Application of remediation techniques for immobilization of metals in soils contaminated by a pyrite tailing spill in Spain

Abstract. Remediation techniques for soil pollution have been studied in the aftermath of a tailing spill from a pyrite-mine holding pond in Aznalcóllar (southwest Spain). Given the extent of the accident and the characteristics of the affected area, we conclude that, after the removal of the tailings, the only feasible remediation measure involves chemical immobilization of the pollutants. The best treatment tested proved to be liming in combination with amendment materials such as soils rich in iron oxides and clay. Monitoring for 3 years has demonstrated that the system is effective for reducing the solubility of the most mobile forms of the main pollutant elements, although further monitoring is recommended.     

Trace metal distribution in the bed,bank and suspended sediment of the Ravensbourne River and its implication for sediment monitoring in an urban river

Journal of Soils and Sediments - This study aims to identify a suitable sediment compartment for sediment quality monitoring by: (a) studying the concentration of trace metals (Cd, Cu, Ni, Pb and...     

Sequential solidification/stabilization and thermal process under vacuum for the treatment of mercury in sediments

Purpose  

Millions of cubic meters of sediments are dredged every year in the world. About 10–20% on weight basis of this material is contaminated by organic and/or inorganic pollutants. This work presents the laboratory tests performed to study a system for the remediation and reuse of mercury-contaminated sediments. The treatment is based on a cement-based granulation step (solidification/stabilization (S/S)), followed by a thermal process under vacuum during which volatile and semi-volatile compounds are removed. The experiments focused on: (1) cement hydration reactions; (2) pollutant removal efficiencies; and (3) leaching behavior, in relation to temperature and duration of the thermal process. Mercury speciation was also investigated.     

生物炭修复重金属污染农田土壤的机制及应用研究进展

将生物质转化为生物炭并用于重金属污染农田土壤修复中,是有效利用生物质资源、保障粮食安全的有效途径之一。然而,生物炭的应用效率受其特性和土壤环境影响极大。该研究综述了生物炭特性,并探讨了生物质和热解温度对其影响规律,阐明了生物炭对重金属的直接固定作用,以及通过影响土壤pH值、阳离子交换量（Cation Exchange Capacity,CEC）、矿物组分和有机质等,进而间接固定重金属的作用机制。同时,该文系统总结了国内外生物炭在田间试验中的应用,从土壤重金属迁移性和生物有效性、作物累积重金属和作物产量等3个方面阐明了生物炭的应用效果和作用规律。针对田间试验条件区别于室内试验的特殊性,探讨了生物炭施撒方式及用量、施肥等田间管理和气候环境等现场条件对生物炭应用的影响,并对今后完善生物炭在土壤修复中作用机制、扩大研究尺度和长期土壤监测等方面研究进行了展望。     

Model experimental study on the migration behavior of heavy metals in electrokinetic remediation process for contaminated soil

Recently in Japan, like in other industrialized countries, treatment of contaminated soil or ground has become an important issue in redeveloping such areas as old factories, mining sites, and other polluted sites. In these cases, measures such as a construction of cut-off walls and disposal to controlled waste disposal sites have been so far taken. But, the treatment of contaminated soils has become more difficult nowadays. Therefore, remediation of contaminated soil by removal or extraction of contaminants is necessary and various methods have been developed and applied in many countries. Authors have tried to develop an electrokinetic remediation method for soil contaminated with heavy metals and some basic and pilot scale experiments have been carried out. In this paper, the results of a model experiment using an artificial soil contaminated with Cu or Ph or Cr are presented as follows. i) In the electrokinetic process, migration of water to the cathode by electroosmosis, migration of ions to the cathode or anode by electrophoresis and electrolysis of water occur spontaneously. ii) Upon DC loading, Cu and Pb migrate to the cathode and accumulate as oxides or hydroxides near the cathode but are not removed from contaminated soil. However, in the case of Cr contaminated soil, Cr in the form of Cr(VI) migrates to the anode and is removed from soil through the drainage water. iii) After DC loading for 2 weeks, the concentration of exchangeable cations and composition of soil changed drastically while the CEC and clay mineralogy did not change appreciably.     

浮水植物对淡水水产品中重金属污染的防治修复作用研究——以银鲫为模型

为研究浮水植物对淡水水产品中重金属污染的防治修复效果,本研究以银鲫为动物模型,评价了凤眼莲、肚兜萍、大薸3种浮水植物混合植株(质量比为1∶1∶1)对鱼体重金属污染的防治修复能力。以GB 8979-1996 《污水综合排放标准》所规定的污染物最高允许排放浓度的1倍、 2倍和5倍分别设置3个暴露水平,通过对比分析实验组与对照组银鲫各组织器官中6种重金属的含量,发现其重金属含量与暴露水平存在明显的浓度-效应关系,且当水环境中重金属含量在污染物最高允许排放浓度的5倍以内时,实验组银鲫体内6种重金属含量均显著小于对照组(P<0.05),这表明混合植株能够通过降低水环境中重金属的含量而减小鱼体的受污染程度。本研究为淡水水产品的质量安全及重金属防治研究提供了相关数据支持。     

污泥资源化处理与利用中控制重金属污染的研究进展

简介了国内外污泥资源化与利用过程中控制重金属污染的研究进展,并提出治理污泥重金属污染的途径。     

A promising amendment for the immobilization of heavy metal(loid)s in agricultural soil,northwest China

Journal of Soils and Sediments - In situ remediation techniques are currently limited for agricultural soil contaminated by heavy metal(loid)s, particularly for alkaline soil. In this study, we...     

Importance of dose metrics for lethal and sublethal sediment metal toxicity in the oligochaete worm Lumbriculus variegatus

Background, Aims, and Scope  There is an increasing demand for controlled toxicity tests to predict biological effects related to sediment metal contamination. In this context, questions of metal-specific factors, sensitivity of toxicity endpoints, and variability in exposure duration arise. In addition, the choice of the dose metrics for responses is equally important and is related to the applicability of the concept of critical body residue (CBR) in exposure assessments, as well as being the main focus of this study. Methods  Experiments were conducted to assess toxicity of Cd, Cr, Cu and Pb to the oligochaete worm Lumbriculus variegatus with the aim of determining CBRs for two response metrics. Mortality and feeding activity of worms exposed to sediment-spiked metals were used as end-points in connection with residue analyses from both the organisms and the surrounding media. Results  LC50 values were 0.3, 1.4, 5.2, and 6.7 mg/L (from 4.7 μmol/L to 128.0 μmol/L), and the order of toxicity, from most toxic to least toxic, was Cu > Cd > Pb>Cr. By relating toxicity to body residue, variability in toxicity among the metals decreased and the order of toxicity was altered. The highest lethal residue value was obtained for Cu (10.8 mmol/kg) and the lowest was obtained for Cd (2.3 mmol/kg). In the 10-d sublethal test, both time and metal exposure were an important source of variation in the feeding activity of worms. The significant treatment effects were observed from worms exposed to Cd or Pb, with the controls yielding the highest feeding rate. However, quantitative changes in the measured endpoint did not correlate with the exposure concentrations or body residues, which remained an order of magnitude lower than in the acute exposures. Discussion  Both response metrics were able to detect a toxic effect of the metals. However, the ranking of metal toxicity was dependant on the choice of the dose metric used. An attempt to form a causal mortality-mediated link between tissue residues and metal toxicity was successful in water-only exposures. The results also indicated that egestion rate was a sensitive toxicity end point for predicting the effects of sediment contamination. Conclusions  By relating the biological response with the tissue metal residues, toxicity data was comparable to both environmental media as well as different response metrics and time scales. The results also revealed the importance of metal toxicity ranking on a molar basis and, furthermore, a direct link to the CBR concept was established. Recommendations and Perspectives  There is a growing demand for methods to assess the effects of contaminated sediments to benthic fauna and whole aquatic ecosystems. Such information is needed for sediment quality guidelines that are currently being developed in many countries and remediation processes. The use of body residues as a dose metric in metal toxicity studies may help to overcome difficulties related to bioavailability issues commonly faced in sediment toxicity studies. ESS-Submission Editor: Prof. Dr. Henner Hollert (henner.hollert@bio5.rwth-aachen.de)     

Effects of heavy metal contamination and remediation on soil microbial communities in the vicinity of a zinc smelter as indicated by analysis of microbial community phospholipid fatty acid profiles

Heavy metal contamination in an area immediately surrounding a zinc smelter has resulted in destruction of over 485 hectares of forest. The elevated levels of heavy metals in these soils have had significant impacts on the population size and overall activity of the soil microbial communities. Remediation of these soils has resulted in increases in indicators of biological activity and viable population size, which suggest recovery of the microbial populations. Questions remain as to how the metal contamination and subsequent remediation at this site have impacted the population structure of the soil microbial communities. In the current study, microbial communities from this site were analyzed by the phospholipid fatty acid (PLFA) procedure. Principal component analysis of the PLFA profiles indicated that there were differences in the profiles for soils with different levels of metal contamination, and that soils with higher levels of metal contamination showed decreases in indicator PLFAs for mycorrhizal fungi, Gram-positive bacteria, fungi, and actinomycetes. PLFA profiles for remediated sites indicated that remediated soils showed increases in indicator PLFAs for fungi, actinomycetes, and Gram-positive bacteria, compared to unremediated metal contaminated soils. These data suggest a change in the population structure of the soil microbial communities resulting from metal contamination and a recovery of several microbial populations resulting from remediation.     

Evaluating recovery strategies for an ocelot (Leopardus pardalis) population in the united states

The ocelot Leopardus pardalis population in the United States was listed as endangered in 1982, with only two known isolated breeding populations occurring in southern Texas. Conservation concerns for ocelots include loss of dense thornshrub habitat, mortality from ocelot-vehicle collisions, and genetic erosion. In this study, we used a population viability analysis (PVA) to evaluate four recovery strategies (i.e., supplementation of additional ocelots, reduced road mortality, habitat protection and restoration, and linkage of two breeding populations) for ocelot conservation management. We used the VORTEX (Version 9.42) program to conduct our PVA for an ocelot population located in Cameron County, Texas. Each scenario was simulated 500 times over 100 years. We compared the effectiveness of recovery strategies and combinations thereof with estimates of extinction probability and final population size. Model scenarios with no recovery strategies predicted an extinction probability of 0.65 for the Cameron population of ocelots over 100 years. The protection and restoration of thornshrub habitat was the most effective recovery strategy, followed by population linkage and reduced road mortality, with the supplementation of ocelots being the least effective strategy. Protection and restoration of ocelot habitat cannot be accomplished without the participation of private landowners. Using an adaptive management approach, future actions need to be taken to monitor ocelot populations and habitats and help to reduce the high probability of extinction predicted in our PVA for the ocelot population in Cameron County.     

Investigation of thermal decomposition as the kinetic process that causes the loss of crystalline structure in sucrose using a chemical analysis approach (part II)

High performance liquid chromatography (HPLC) on a calcium form cation exchange column with refractive index and photodiode array detection was used to investigate thermal decomposition as the cause of the loss of crystalline structure in sucrose. Crystalline sucrose structure was removed using a standard differential scanning calorimetry (SDSC) method (fast heating method) and a quasi-isothermal modulated differential scanning calorimetry (MDSC) method (slow heating method). In the fast heating method, initial decomposition components, glucose (0.365%) and 5-HMF (0.003%), were found in the sucrose sample coincident with the onset temperature of the first endothermic peak. In the slow heating method, glucose (0.411%) and 5-HMF (0.003%) were found in the sucrose sample coincident with the holding time (50 min) at which the reversing heat capacity began to increase. In both methods, even before the crystalline structure in sucrose was completely removed, unidentified thermal decomposition components were formed. These results prove not only that the loss of crystalline structure in sucrose is caused by thermal decomposition, but also that it is achieved via a time-temperature combination process. This knowledge is important for quality assurance purposes and for developing new sugar based food and pharmaceutical products. In addition, this research provides new insights into the caramelization process, showing that caramelization can occur under low temperature (significantly below the literature reported melting temperature), albeit longer time, conditions.     

黄丘一副区小流域暴雨洪水输沙过程预报模型

本文根据黄丘—副区小流域暴雨洪水特性,应用霍尔顿(R·E·Horton)下渗理论和河网汇流理论建立小流域降雨径流概念模型,采用相关分析提出输沙过程预报模型,并用该区一些代表小流域实测洪水资料对模型进行验证,指出了模型的应用途径。     

SPME-MS-MVA as an electronic nose for the study of off-flavors in milk

A new technique using solid-phase microextraction, mass spectrometry, and multivariate analysis (SPME-MS-MVA) was developed for the study of off-flavors in milk. The analytical column of a GC/MS system was replaced with a 1-m deactivated fused-silica column, which served as a transfer line to deliver volatiles extracted from milk samples with a Carboxen-SPME fiber to the mass spectrometer. Mass fragmentation data resulting from the unresolved milk volatile components were subjected to MVA. Principal component analysis based on SPME-MS-MVA provided rapid differentiation of control reduced-fat milk (2% butterfat content) samples from reduced-fat milk samples abused by light, heat, copper, and microbial contamination. The three psychrotrophic bacteria studied included Pseudomonas fluorescens, Pseudomonas aureofaciens, and Pseudomonas putrefaciens. SPME-MS-MVA is rapid and offers significant advantages over commercial electronic nose instruments currently being used as quality assurance tools to differentiate normal-tasting food and beverage samples from those containing off-flavors and malodors.     

Abiotic reduction of mercury by humic substances in aquatic system — an important process for the mercury cycle

The potential ability of humic substances to reduce Hg(II) to Hg(0) in aqueous systems and, consequently, strongly influence Hg speciation and mobility in the environment is known but has not been studied in detail. A demonstration of the redox behavior of Hg in the presence of humic substances is made in the present work. Calculations show that the reduction is thermodynamically possible. The effects of some chemical parameters (pH, aerobic/anaerobic conditions, presence of chloride) on the process were studied experimentally. Hg(0) production was highest in O₂-free systems in the absence of chloride at pH ca 4.5, when ca 25% of initially 2x10^?6 M Hg(II) was reduced to Hg(0) in 50 hr. The presence of a competing ion (10^?4 M Eu) in the system as well as methylation of the carboxyl groups in the humic substance considerably reduced the Hg(0) production. The practical importance of the abiotic reduction of Hg in the environment is pointed out.     

Podzolization as a deferralitization process: a study of an Acrisol–Podzol sequence derived from Palaeozoic sandstones in the northern upper Amazon Basin

Morphological, geochemical and mineralogical studies were carried out in a representative soil catena of the low‐elevation plateaux of the upper Amazon Basin to interpret the steps and mechanisms involved in the podzolization of low‐activity clay soils. The soils are derived from Palaeozoic sandstones. They consist of Hydromorphic Podzols under tree savannah in the depressions of the plateaux and predominantly of Acrisols covered by evergreen forest elsewhere. Incipient podzolization in the uppermost Acrisols is related to the formation of organic‐rich A and Bhs horizons slightly depleted in fine‐size particles by both mechanical particle transfer and weathering. Weathering of secondary minerals by organic acids and formation of organo‐metallic complexes act simultaneously over short distances. Their vertical transfer is limited. Selective dissolution of aluminous goethite, then gibbsite and finally kaolinite favour the preferential cheluviation of first Fe and secondly Al. The relatively small amount of organo‐metallic complexes produced is related to the quartzitic parent materials, and the predominance of Al over Fe in the spodic horizons is due to the importance of gibbsite in these low‐activity clay soils. Morphologically well‐expressed podzols occur in strongly iron‐depleted topsoils of the depression. Mechanical transfer and weathering of gibbsite and kaolinite by organic acids is enhanced and leads to residual accumulation of sands. Organo‐metallic complexes are translocated in strongly permeable sandy horizons and impregnate at depth the macro‐voids of embedded soil and saprolite materials to form the spodic Bs and 2BCs horizons. Mechanical transfer of black particulate organic compounds devoid of metals has occurred later within the sandy horizons of the podzols. Their vertical transfer has formed well‐differentiated A and Bh horizons. Their lateral removal by groundwater favours the development of an albic E horizon. In an open and waterlogged environment, the general trend is therefore towards the removal of all the metals that have initially accumulated as a response to the ferralitization process and have temporarily been sequestrated in organic complexes in previous stages of soil podzolization.     

Evaluation of the Mehlich 3 Reagent as an Extractant for Cations and Available Phosphorus for Soils in Mozambique

Accurate soil testing procedures contribute to agricultural development of Mozambique. The Mehlich 3 (M-3) procedure has not been evaluated for Mozambican soils despite its wide applicability. Results showed M-3 solution could extract exchangeable calcium (Ca), magnesium (Mg), and potassium (K) as well as 1 M ammonium acetate (NH₄OAc), while M-3 was not appropriate for extraction of exchangeable sodium (Na). M-3 was an alternative procedure to Bray-I for available phosphorus (P) extraction. Although M-3 extracted 1.6 times more P than Bray-I, determination coefficient between the two procedures showed significantly high value. P content in M-3 extracts can determine using inductively coupled plasma spectrophotometers (ICP) to maximize the merits of M-3. In conclusion, M-3 is applicable for determination of exchangeable Ca, Mg, K, and available P, in a single determination using ICP, and should contribute to development of effective and accurate soil diagnosis in Mozambique.     

Podzolization as a deferralitization process: dynamics and chemistry of ground and surface waters in an Acrisol – Podzol sequence of the upper Amazon Basin

Hydrochemical processes involved in the development of hydromorphic Podzols are a major concern for the upper Amazon Basin because of the extent of the areas affected by such processes and the large amounts of organic carbon and associated metals exported to the rivers. The dynamics and chemical composition of ground and surface waters were studied along an Acrisol‐Podzol sequence lying in an open depression of a plateau. Water levels were monitored along the sequence over a period of 2 years by means of piezometers. Water was sampled in zero‐tension lysimeters for groundwater and for surface water in the drainage network of the depression. The pH and concentrations of organic carbon and major elements (Si, Fe and Al) were determined. The contrasted changes reported for concentrations of Si, organic carbon and metals (Fe, Al) mainly reflect the dynamics of the groundwater and the weathering conditions that prevail in the soils. Iron is released by the reductive dissolution of Fe oxides, mostly in the Bg horizons of the upslope Acrisols. It moves laterally under the control of hydraulic gradients and migrates through the iron‐depleted Podzols where it is exported to the river network. Aluminium is released from the dissolution of Al‐bearing minerals (gibbsite and kaolinite) at the margin of the podzolic area but is immobilized as organo‐Al complexes in spodic horizons. In downslope positions, the quick recharge of the groundwater and large release of organic compounds lead to acidification and a loss of metals (mainly Al), previously stored in the Podzols.     

Total and size-fractionated mass of road-deposited sediment in the city of Prince George,British Columbia,Canada: implications for air and water quality in an urban environment

Purpose  

The urban sedimentary system is attracting increasing interest because of its role in influencing air and water quality. A large amount of road-deposited sediment (RDS) lies on the road network of Prince George, a city of about 80,000 people, in British Columbia, Canada. The objectives of this study were: (1) to determine the total mass of RDS within the city, and how this varied over time and space; and (2) to determine the temporal and spatial variations in the particle-size fractions of the RDS.     

Suitability of inorganic and organic amendments for in situ immobilization of Cd,Cu, and Zn in a strongly contaminated Kastanozem of the Mashavera valley,SE Georgia. I. Effect of amendments on metal mobility and microbial activity in soil

The aim was to find an adequate, cost‐efficient in situ remediation technique for the Mashavera valley, a mining area in SE Georgia heavily contaminated with Cd, Cu, and Zn. A 12‐month experiment was conducted to test: iron grit, natural zeolite, biochar, and Divergan® (a scavenger) for soil melioration. The amendments were added in different concentrations to the topsoil of a Kastanozem. Mobile metal concentrations decreased with increasing concentrations of amendments in the sequence Divergan® >> iron grit ≈ natural zeolite > biochar. In the same order amendments enhanced activities of soil microbial respiration, alkaline phosphatase, and dehydrogenase; microbial C also followed this trend. A sequential extraction confirmed a shift from easily mobilized to heavily bound fractions. The addition of 2% (w/w) of Divergan® was sufficient to lower mobile trace metal concentrations below German thresholds by chemisorption, and soil microbial activity was significantly increased. The effects of all other treatments were at a much lower level and not found suitable due to needed application rates.