Assessing potential bioavailability of metals in sediments: A proposed approach

Due to anthropogenic inputs, elevated concentrations of metals frequently occur in aquatic sediments. In order to make defensible estimates of the potential risk of metals in sediments and/or develop sediment quality criteria for metals, it is essential to identify that fraction of the total metal in the sediments that is bioavailable. Studies with a variety of benthic invertebrates indicate that interstitial (pore) water concentrations of metals correspond very well with the bioavailability of metals in test sediments. Many factors may influence pore water concentrations of metals; however, in anaerobic sediments a key phase controlling partitioning of several cationic metals (cadmium, nickel, lead, zinc, copper) into pore water is acid volatile sulfide (AVS). In this paper, we present an overview of the technical basis for predicting bioavailability of cationic metals to benthic organisms based on pore water metal concentrations and metal-AVS relationships. Included are discussions of the advantages and limitations of metal bioavailability predictions based on these parameters, relative both to site-specific assessments and the development of sediment quality criteria.     

Mobilization of trace metals and inorganic compounds during resuspension of anoxic sediments from Trepangier Bayou, Louisiana

The release of trace metals (Mn, Ni, Co, Cu, Zn, Pb, and Cd) and inorganic compounds (As) from initially anoxic Trepangier Bayou sediments, Louisiana and the sources of the released metals were investigated. After 1 to 2 d aeration, significant amounts of trace metals (Mn, Zn, Cd, Ni, and Co) were released to the aqueous phase with increased acidity, primarily due to the oxidation of acid-volatile sulfide and ferrous iron and iron sulfide minerals. The addition of a bacterial inhibitor, NaN,, to the Trepangier sediment during resuspension inhibited metal release, suggesting that microbial catalysis can regulate metal mobilization during sediment resuspension. In a well buffered system, oxidation of iron sulfides alone did not appear to induce trace metal release. Moreover, when Trepangier sediment was resuspended in anoxic conditions at neutral pH, <1% of the trace metal content was released, whereas a significant release of metal was observed under acidic anoxic conditions. Although oxidation of iron sulfide minerals is an essential prerequisite for the release of Zn, Co, Cd, and Ni, carbonates and oxides also play a role. The trace metals and inorganic compounds investigated could be classified into three groups according to their release characteristics: (i) Mn, Zn, Cd, Ni, and Co; (ii) Fe, Pb, and As; and (iii) Cu. The groupings appeared to depend on the sources of compounds and their relative affinity, after oxidation, to iron oxyhydroxides or organic matter.     

Acid Volatile Sulfides,Equilibrium Partitioning,and Hazardous Waste Site Sediments

/ Information provided by acid volatile sulfide (AVS) andequilibrium partitioning (EqP) theory is described, including two caseexamples, relative to hazardous waste site sediments. AVS and EqP are toolsin the toolbox, which can serve three main functions: screening,prioritization, and assisting in explaining observed effects. They should notbe used in isolation for decision making, particularly at hazardous waste orother sites where the sediments are contaminated by materials such as coal,coke, and pitch.KEY WORDS: Acid volatile sulfides; Equilibrium partitioning; Sediments;Hazardous waste     

Fractionation of selected metals in the sediments of Cochin estuary and Periyar River, southwest coast of India

Cochin estuary is one of the highly polluted aquatic systems of the southwest coast of India. The present study focuses on the assessment of heavy metals (Zn, Cd, Pb, and Cu) present in the sediments of Cochin estuary and the adjoining Periyar River. The sediments were analyzed for total metal content and various chemically bound fractions such as exchangeable, carbonate bound, easily reducible, organic, and residual. Total metal content of sediment was found higher than the average values reported from other Indian rivers. The mean concentration of Zn, Cd, Pb, and Cu in the sediments was 1,249.44, 9.5, 221.37, and 166.14???g/g, respectively. The results of sequential extraction showed that the concentration of Cd was high in the first two weakly bound fractions (exchangeable and carbonate bound) than the other metals, which are high in residual and organic bound fractions. Risk-assessment code analysis and environmental indices (enrichment factor and pollution load index) suggest that the sediments are highly polluted with metals, especially Cd.     

Metal bioavailability and speciation in a wetland tailings repository amended with biosolids compost,wood ash,and sulfate

Lead poisoning of waterfowl from direct ingestion of wetland mine tailings has been reported at the Coeur d'Alene River basin in Idaho. A greenhouse study was conducted to evaluate the effects of surface applications of amendments on lead bioavailability in the tailings. Treatments included sediment only, and sediment with three different surface amendments: (i) biosolids compost plus wood ash, (ii) compost + wood ash + a low SO4(2-) addition as K2SO4, and (iii) compost + wood ash + a high SO4(2-) addition. Measured variables included growth and tissue Pb, Zn, and Cd concentration of arrowhead (Sagittaria latifolia Willd.) and cattail (Typha latifolia L.) and soil pH, redox potential (Eh), pore water Pb, Pb speciation by X-ray absorption spectroscopy, and in vitro Pb bioavailability. The compost + ash amendment alleviated phytotoxicity for both plant species. Bioavailability of Pb as measured by a rapid in vitro extract decreased by 24 to 34% (over control) in the tailings directly below the amendment layer in the compost + SO4 treatments. The ratio of acid volatile sulfide (AVS) to simultaneously extracted metals (SEM) also indicated a reduction in Pb bioavailability (1:40 control, 1:20 compost, 1:8 compost + low SO4, and 1:3 compost + high SO4). Extended X-ray adsorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy data indicated that lead sulfide was greater after 99 d in the treatments that included additions of sulfate. These results indicated that, under reducing conditions, surface amendments of compost + wood ash (with or without sulfate) decreased the bioavailability of Pb in metal-contaminated mine tailings.     

柴窝堡湖表层底泥重金属污染评价

研究了乌鲁木齐市柴窝堡湖表层底泥的重金属含量,并采用Hakanson潜在生态危害指数法对底泥中的重金属潜在生态风险进行评价。结果表明:底泥中Cu、Zn、Pb、Cd含量均超出乌鲁木齐市土壤背景值。除湖心区外,Cd在5个监测区域中的潜在生态危害均为中等;其它重金属在5个采样点的潜在生态危害均为轻微。各重金属间的相关性分析表明,Zn与Cu,Pb与Cd、Cu呈显著正相关,说明这4种元素污染源可能相同。柴窝堡湖表层底泥受到Cu、Zn、Pb、Cd污染,需采取相应措施防止重金属由底泥进入水相。     

西湖和东苕溪沉积物重金属化学形态分析

不同赋存形态重金属的环境行为和生态效应不同,水体沉积物中重金属的迁移转化及其潜在环境危害更大程度上取决于其赋存形态。本研究在西湖和东苕溪设置12个采样点采集沉积物样品,采用改进BCR分步提取法,提取了重金属污染物的4种化学形态,分别为弱酸提取态、可还原态、可氧化态及残渣态。结果表明:沉积物中Cd以弱酸提取态为主,对外界环境的变化极其敏感,并易于发生迁移转化,生态风险较高。Cu离子对有机质表现出极强的亲和力导致Cu的可氧化态含量较高也有一定的生态风险。Pb会被Fe-Mn氧化物所吸附导致Pb的可还原态含量较高,存在较高的潜在生态危害。Mn的弱酸提取态、可还原态和残渣态含量都较高,在迁移的过程中变化地较快,能够逐渐降低Mn对自然环境的危害。其他各重金属(As、Cr、Zn)则都以残渣态为主,潜在危害较低。     

Short- and longer-term effects of the willow root system on metal extractability in contaminated dredged sediment

Willow (Salix spp.) stands are often proposed as vegetation covers for the restoration and stabilization of contaminated and derelict land. Planting willows on dredged sediment disposal sites for biomass production can be an alternative to traditional capping techniques. However, with the introduction of willow stands on dredged sediment disposal sites, the possibility of increased contaminant availability in the root zone must be acknowledged as it can increase the risk of leaching. Two trials investigated the availability of Cd, Zn, Cu, and Pb in the root zones of willows grown on contaminated sediment. To assess the effects of willow root growth on metal extractability and mobility, bulk and rhizosphere sediment samples were extracted with deionized water, ammonium acetate at pH 7, and ammonium acetate-EDTA at pH 4.65. A rhizobox experiment was used to investigate the short-term effect of willow roots on metal availability in oxic and anoxic sediment. Longer-term effects were assessed in a field trial. The rhizobox trial showed that Cd, Zn, and Cu extractability in the rhizosphere increased while the opposite was observed for Pb. This was attributed to the increased willow-induced oxidation rate in the root zone as a result of aeration and evapotranspiration, which masked the direct chemical and biological influences of the willow roots. The field trial showed that Cu and Pb, but not Cd, were more available in the root zone after water and ammonium acetate (pH 7) extraction compared with the bulk sediment. Sediment in the root zone was better structured and aggregated and thus more permeable for downward water flows, causing leaching of a fraction of the metals and significantly lower total contents of Cd, Cu, and Pb. These findings indicate that a vegetation cover strategy to stabilize sediments can increase metal availability in the root zone and that potential metal losses to the environment should be considered.     

The desorption of antimony(V) from sediments, hydrous oxides, and clay minerals by carbonate, phosphate, sulfate, nitrate, and chloride

The desorption of antimony, Sb(V), from two sediment samples by phosphate, carbonate, sulfate, chloride, and nitrate at pH 8 was examined. One highly contaminated sediment sample was taken from an Sb mine (Goesdorf, Luxembourg); the other sample was the certified reference material PACS-2 (marine sediment). Phosphate was found to have a strong mobilizing ability, whereas that of carbonate was in general weaker. For comparison, and to understand better the possible importance of individual components of the sediments, desorption experiments were performed on pure phases (i.e., hydrous oxides of Fe, Mn, and Al) and the clay minerals kaolinite and montmorillonite. In the cases of hydrous metal oxides, Sb(V) was most effectively desorbed by phosphate, followed by carbonate. Phosphate also desorbed Sb(V) from the clay minerals, whereas carbonate had no effect. The pH dependence of adsorption of Sb(V) in the absence and presence of carbonate revealed that adsorption densities were higher (except in the case of montmorillonite) in the absence of carbonate, suggesting a competition between carbonate and [Sb(OH)] for surface sites generally and a lowering of surface charge in the case of hydrous aluminum oxide. The observations are unlikely to be due to ionic strength effects because activity coefficients in the blank and spiked solutions differ by <4%. Desorption experiments on sediments with varying concentrations of phosphate and carbonate demonstrated that at environmentally relevant concentrations, desorption by phosphate is negligible, whereas the effect of carbonate is not. Sulfate, chloride, and nitrate generally had little effect. The proportion of Sb desorbed in blank experiments coincides with that mobilized in the first fraction of the Bureau Communautaire de Référence (BCR) sequential extraction (easily exchangeable and carbonate-bound fraction).     

Speciation of some heavy metals in River Nile sediments,Cairo, Egypt

River sediments are basic components of our environment. It also constitutes a major source of persistent bioaccumulative toxic chemicals which may pose threats to ecological and human health even after contaminants are no longer released from point and non-point sources. Therefore, the aim of this study was to investigate the mobility and the availability of metals in sediments from different sites along the Nile River in Cairo district using sequential chemical extraction technique. The speciation data showed that most metals were associated with organic/sulfide and residual fractions. The order of total metal concentrations in sediment samples was found to be Fe > Mn > Zn > Ni > Cu ≥ Cr > Pb > Cd.     

铁尾矿路用对土壤环境质量影响及安全修复研究

为分析铁尾矿路用对道路沿线土壤环境质量影响的程度,对铁尾矿化学成分及有害物质进行测定,以秦巴山区的山地黄棕壤作为道路建设的耕土环境,把铁尾矿按70%~90%的推荐比例掺入,铁尾矿中的重金属按照最不利的全浸入式扩散进行分析,对黄棕壤中重金属含量超过限制要求的重金属进行安全修复,使铁尾矿道路沿线黄棕壤的重金属含量满足限制要求。结果表明:铁尾矿硫化物含量高达到2.89%,不满足配制混凝土的硫化物限量要求;铁尾矿路用的土壤中重金属Cr最大含量103.24 mg/kg、Cu最大含量116.4 mg/kg,国评标准污染等级均为Ⅱ级,其余重金属元素含量都在国家标准正常范围以内;高生物量的非超富集植物、细菌微生物、城市的污泥、工业粉煤灰(5%粉煤灰+50%尾矿砂+45%黄褐土)能够很好修复重金属Cr、Cu污染的土壤;含钙类物质的钝化剂处置重金属Cr、Cu污染效果好,腐殖酸、凹凸棒土、膨润土可以钝化土壤中的重金属Cu;高生物量非超富集植物、微生物钝化剂联合使用,具有更好的修复效果;当控制铁尾矿掺加比例不超过73%时,铁尾矿道路沿线的土壤重金属含量能够满足国家标准限值的要求。     

Metal and oxalate contamination in a suburban watershed in the greater Toronto area: the benefits of combining acid leach and selective extraction procedures

Environmentally available concentrations of Fe, Mn, Zn, Cu, Pb, Cr and Ni in soils and sediments from a small suburban catchment, obtained using an acid leach procedure, are compared to the Ontario Ministry of the Environment lowest effect level (LEL) and severe effect levels (SEL) and to Provincial sediment quality guidelines (PSQG's). These data are then compared to the bioavailability, potential bioavailability and non-bioavailability of the same metals, plus oxalate concentration, identified using a selective extraction procedure. This combination of techniques enhanced analytical interpretation with respect to metal mobility and potential metal contamination. Selective extraction highlighted the presence of oxalate as a potential contaminant, especially in poorly drained valley floor deposits (33,633 mg kg(-1) and 26,284 mg kg(-1)) and lakeshore sediments (27,095 mg kg(-1) and 13,729 mg kg(-1)). These levels are considerably in excess of those previously documented in a similar study from Rio de Janeiro, where contamination of urban sediment by sewage is a recognised environmental problem, and could possibly be used both as an indicator of similar contamination and the identification of those areas that warrant further investigation.     

Metal release from bottom sediments of Ocoee Lake No. 3, a primary catchment area for the Ducktown Mining District

Ocoee Lake No. 3 is the first reservoir receiving suspended sediments contaminated with trace metals discharged by acid mine effluents from the Ducktown Mining District, Tennessee. Bottom sediments (0-5 cm) from the lake were sampled to assess the potential for future adverse environmental effects if no remediation controls or activities are implemented. The sediments were found to include a major component (173 +/- 19 g kg(-1)) that dissolved in 6 mol L(-1) HCl within 24 h. This acid-soluble and relatively labile fraction contained high concentrations of Fe (460 +/- 40 g kg(-1)), Al (99 +/- 11 g kg(-1)), Mn (10 +/- 8 g kg(-1)), Cu (2000 +/- 700 mg kg(-1)), Zn (1300 +/- 200 mg kg(-1)), and Pb (300 +/- 200 mg kg(-1)). When the pH of water in contact with the sediment was decreased experimentally from 6.4 to 2.6, the concentrations of dissolved trace metals increased by factors of 2200 for Pb, 160 for Cu, 21 for Zn, 9 for Cd, 8 for Ni, and 5 for Co. The order in which metals were released with decreasing pH was the reverse of that reported for pH-dependent sorption of these metals in upstream systems. Substantial release of trace metals from the sediment was observed even by a modest decrease of pH from 6.4 to 5.9. Therefore, the metal-rich sediment of the lake should be considered as potentially hazardous to bottom-dwelling aquatic species and other organisms in the local food chain. In addition, if the reservoir is dredged or if the dam is removed, the accumulated sediment may have to be treated for recovery of sorbed metals.     

Comparison of trace metal contents of sediments and mussels collected within and outside Tolo Harbour,Hong Kong

Sediments collected from Tap Mun (within Tolo Harbour) and Yim Tin Tsai (outside Tolo Harbour) were extracted sequentially and the copper, cadmium, and chromium contents were determined. Total contents of copper, cadmium, chromium, and arsenic were also detected by acid digestion. The level of heavy metal extracted was higher in sequential extraction (which extracted all forms of metal ions) than total acid digestion. Among the four heavy metals studied, only copper showed a significantly higher (P<0.001) level in samples collected from Yim Tin Tsai (16.10 mg/kg) than that from Tap Mun (3.19 mg/kg). Such a difference in copper level is mainly attributed to the significantly higher (P<0.05) levels of copper in the organic, carbonate, and sulfide forms, whereas there was no significant difference (P>0.05) in the exchangeable and sorbed forms. Green-lipped mussel (Perna viridis) samples collected from the two sites were dissected into seven parts (gill, byssus, siphon, shell, digestive gland, soft tissue, and adductor muscle) and the concentrations of copper, cadmium, chromium, and arsenic were measured. The highest concentration of copper was obtained in the byssus. A higher concentration of copper was also noted in the mussels collected from Yim Tin Tsai than those collected from Tap Mun. No specific trend was revealed for the other metals tested. Chromium and arsenic concentrations were found to be independent of the body size of the mussels. Copper had a lower concentration in larger mussels and cadmium level was found to decrease with size. In addition, the mussels collected from Tap Mun were much larger than those collected from Yim Tin Tsai.     

Potential anthropogenic mobilisation of mercury and arsenic from soils on mineralised rocks, Northland, New Zealand

Eroded roots of hot spring systems in Northland, New Zealand consist of mineralised rocks containing sulfide minerals. Marcasite and cinnabar are the dominant sulfides with subordinate pyrite. Deep weathering and leached soil formation has occurred in a warm temperate to subtropical climate with up to 3 m/year rainfall. Decomposition of the iron sulfides in natural and anthropogenic rock exposures yields acid rock drainage with pH typically between 2 and 4, and locally down to pH 1. Soils and weathered rocks developed on basement greywacke have negligible acid neutralisation capacity. Natural rainforest soils have pH between 4 and 5 on unmineralised greywacke, and pH is as low as 3.5 in soils on mineralised rocks. Roads with aggregate made from mineralised rocks have pH near 3, and quarries from which the rock was extracted can have pH down to 1. Mineralised rocks are enriched in arsenic and mercury, both of which are environmentally available as solid solution impurities in iron sulfides and phosphate minerals. Base metals (Cu, Pb, Zn) are present at low levels in soils, at or below typical basement rock background. Decomposition of the iron sulfides releases the solid solution arsenic and mercury into the acid rock drainage solutions. Phosphate minerals release their impurities only under strongly acid conditions (pH<1). Arsenic and mercury are adsorbed on to iron oxyhydroxides in soils, concentrated in the C horizon, with up to 4000 ppm arsenic and 100 ppm mercury. Waters emanating from acid rock drainage areas have arsenic and mercury below drinking water limits. Leaching experiments and theoretical predictions indicate that both arsenic and mercury are least mobile in acid soils, at pH of c. 3-4. This optimum pH range for fixation of arsenic and mercury on iron oxyhydroxides in soils is similar to natural pH at the field site of this study. However, neutralisation of acid soils developed on mineralised rocks is likely to decrease adsorption and enhance mobility of arsenic and mercury. Hence, development of farmland by clearing forest and adding agricultural lime may mobilise arsenic and mercury from underlying soils on mineralised rocks. In addition, arsenic and mercury release into runoff water will be enhanced where sediment is washed off mineralised road aggregate (pH 3) on to farm land (pH>6). The naturally acid forest soils, or even lower pH of natural acid rock drainage, are the most desirable environmental conditions to restrict dissolution of arsenic and mercury from soils. This approach is only valid where mineralised soils have low base metal concentrations.     

A novel continuous-flow sequential extraction procedure for metal speciation in solids

A continuous-flow extraction system was developed to speed up, facilitate, and improve the accuracy of the chemical fractionation of metals in solid materials. A three-step sequential extraction scheme was used to evaluate the novel system by analyzing calcium (Ca), iron (Fe), manganese (Mn), copper (Cu), and zinc (Zn) in a soil certified reference material (National Institute of Standards and Technology [NIST] SRM 2710). In the proposed system, extraction occurred in a closed chamber through which extractants were passed sequentially. The extracts were collected in a number of subfractions for subsequent name atomic absorption analysis. Apart from the advantages of simplicity, speed, and less risk of the contamination that flow analysis systems usually possess, the continuous-flow system can improve the accuracy of chemical fractionation of metals by sequential extraction. The system ensures that extraction is performed at designated pH values without any need of adjustment. Variation of sample weight to chamber volume ratios from 1:12 to 1:40 had no effect on the extractability of the metals studied. In the extraction of the acid soluble fraction, concentrations of acetic acid in the range 0.11 to 0.5 mol L(-1) had no significant effect on the amounts of metals extracted, except Fe. Increasing the concentration of hydroxylamine in the reducible fraction step from 0.04 to 0.5 mol L(-1) affected the extraction efficiency for Fe, Mn, and Zn. The extraction profile, rather than a single value of extracted concentration, of each element offers additional information about the kinetics of leaching processes and chemical associations between elements in the solid materials.     

Changes in Extractable Metal Concentrations During Storage of Surface Water Samples Containing Sediments1

ABSTRACT: Changes in metal concentrations during storage of acidified water samples were studied. Water samples with high concentrations of suspended sediment were collected from the Fraser River, British Columbia. These samples were analyzed for “extractable” metals, which are defined to be the dissolved metals plus those metals extracted from suspended sediment by dilute mineral acid. Concentrations of extractable Cu, Fe, Pb, Zn, Ni, Co, Mn, and Cd were determined over time. Metal concentrations in these water samples were not stable and showed significant increases throughout the storage period. These results suggest that the extractable metal technique is inappropriate for the analysis of water samples containing suspended sediment.     

THE IMPACT OF URBANIZATION ON THE DISTRIBUTION OF HEAVY METALS IN BOTTOM SEDIMENTS OF THE SADDLE RIVER1

ABSTRACT: A three-year study has been conducted on a 4.6 mile stretch of the Saddle River near Lodi, New Jersey. The primary objectives of this investigation were (1) to provide baseline information on the concentration and distribution of heavy metals in bottom sediments of the Saddle River; (2) to qualitatively evaluate which parameters affect this distribution; and (3) to determine the effect of urbanization on the concentration and distribution of these materials. Significant enrichments of several heavy metals were observed in bottom sediments of the lower Saddle River near Lodi, New Jersey, as compared to the upper Saddle River. Attempts to correlate metal concentrations in bottom sediments with chemical-oxygen demand were not successful in demonstrating a relationship between these two factors. Metal concentrations were found to be strongly dependent upon particle size. In general, metal concentrations in bottom sediments increased with decreasing partical diameter. However, metals enrichment was observed to be considerably greater in the larger sediment fractions studied (>420μ) than the smaller sediment fractions as one proceeded downstream through the urban area. Since the larger sediment fractions are least effected by scour and transport they may best reflect the effect of urbanization on the distribution of heavy metals over an extended period of time at a given location.     

REVERSIBLE ADSORPTION OF AQUEOUS DIVALENT COPPER ION BY ESTUARINE SEDIMENTS1

Sediments were equilibrated with solutions containing divalent copper ion. A colorimetric method using the triethylenete-tramine complex of the metal ion was employed to measure changes in uptake of copper by the sediments. Studies were made with sediments from rivers in the British Isles which were in the proximity of areas which had been mined for metals for several hundred years. For comparison, similar studies were performed with a sample of sand and a soil with a high organic content. It was possible to follow the uptake of copper ion by the materials and estimate their abilities to adsorb copper ion. In particular, a strong correlation was observed between the organic content of the sediment and the total amount of copper adsorbed by the sample. Under the employed circumstances it was possible to demonstrate that the adsorption of the metal ion was reversible.     

Study of Fractionation and Potential Mobility of Metal from the Guadalquivir Estuary: Changes in Mobility with Time and Influence of the Aznalcollar Mining Spill

This study analyzed the evolution of metal levels in surface sediments from the Guadalquivir estuary between 1997 and 2002 and assessed the impact of the April 1998 Aznalcollar tailings dam failure and subsequent cleanup on metal concentrations in surface sediments. We also analyzed metal distribution with time in five chemical fractions of the surface sediments: exchangable, carbonate, reducible, oxidizable, and residual. This work showed that the April 1998 Aznalcollar tailings dam failure caused a considerable increase in the concentrations of Cd, Zn, Cu, and Pb in the surface sediments of the Guadalquivir estuary. It was also found there was a change in the distribution of Cd, Zn, Cu, and Pb between the chemical fractions of the sediment after the failure of the dam. There were increases in the percentages of Cd in the carbonate fraction, of Zn and Pb in the reducible fraction, and of Cu in the oxidizable fraction, whereas the percentages of these elements associated with the residual fraction decreased. In 1999, there was a decrease in the metal concentrations in the surface sediments from the Guadalquivir estuary, and by 2000 the chemical distribution and metal levels had returned to levels similar those before the dam failure.