mobilization of Fe and Mn oxides but are also closely linked to the bacterial degradation of organic matter in the surface sediments as to the precipitation of metal sulfides in the deeper layers.     

Relationship Between Extractable Metals in Acid Soils and Metals Taken Up by Tea Plants

Abstract

The accumulation of heavy metals in plants is related to concentrations andchemical fractions of the metals in soils. Understanding chemical fractions and availabilities of the metals in soils is necessary for management of the soils. In this study, the concentrations of copper (Cu), cadmium (Cd), lead (Pb), and zinc (Zn) in tea leaves were compared with the total and extractable contents of these heavy metals in 32 surface soil samples collected from different tea plantations in Zhejiang province, China. The five chemical fractions (exchangeable, carbonate‐bound, organic matter‐bound, oxides‐bound, and residual forms) of the metals in the soils were characterized. Five different extraction methods were also used to extract soil labile metals. Total heavy metal contents of the soils ranged from 17.0 to 84.0 mgCukg^?1, 0.03 to 1.09 mg Cd kg^?1, 3.43 to 31.2 mg Pb kg^?1, and 31.0 to 132.0 mg Zn kg^?1. The concentrations of exchangeable and carbonate‐bound fractions of the metals depended mainly on the pH, and those of organic matter‐bound, oxides‐bound, and residual forms of the metals were clearly controlled by their total concentrations in the soils. Extractable fractions may be preferable to total metal content as a predictor of bioconcentrations of the metals in both old and mature tea leaves. The metals in the tea leaves appeared to be mostly from the exchangeable fractions. The amount of available metals extracted by 0.01 mol L^?1 CaCl₂, NH₄OAc, and DTPA‐TEA is appropriate extractants for the prediction of metals uptake into tea plants. The results indicate that long‐term plantation of tea can cause sol acidification and elevated concentrations of bioavailable heavy metals in the soil and, hence, aggravate the risk of heavy metals to tea plants.     

The role of earthworms (<Emphasis Type="Italic">Eisenia fetida</Emphasis>) in influencing bioavailability of heavy metals in soils

The effects of earthworm (Eisenia fetida) activity on soil pH, dissolved organic carbon (DOC), microbial populations, fraction distribution and bioavailability of heavy metals (Zn, Cu, Cr, Cd, Co, Ni, and Pb) in five Chinese soils were investigated using pot experiments. A three-step extraction procedure recommended by the European Community Bureau of Reference (BCR; now Standards, Measurements and Testing Programme of the European Community) was used to fractionate the metals in soils into water soluble, exchangeable and carbonate bound (B1), Fe-oxides and Mn-oxides bound (B2) and organic matter and sulfide bound (B3). After the soils were treated with earthworms, the soil pH, water-soluble metal fraction and DOC increased. A significant correlation was obtained between the increased DOC and the increased metals in the water-soluble fraction. The heavy metals in fraction B1 increased after earthworm treatments, while those in fraction B3 decreased. No significant differences were observed for heavy metals in fraction B2. The microbial populations in soil were enumerated with the dilution plate method using several media in the presence of earthworms. The microbial populations increased due to earthworm activity. The biomass of wheat shoots and roots, and the heavy metal concentrations in wheat roots and shoots, were also increased due to the earthworm activity. The present results demonstrated that earthworm activity increases the mobility and bioavailability of heavy metals in soils.     

Methods for remediation of metal‐contaminated soils: Preliminary results

Abstract

Contamination of soils by heavy metals is one of the environmental problems that the scientific community faces today. Such soils are difficult to treat because the heavy metals cannot be destroyed. Moreover, they are usually bonded with other contaminants, in particular organic ones. The presence of these organic pollutants can make the removal of metals from soils substantially more complicated. One way of coping with the problem which has been studied in recent years is the use of fixing agents which make the heavy metals unavailable to the plants, or prevent their leaching towards the groundwater. Inorganic fixing agents in particular have been tested and found to be suitable, but some organic ones can also be used, at least as temporary fixing materials. This paper gives preliminary results on remediation techniques using compost and Trichoderma viride Pers.: Fr. as heavy metal fixing agents.     

Arsenic and metals mobility in soils impacted by tailings at Zimapán,México

Purpose

Mining wastes may cause important environmental impacts in soil, water, and air due to their high metals and arsenic contents. The aim of this work was the assessment of the mobility of arsenic and several heavy metals in soils located near different types of tailing heaps in the town of Zimapán, México.

Materials and methods

One hundred twenty soil samples were collected nearby to three tailing heaps, one oxidized presenting a red color (RT), and two with gray wastes (OSM and NSM) but with different age, during the dry and rainy seasons at the surface and to 40 cm depth, as well as to different distances from the deposits. Arsenic, Cd, Cu, Fe, Mn, Pb, V, and Zn total concentrations were determined; in addition, geochemical phase distribution of As, Cu, Mn, and Zn in selected samples was determined by sequential extraction. Concentrations were measured by graphite furnace atomic absorption spectrometry and inductively coupled plasma. To interpret the results, statistical analyses were performed.

Results and discussion

All samples presented high As concentrations reaching more than 50,000 mg kg^?1 close to OSM tailings, although the highest concentrations in the available fractions were measured in NSM impacted soils. Arsenic and metals concentrations exceeded the screening limits recommended for industrial sites. In samples influenced by OSM tailings, most of the elements analyzed were in the residual fraction, whereas in NSM and RT they were mostly in the organic and sulfide fractions and in the Fe and Mn oxides fractions, respectively. Larger concentrations of As and metals than those allowed by the screening values in Canada and the Netherlands were measured in the residential area representing a health threat for the inhabitants and the environment.

Conclusions

Acid mine drainage, water, and wind erosion of tailings have polluted nearby soils. Higher concentrations of As and metals were measured during the rainy season in gray tailings impacted soils and during the dry season in red tailings, showing both deposit types’ different mobility. Elements fractionation in soils depends mainly on tailings characteristics. Low metals and As proportions were found in the fraction with the highest mobility. Metals and arsenic are more stable in soils impacted by gray tailings, mainly in the organic and sulfides and residual fractions, while in RT, most are linked to Fe and Mn oxyhydroxides. Polluted soils in residential areas constitute a health hazard. Remedial actions must be taken to stop the population exposure.

     

苏南某焦化厂场地土壤和地下水特征污染物分布规律研究

以苏南某焦化厂为研究对象,在对污染区域初步识别的基础上,采集了0～4.5 m深的22个土壤样品和2个地下水样品,利用GC/MS等检测了多环芳烃类、总石油烃、苯系物、重金属,总氰化物、挥发酚、硫化物的含量,并研究了其在不同功能区土壤和地下水中的特征分布。结果表明：（1）该焦化场土壤和地下水受到了不同程度的污染,其中炼焦炉周边、焦油和洗油储罐区、焦油和粗苯加工车间是污染最严重的区域;（2）土壤中主要超标污染物是多环芳烃、总氰化物、总石油烃、单环芳香烃、二苯呋喃、苯胺、硫化物、挥发酚和一些苯酚类化合物;（3）地下水重点污染区域粗苯车间受到总氰化物、苯胺、苯酚类、萘、总石油烃、单环芳香烃的严重污染,污水处理站区域地下水主要污染物包括总氰化物、萘、总石油烃、苯。     

土壤重金属形态对径流中重金属流失的影响

土壤重金属的积累可促进地表径流中重金属的流失,流失量与土壤中重金属的形态有关。田间观测和室内模拟淋洗试验的结果都表明,径流或淋出液中重金属主要来源于土壤的交换态(包括水可溶态)重金属;土壤重金属总量与径流中重金属浓度相关不明显;用稀盐(0.01mol/LCaCl2)和1mol/LNH4OAc提取的土壤重金属量与径流和淋出液中重金属浓度都呈显著的相关,可较好地表征土壤中重金属流失潜力。     

Dissolution of magnetite and redistribution of heavy metals in urban soils (model experiment)

Technogenic magnetite in urban soils is extremely various in properties. Its particles strongly differ in magnetic susceptibility and degree of association with heavy metals. In the city of Perm, particles of magnetite enriched with different heavy metals are precipitated, which indicates different sources of technogenic magnetite within the limits of the city. The dissolution of magnetite and the effect of this process on the behavior of heavy metals have been simulated by the magnetochemical method. In strongly magnetic soils, the dissolution of highly magnetic macrocrystalline magnetite is accompanied by the dissolution of heavy metals: Cr, Mn, Ni, Zn, Pb, and Cu. The secondary precipitates of hydroxides of iron and heavy metals (predominantly Pb, Cu, and Ni) are formed relatively rarely, mainly in weakly magnetic soils, where slightly magnetic and dispersed magnetite is present. In cities, the dissolution of magnetite is favored by the added salts and organic acids released by plants.     

Biodegradation of Synthetic Dyes—A Review

The upper Great Egg Harbor River watershed in New Jersey’s Coastal Plain is urbanized but extensive freshwater wetlands are present downstream. In 2006–2007, studies to assess levels of total mercury (THg) found concentrations in unfiltered streamwater to range as high as 187 ng/L in urbanized areas. THg concentrations were <20 ng/L in streamwater in forested/wetlands areas where both THg and dissolved organic carbon concentrations tended to increase while pH and concentrations of dissolved oxygen and nitrate decreased with flushing of soils after rain. Most of the river’s flow comes from groundwater seepage; unfiltered groundwater samples contained up to 177 ng/L of THg in urban areas where there is a history of well water with THg that exceeds the drinking water standard (2,000 ng/L). THg concentrations were lower (<25 ng/L) in unfiltered groundwater from downstream wetland areas. In addition to higher THg concentrations (mostly particulate), concentrations of chloride were higher in streamwater and groundwater from urban areas than in those from downstream wetland areas. Methylmercury (MeHg) concentrations in unfiltered streamwater ranged from 0.17 ng/L at a forest/wetlands site to 2.94 ng/L at an urban site. The percentage of THg present as MeHg increased as the percentage of forest + wetlands increased, but also was high in some urban areas. MeHg was detected only in groundwater <1 m below the water/sediment interface. Atmospheric deposition is presumed to be the main source of Hg to the wetlands and also may be a source to groundwater, where wastewater inputs in urban areas are hypothesized to mobilize Hg deposited to soils.