Lethal critical body residues as measures of Cd,Pb, and Zn bioavailability and toxicity in the earthworm<Emphasis Type="Italic">Eisenia fetida</Emphasis>

Background. Earthworm heavy metal concentrations (critical body residues, CBRs) may be the most relevant measures of heavy metal bioavailability in soils and may be linkable to toxic effects in order to better assess soil ecotoxicity. However, as earthworms possess physiological mechanisms to secrete and/or sequester absorbed metals as toxicologically inactive forms, total earthworm metal concentrations may not relate well with toxicity. Objective  The objectives of this research were to: i) develop LD₅₀s (total earthworm metal concentration associated with 50% mortality) for Cd, Pb, and Zn; ii) evaluate the LD₅₀ for Zn in a lethal Zn-smelter soil; iii) evaluate the lethal mixture toxicity of Cd, Pb, and Zn using earthworm metal concentrations and the toxic unit (TU) approach; and iv) evaluate total and fractionated earthworm concentrations as indicators of sublethal exposure. Methods  Earthworms (Eisenia fetida (Savigny)) were exposed to artificial soils spiked with Cd, Pb, Zn, and a Cd-Pb-Zn equitoxic mixture to estimate lethal CBRs and mixture toxicity. To evaluate the CBR developed for Zn, earthworms were also exposed to Zn-contaminated field soils receiving three different remediation treatments. Earthworm metal concentrations were measured using a procedure devised to isolate toxicologically active metal burdens via separation into cytosolic and pellet fractions. Results and Discussion  Lethal CBRs inducing 50% mortality (LD₅₀, 95% CI) were calculated to be 5.72 (3.54-7.31), 3.33 (2.97-3.69), and 8.19 (4.78-11.6) mmol/kg for Cd, Pb, and Zn, respectively. Zn concentrations of dead earthworms exposed to a lethal remediated Zn-smelter soil were 3-fold above the LD₅₀ for Zn and comparable to earthworm concentrations in lethal Zn-spiked artificial soils, despite a 14-fold difference in total soil Zn concentration between lethal field and artificial soils. An evaluation of the acute mixture toxicity of Cd, Pb, and Zn in artificial soils using the Toxic Unit (TU) approach revealed an LD₅₀ (95% CI) of 0.99 (0.57-1.41) TU, indicating additive toxicity. Conclusions  Total Cd, Pb, and Zn concentrations in earthworms were good indicators of lethal metal exposure, and enabled the calculation at LD₅₀s for lethality. The Zn-LD₅₀ developed in artificial soil was applicable to earthworms exposed to remediated Zn-smelter soil, despite a 14-fold difference in total soil Zn concentrations. Mixture toxicity evaluated using LD₅₀s from each single metal test indicated additive mixture toxicity among Cd, Pb, and Zn. Fractionation of earth worm tissues into cytosolic and pellet digests yielded mixed results for detecting differences in exposure at the sublethal level Recommendation and Outlook  CBRs are useful in describing acute Cd, Pb, and Zn toxicity in earthworms, but linking sublethal exposure to total and/or fractionated residues may be more difficult. More research on detoxification, regulation, and tissue and subcellular partitioning of heavy metals in earthworms and other invertebrates is needed to establish the link between body residue and sublethal exposure and toxicity. Keywords: Bioavailability; Cd; critical body residues; earthworms; metals; Pb; soil; Zn An erratum to this article is available at .     

Sediment toxicity and heavy metals in eleven lime reference lakes of Sweden

Sediments from an eutrophic reference lake (L. HjÄlmaren) and eleven oligotrophic Swedish lakes were analyzed for heavy metals (Cd, Cr, Cu, Hg, Ni, Pb, and Zn) and tested for whole sediment toxicity to Daphnia magna. Whole sediment toxicity, expressed as 48-hr EC50 on a wet weight basis in reconstituted dilution water, ranged from 2.8% (most toxic) to >32% (least toxic). Correlations between bulk sediment heavy metal concentrations and toxicity were significant (P≤0.05) for Hg, Pb, and Zn. However, a causal connection between the concentrations of these metals and toxicity was not supported by the results from metal-spiked sediment toxicity tests. In addition sediment toxicity was not affected by the addition of EDTA, which is a strong chelator known to reduce metal toxicity. After storage for several months test sediments either remained nontoxic, toxic, or increased in toxicity. These results illustrate some of the difficulties in the interpretation of bulk sediment chemistry data and the release of toxic chemicals from sediment samples, highlighting the effect of sediment storage on toxicity.     

Review of impact of heavy metals on stream invertebrates with special emphasis on acid conditions

Studies of the accumulation and toxicity of Cd, Zn, Fe, Pb and Cu under acid conditions to stream invertebrates are reviewed. The influence of pH on metal speciation decreases in the following order: Cu > Pb > Cd > Zn. The free metal ion is one of the most toxic species and is generally taken up directly from the water by organisms. The role of food in the uptake of metals depends mainly on feeding habits of the species, body size, life span and duration of the exposure. Surface adsorption can be regarded as a form of metal ‘uptake’ which increases at high pH. Biomagnification of metals along aquatic trophic food chains has not been proved for many metals. Toxicity of Cd, Fe, Zn and Pb increases at low pH, however not for all invertebrates. More knowledge is needed concerning sublethal effects of metals on invertebrates at different pH values and uptake, bioconcentration and biomagnification of metals at different pH values. Future studies should include experiments in artificial streams or in the field instead of short term tests and simple recording of field data.     

Zn对大麦Cd、Cu毒性的影响及其联合毒性效应

通过模拟土壤溶液进行水培试验,研究了锌（Zn）对大麦（Hordeum Vulgate）镉（Cd）、铜（Cu）毒性的影响,以及Zn-Cd和Zn-Cu的联合毒性效应。结果表明：Zn、Cd和Cu单独作用于大麦时,EC。分别为78．01、2．98、0．64μmol·L^-1,Zn的毒性远远小于Cd和Cu。在Zn-Cd混合体系中,当Zn浓度低于5μmol·L^-1时,随着溶液中Zn浓度的增加,EC50（Cd）呈显著的线性增加,表明低浓度Zn对大麦Cd毒性具有抑制作用;利用毒性单位（TU）模型计算了Zn-Cd混合体系的TUmix值,结果显示TUtax≥1TU,且Tu。随Zn浓度的升高而增加,表明Zn、Cd联合作用于大麦时主要表现为拮抗作用,且这种作用和混合体系中Zn的比例有关。在Zn-Cu混合体系中,随着Zn浓度的增加,大麦相对根长（RE）明显减小,EC50（Cu）逐渐降低,表明Zn增强了大麦Cu的毒性;Zn-Cu的Tumix。均小于1TU,Zn、Cu联合作用于大麦时表现为协同毒性作用。     

Toxicity of metals to the earthworm Eisenia fetida

Summary Development of methods to measure the effect of man's residuals on soil ecosystems is desirable. Earthworms, as one of the largest and most easily obtained components of the soil biota, are suitable for evaluating perturbations to soil ecosystems.The impact of five metals (Cd, Cu, Ni, Pb, and Zn) on the survival of the earthworm Eisenia fetida (Savigny) was evaluated using the contact and artificial soil tests. There was no difference in toxicity between the different metal salts (acetate, chloride, nitrate, and sulfate) of each of the five metals using the contact test. In the contact test, the order of toxicity, from most toxic to least toxic, was Cu > Zn > Ni Cd > Pb. The nitrate salt of the five metals was tested using the artificial soil test and the order of toxicity, from most toxic to least toxic, was Cu Zn Ni > Cd > Pb. Stress on earthworm populations, as shown by weight loss, was shown to increase with increasing concentrations of metal salts.These studies indicate that: (a) earthworms can be a suitable biomonitoring tool to assist in measuring the effect of metals in wastes added to soils and (b) the contact and artificial soil tests can measure the biological impacts.Research Associate, Research Technician, and Research Support Specialist, respectivelyAt the time of this research, Dr. Loehr was a Professor of Agricultural Engineering and of Environmental Engineering, Cornell University. He currently is the H.M. Alharthy Centennial Chair Professor, Civil Engineering Department, University of Texas, Austin, Texas 78712     

Short- and long-term effects of heavy metals on phosphatase activity in soils: An ecological dose-response model approach

Summary The aim of this study was to provide manageable data to help establish permissible limits for the pollution of soil by heavy metals. Therefore the short-and long-term effects of heavy metal pollution on phosphatase activity was studied in five different soil types. The results are presented graphically as logistic dose-response curves. It was possible to construct a curve for sand and silty loam soil but it was more difficult to establish a curve for sandy loam and clay soil and nearly impossible (except for Cu) for peat. The toxicity of the various metals can be compared on the basis of mmol values. In clay soils, for Cd, Cr, Cu, and Zn, the 50% effective ecological dose (ED₅₀) values were comparable (approximately 45 mmol kg^–1), but the ED₁₀ values were very different, at 7.4, 41.4, 15.1, and 0.55, respectively. At the ED₅₀ value, toxicity did not decrease with time and, in sandy soils, was approximately 2.6 mmol kg ^–1 dry soil for Cd, Cu, and Zn. In four out of five soils, the Cd toxicity was higher 1.5 years after the addition of heavy metal salts than after 6 weeks. Toxicity was least in the sandy loam, silty loam, and clay soil, and varied in general between 12 and 88 mmol kg^–1. In setting limits, the criteria selected (no-effect level, ED₁₀ or ED₅₀) determine the concentration and also the toxicity of the sequence. It is suggested that the data presented here could be very useful in helping to set permissible limits for heavy metal soil pollution.     

Toxicity of heavy metals (Zn,Cu, Cd,Pb) to vascular plants

The literature on heavy metal toxicity to vascular plants is reviewed. Special attention is given to forest plant species, especially trees, and effects at low metal concentrations, including growth, physiological, biochemical and cytological responses. Interactions between the metals in toxicity are considered and the role of mycorrhizal infection as well. Of the metals reviewed, Zn is the least toxic. Generally plant growth is affected at 1000 μg Zn L^?1 or more in a nutrient solution, though 100 to 200 µg L^?1 may give cytological disorders. At concentrations of 100 to 200 μg L^?1, Cu and Cd disturb metabolic processes and growth, whereas the phytotoxicity of Pb generally is lower. Although a great variation between plant species, critical leaf tissue concentrations affecting growth in most species being 200 to 300 μg Zn g^?1 dry weight, 15 to 20 μg Cu g^?1 and 8–12 μg Cd g^?1. With our present knowledge it is difficult to propose a limit for toxic concentrations of Zn, Cu, Cd and Pb in soils. Besides time of exposure, the degree of toxicity is influenced by biological availability of the metals and interactions with other metals in the soil, nutritional status, age and mycorrhizal infection of the plant.     

Comparisons of metal accumulation and excretion kinetics in earthworms (Eisenia fetida) exposed to contaminated field and laboratory soils

The uptake and excretion kinetics of cadmium, copper, lead and zinc were studied for Eisenia fetida exposed to mixtures of these metals in field and OECD artificial soil. Body burdens in worms exposed to all contaminated soils increased over the duration of the experiment. Highest accumulation rates were for worms exposed to the most polluted soils. Pronounced differences were found in the uptake and excretion patterns for essential and non-essential elements (particularly in field soils). For cadmium and lead (non-essential), an equilibrium plateau was not reached during the uptake study and slow excretion was found on transfer of worms to clean soil. For copper and zinc (essential), fast initial uptake was followed by equilibrium after only a few days exposure. Rapid excretion was found after transfer to clean soil, with half-lives of less than 1 day for both metals. A previous study of the effects of metals on worms exposed in OECD and field soils had indicated a higher toxicity in the artificial medium. Thus, in the present study, it was anticipated that greater toxicity would be reflected by increased body burdens for worms in OECD soil. This was, however, not the case. Explanations are given that might account for the fact that the greater toxicity in OECD soil is not invariably accompanied by higher metal burdens. These include the presence of high concentrations of very toxic and highly available ions in laboratory tests and potential differences in the importance of soluble and total metal concentration for determining toxicity and body burdens.     

Assessing metal bioaccumulation from estuarine sediments: comparative experimental results for the polychaete Arenicola marina

Purpose

The purpose of this paper is to compare three approaches for providing information on the bioaccumulation potential of metals from contaminated sediments to the deposit-feeding polychaete Arenicola marina.

Materials and methods

We present metal (Ag, As, Cd, Cu, Pb and Zn) bioaccumulation results from field-collected sediments quantified through direct measurements of bioaccumulated concentrations in A. marina over a period of 30 days under controlled laboratory exposures and compare these results with bioaccumulated metal concentrations in field-collected organisms from the same sites of collection of the sediments used in the laboratory exposures. For the metals for which model parameters are available (Ag, As, Cd and Zn), we also compare these results with biodynamic model predictions. We considered three UK estuaries characterised by a well-reported history of trace metal contamination and bioavailability in addition to the (control) site of collection of the worms.

Results and discussion

The results from laboratory-exposed organisms showed that the standard 28-day exposure duration may be adequate to identify the potential for metal bioaccumulation in this polychaete at the sites considered here. However, the time course of bioaccumulated concentrations and the comparison with measured concentrations in field-collected worms show that a steady state has not been reached, confirming the need for extended exposure periods. The worms showed symptoms of stress in feeding and growth during the initial 10 days of exposure and subsequent partial recovery during the following 20 days, suggesting that stress was not always caused by sediment contamination but that it was likely associated with handling and acclimation. At this last stage of the exposure, a generalised biodynamic model was used to provide estimates of bioaccumulated metal concentrations and net accumulation rates in worms.

Conclusions

The results of this study highlight the number of factors that should be considered for the interpretation of bioaccumulated metal concentrations in A. marina under laboratory exposures for contaminated sediment assessment, factors that appear to be common to most deposit-feeding polychaetes. A general biodynamic model proved to be a cost-effective method for an initial estimation of the extent and pattern of metal bioaccumulation under specified exposure conditions.     

Contaminated sediments as a potential source of Zn, Pb, and Cd for a river system in the historical metalliferous ore mining and smelting industry area of South Poland

Background, aim, and scope  Elevated levels of heavy metals in the aquatic and soil systems can be caused by the weathering of mineralized rocks. This enrichment is often considerably enlarged by historical and current mining and smelting activities. In Poland, the most contaminated river systems are those in the Silesia region. The metalliferous ore mining and smelting industries have been the main sources of heavy metal pollutions over the last 100–170 years. The previous and present studies have shown very high concentrations of heavy metals in the bottom sediments of the Mala Panew River, the most polluted tributary of the Oder River. The main objective of this work was to study temporary changes of selected metal (Zn, Pb, and Cd) concentrations in upper layer of bottom sediments at the measuring point near the outlet of the Mala Panew River into the Oder River, and to determine the vertical distribution of the metals in the sediment cores from the most polluted middle part of this river. The mobility of the metals and their potential bioavailability were assessed based on metal partitioning in the sediments and metal concentrations in pore waters. The presented data were compared with metal concentrations in aquatic sediments from similar historical mining and smelting sites in Poland and other countries. Methods  The upper layer of bottom sediment samples from the same Mala Panew River measuring point were collected six times in the period 1997–2005, while five sediment cores were collected once from the middle course of Mala Panew River in 2006. Abiotic parameters such as pH and Eh have been determined in situ. Metal contents were determined in the <20 and <63 μm size fractions of sediments after digestion in a microwave oven with aqua regia or concentrated nitric acid. Metal mobility was assessed in the selected sediment cores by the chemical forms of metals (sequential extraction method) and their concentrations in pore waters were investigated. Results  The concentrations of Cd, Pb, and Zn in the upper layer of sediments varied, depending on both the season and the year of sampling. Their mean concentrations (from six samplings) are [mg/kg]: Zn 1,846, Pb 229 and Cd 73. The metal concentrations in the sediment cores varied with the depth in the range of [mg/kg]: 0.18–559 for Cd, 26.2–3,309 for Pb and 126–11,153 for Zn, although the highest accumulations generally could be observed in the deeper layers. The most mobile metal fractions, i.e., exchangeable, carbonate and easily reducible fractions, are typical of Zn and Cd. Cadmium was found to be the most mobile metal and its relative contribution ranges from 84 to 96%, while in the case of Zn it ranged from 45 to 94%. Lead is mainly associated with the moderately reducible fraction (30–60%). Relative contributions of metal chemical forms slightly vary with the depth in the sediment profile. The results obtained for the pore water samples show very high concentrations of the metals studied, especially in the case of Cd (31–960 μg/dm³) and Zn (300–4,400 μg/dm³). Discussion  Accumulation of Cd, Pb, and Zn in the upper layer of the bottom sediments and in the sediment core samples from the Mala Panew River is very high, considerably exceeding the local geochemical background. High contributions of mobile Cd and Zn and the toxicity of cadmium can cause environmental risk. Our measurements also suggest that mobile metals can migrate into groundwater, whereas the groundwater itself can leach some chemicals from river sediments, because of a relatively high water table in the study area, especially during rainfall periods. Comparison of the results obtained with the literature data from the last decade shows that the concentrations of Cd and Zn in the sediments from the Mala Panew River are the highest among other submersed sediments in Poland and other regions (e.g., the Mulde River, Germany). Conclusions  The Mala Panew River is one of the most polluted rivers when compared with similar historical mining and smelting areas in Poland and elsewhere. The sediments studied are strongly polluted with the metals analyzed. In the upper layer of the bottom sediments there has been no reduction of Zn and Cd amounts over the last decade, which could suggests a long-term migration and a secondary contamination. Considerably higher accumulations of metals in overbank sediment cores and in the deeper core section could result from strong contamination in previous decades and translocation of Cd and Zn (secondary pollutants). The relatively high concentrations of the two metals in pore waters support these findings. Cadmium is crucial in the environmental risk assessment because of its high mobility and toxicity. These data are important for water/sediment management in the transboundary Oder River catchment, situated in Poland, Germany and the Czech Republic. Recommendations and perspectives  It is important to assess mobility phase and pore water in the contaminated historical aquatic sediments. Such studies may help explain the changes, which take place in the sediment layers as well as at the water–sediment interface. Obtained results should be used for the risk assessment of the historical contaminated sediments at the local river-basin scale. The treatment of contaminated sediments, e.g., dragging activity, should be considered as very important in management strategies in order to avoid remobilization of metals.     

Toxicity and binding of copper,zinc, and cadmium by the blue-green alga,Chroococcus paris

The toxic effects and accumulation of the heavy metals, Cd, Cu, and Zn by the sheath forming blue-green alga Chroococcus paris were investigated. All three of the metals were bound rapidly. Approximately 90% of the total amount of the added metal was bound within 1 min. Further significant binding occurred at a slower rate. The maximum metal binding capacity, as determined by filtration studies, was determined to be 53, 120, and 65 mg g^?1 dry algal weight for Cd, Cu, and Zn, respectively. Binding curves for the metals followed the Langmuir adsorption isotherm model. The amount of metal bound increased with increasing pH. Metal binding increased significantly when pH was increased from 4 to 7. Nearly all of the metal was found to be rapidly EDTA extractable. Metals were found to be increasingly toxic to growing cultures in the order, Zn, Cd, and Cu. All of the metals studied exhibited toxic effects at concentrations greater than 1.0 mg L^?1. The lowest concentrations used which showed detectable toxicity were 0.1 mg L^?1 for Cu and >0.4 mg L^?1 for Cd and Zn.     

A geochemical analytical approach for the evaluation of heavy metal distribution in lagoon sediments

Background, Aim, and Scope  Italian lagoon environments are of great importance due either to their frequency and distribution along the coasts or to their management. Agriculture, urban and industrial activities in lagoon catchments can be sources of heavy metal (HM) pollution by direct waste dumping, atmospheric deposition of fumes or, simply, as a consequence of a lack of natural water recharge. HM concentration in lagoon sediments is a tool of HM monitoring in the surrounding environment. Application of sequential extraction procedures (SEP) to sediments makes it possible to study the HM distribution among the main geochemical phases and to assess their potential mobilization as a consequence of environmental condition variations. In the present study, the three-step SEP (0.11 m HOAc; 0.1 m NH₂OH·HCl; 8.8 m H₂O₂ and then 1 m NH₄OAc), developed by the Measurement and Testing Programme of the European Commission (BCR), was combined with information on the chemical and mineralogical properties of the sediments in order to assess the level and risk of mobility of HM (Cu, Cr, Cd, Pb, Ni, Zn) in sediments from the Fusaro volcanic coastal lagoon of southern Italy. The effect of sediment air drying and physico-chemical properties on the metal distribution in various geochemical forms and fractions was considered. Materials and Methods  Surface (5 cm depth) sediment samples were collected from twenty-one sites on the Fusaro lagoon. Moisture, pH, organic carbon, carbonates, particle-size distribution and HM total content were determined on the dried sediment samples. The mineralogy of the clay fraction was determined at room temperature on random and oriented samples. The different forms of Al, Si and Fe in the bulk sediment (< 2 mm) were analyzed after oxalate, dithionite-citrate and pyrophosphate extractions. The BCR-SEP was used to fractionate trace element chemical forms in nine selected sediment samples. Effects of sediment air-drying on HM fractionation were analyzed. Results  Middle (Cu, Cr) and low (Cd, Pb, Zn) concentrations of heavy metals in sediment samples from the deeper central part of the lagoon were observed. Cadmium resulted in mainly being associated with carbonate forms (∼60%), whereas Cr and Ni occurred primarily as residual mineral phases (>50%). Zn appeared uniformly distributed among the main geochemical forms. Considerable presence of Cr, Cu and Pb was found in the oxidizable fraction (∼50%), indicating organic matter and/or sulphides major sinks for these metals. Differences of heavy metal distribution among sediment samples were observed, depending on the total metal content and on sediment properties. Modifications in metal speciation induced by sediment air drying mainly consist of a transfer of the actual and potentially mobile fractions towards immobile fractions (mineral residue) by oxidation and formation of Fe and Mn oxides. Discussion  Both total content and sequential extraction results did not show an environmental critical situation: the only possible risk, associated with heavy element mobility, could occur in consequence of a drastic pH and redox equilibria variation at the water-sediment interface. Conclusions  Despite all limitations, the BCR-SEP combined with information on the chemical and mineralogical properties of the sediment solid matrix provides a valuable approach to describe the risks related to the potentially toxic HM occurring in sediments (in this paper the case of the Fusaro lagoon is examined). HM distribution among the sequentially extracted geochemical forms is affected by sediment properties, such as pH (Zn), clay (Cd), Fe easily reducible oxides (Pb) and organic matter (Cu) content. Recommendations  Political managers, usually facing limitations of time and resources, have to optimize the cognitive phases, selecting the most useful information to make ‘effective and correct decisions’ in the environmental field. Therefore, although conscious of the limits of the adopted quality assessment, we believe it represents a good compromise between time and resource availability (i.e. type and quality of information). Outlook  The complementary use of the simple and rapid European fractionation scheme with information on the chemical and mineralogical properties of the sediments provides more awareness about the nature of the sediment components involved and offers a more reliable way for studying HM speciation in sediments.     

Hydrocarbons in Seawater and Water Extract of Jarzouna-Bizerte Coastal of Tunisia (Mediterranean Sea): Petroleum Origin Investigation Around Refinery Rejection Place

In this study, the occurrence of toxic heavy metals (As, Cd, Cr, Cu, Pb, and Zn) and relative bioaccumulation in biota samples were investigated in a freshwater ecosystem, the Basento river, one of the main aquatic systems in the south of Italy, which over the last years has been transformed into a sink of urban and industrial wastes. Therefore, the levels of arsenic, cadmium, chromium, copper, lead, and zinc were determined in water, sediments, and tissues of some macroinvertebrate—which are natural assessment endpoints for the evaluation of ecological risk in aquatic systems. Accumulation factors, as a ratio between the concentration of a given contaminant in biota and the one in an abiotic medium, were considered in order to estimate heavy metal contamination loads in biota. Statistical analysis was performed for a comparative evaluation of bioaccumulation among various macroinvertebrates, according to different feeding guilds. The Tukey honestly significantly different test showed significant differences in the bioaccumulation of As, Cd, and Cr among the considered biological receptors (collector–gatherer, predator, and filterer), suggesting that the biological uptake from immediate contact with the sediment or solid substratum (collector–gatherer), instead of the bioconcentration from water (filterer) or biomagnification along the biotic food webs (predators), is the more effective biological sequestering pathway for these metals. Biota–sediment accumulation factors, commonly used for the evaluation of sediment’s role in aquatic systems contamination, were determined for the considered metals. A linear correlation between the concentrations of As, Cd, Cr, and Zn in macroinvertebrates and those in the sediments suggested that the metal uptake data in macroinvertebrates can provide useful information for the estimation of heavy metal exposure risk or bioavailability when making assessments of sediment toxicity in freshwater ecosystems.     

滇池内湖滨带重金属污染及其生态风险评价

水体沉积物是重金属元素的重要载体,其含量高低能反映水环境质量现状。采集滇池内湖滨带沉积物样品,分析了滇池内湖滨带表层沉积物中Pb、Cd、Cu、Zn、Cr、Ni、Fe、Mn 8种重金属元素含量特征,并用Hakanson潜在生态危害指数法评价其生态危害,旨在为合理预防和治理滇池内湖滨带的重金属污染以及内湖滨带生态系统的修复提供基础资料。结果表明,与“全国土壤环境质量标准”对比,表层沉积物中主要是Cd、Cu、Zn超标,重金属污染强度总体上是草海＞外海。不同重金属间的相关性分析结果表明,Cu-Cd之间呈极显著相关,说明这两种元素污染源可能相同,几种污染重金属与胶体矿物元素Fe、Mn间的相关性不大,说明在所调查沉积物中,Fe/Mn氧化物或氢氧化物共沉淀或吸附Pb、Cd、Cu、Zn、Cr、Ni元素量较少。由潜在生态风险评价结果可知,滇池内湖滨带表层沉积物已具极强生态危害,各重金属对滇池内湖滨带生态风险影响程度由高到低依次为：Cd〉Cu〉Pb〉Ni〉Zn≈Cr。     

赤子爱胜蚓谷胱甘肽和丙二醛含量变化指示重金属污染土壤的生态毒性

为探讨赤子爱胜蚓谷胱甘肽(GSH)和丙二醛(MDA)含量变化对重金属污染土壤生态毒性的指示作用,在试验室模拟条件下,利用人工土壤和自然土壤,研究了重金属含量与蚯蚓GSH和MDA含量变化的剂量效应关系。结果显示,在人工土壤试验中,Cu可诱导蚯蚓GSH和MDA含量上升,暴露2 d、7 d、14 d后,Cu浓度与蚯蚓GSH含量的相关系数分别为0.556、0.807和0.775,与MDA含量的相关系数分别为0.760、0.672和0.544,均存在显著的剂量效应关系(p<0.05)。自然土壤试验结果显示,赤子爱胜蚓的GSH和MDA含量与土壤Cu全量的偏相关系数分别为-0.830(p<0.001)和-0.599(p<0.05),与Cd全量的偏相关系数分别为-0.697(p<0.05)和-0.690(p<0.05)。同时发现,赤子爱胜蚓GSH含量变化对土壤重金属响应的敏感性要高于MDA。     

Additive effects of copper and zinc on cadmium toxicity on phosphatase activities and ATP content of soil as estimated by the ecological dose (ED50)

The ecological dose (ED₅₀) of Cd on alkaline and acid phosphatase activity and the ATP content of three contrasting forest soils was measured with or without Cu and Zn to assess the additive toxic effects of these two metals. Soils polluted with Cu and/or Zn were treated with increasing Cd concentrations to give the following metal combinations: Cd, Cd+Cu, Cd+Zn and Cd+Cu+Zn. Alkaline and acid phosphatase activities and ATP content of the three soils were analysed 4 h, 7 and 28 days after the metal additions. The ED₅₀ values were obtained by interpolating the enzyme activities or ATP data with a kinetic model and the goodness of fit was satisfactory.Generally, the ED₅₀ values of both acid and alkaline phosphatase activities for Cd were lower (higher toxicity) with than without Cu and Zn and the effect of Cu and Zn was particularly adverse when these two metals were both added to soils. The alkaline phosphatase was more sensitive in the acid and neutral soil whereas the acid phosphatase was more sensitive in the alkaline soil. Both phosphatase activities and the ATP content were more sensitive in the sandy than in the finer textured soils. The ATP content was less sensitive to the additive effects. Increasing toxicity was observed during the incubation.Analysis of 1 M NH₄NO₃-extractable Cd, Cu and Zn revealed that Cd competed with Zn for the adsorption sites but not with Cu. However, the lower ED₅₀ values for Cd of the two phosphatase activities and of the ATP content in the presence of heavy metal combinations could be not explained by the heavy metal solubility data. It is concluded that the ED₅₀ may be a sensitive tool for assessing additve toxic effects to soil biochemical parameters.     

The Influence of Heavy Metals on Carbon Dioxide Evolution from a Typic Xerochrept Soil

In a laboratory study the effects on soil respiration of trace metals (Ni, Cd, Cu, Mn, Pb, Zn)added at loading rates ranging from 0 to 1000 µg g-1 were determined. Differences intoxicity with respect to the type of metal salt added were also evaluated. The inhibitory effect onsoil respiration differed considerably among the heavy metals and increased with the increasingloading rate. No linear relationships were found between the degree of inhibition and the levels oftotal and available metals. Toxicity evaluation at 20 and 50% inhibition of soil respiration showedCu as the most toxic and Mn as the most tolerable metal. A ‘metal equivalent’ was calculated asthe sum of the amounts of the available metals weighted to their relative toxicity with respect tothe least toxic one: Mn equivalent = Mn + 1.9Pb + 2.1Ni + 2.5Zn + 6.7Cd + 6.7Cu. The ionicpotential of the heavy metals was found to be positively related to the percent inhibition of soilrespiration. Chlorides and sulphates appeared to depress soil respiration more than nitrates, thelatter counter-balancing the toxic effect of the heavy metals.     

Fractionation and Distribution of Metals in Guadiamar River Sediments (SW Spain)

Traditionally, the Guadiamar River (Seville, Southwest Spain) has received pollution from two different sources, in its upper section, from a pyrite exploitation (Los Frailes mine) and, in its lower section, from untreated urban and industrial wastes and from intensive agricultural activities. In 1998, the accidental spillage of about 6 million m³ of acid water and sludge from mine tailings to Guadiamar River worsened the pollution of an already contaminated area. The main polluting agents of the spillage were heavy metals. The total concentration of a metal provides scarce information about the effects on environmental processes or about the toxicity of the sediment samples. A more sophisticated fractionation of the sediment samples based on a species distribution can help to understand the behaviour and fate of the metals. This article describes a distribution study of the metals Al, Cd, Cu, Fe, Mn, Pb and Zn by fractionation analysis of sediments from eleven sample sites alongside the Guadiamar Riverbed. The samples were collected in summer 2002, four years after the spillage and after the area had been cleaned. Sequential extraction analysis resulted in the definition of four fraction categories: exchangeable metal (the most available fraction), reducible metal (bound to hydrous oxides of Fe and Mn), oxidizable metal (bound to organic matter and sulphides) and a residual fraction (bound to minerals). Significant increases in the available fraction of several potentially toxic metal ions like Cd, Mn and Zn were found. The distribution pattern was variable along the River. At the site closest to the mineworks, the soluble forms of Cd, Mn and Zn were significantly more abundant that those downstream. Cu and Pb were present in the reducible fraction while Fe was present associated in the residual fraction.     

Trace metal composition and speciation in street sediment: Sault Ste. Marie,Canada

Street sediment collected in Sault Ste. Marie, Ontario was examined for trace element composition (As, Cd, Cr, Cu, Fe, Pb, Hg, Ni and Zn) and the metal partitioning to various sediment properties was determined by sequential extraction. Total Ni, Cu, Zn and Pb concentrations exceeded the lowest effect levels specified in the Ontario Provincial Sediment Quality Guidelines for Metals (Environment Ontario, 1992) and derived from bioassay studies. According to these Guidelines, the disposal of such sediment has to be guided by environmental considerations. A significant fraction of these metals was extractable in 0.5 N HCl over a 12-hour period and considered as potentially bioavailable. The major accumulative phases of toxic metals in this sediment are exchangeable, carbonate, Fe/Mn oxides and organic matter but the relative importance of each phase varied for individual metals. Approximately 20% of the total extractable Cd is found in each of these four fractions. Pb, Zn and Mn are predominantly bound to carbonates, Fe/Mn oxides and organic matter. Cu shows a high affinity for organic matter and to a lesser extent for carbonates. Elevated levels of Cd, Pb, Cu, Zn, Mn and Cr in the exchangeable and/or soluble phase suggest that sediment associated metals, mobilised from streets in Sault Ste. Marie during runoff and snowmelt, would adversely impact water quality in the receiving waters. However, large fractions of the total metal load are associated with coarser particles which are unlikely to be transported through the drainage system into receiving waters.     

乐清湾养殖区表层沉积物重金属含量分布及污染评价

以乐清湾养殖区表层沉积物中Cu等7种重金属为研究对象,在野外实地调查取样及重金属含量测定基础上,以中国海洋沉积物质量(GB18668-2002)一类标准值为评价标准,利用单因子指数评价法、内梅罗综合污染指数评价法和沉积物质量基准(sediment quality guideline,SQG),对单项重金属污染程度、多种重金属综合污染效应及重金属潜在生物毒性风险进行了评价。结果表明,乐清湾养殖区表层沉积物重金属含量分布差别明显,所有采样点表层沉积物均受到Cu污染,局部受到严重Hg污染;大部分养殖区表层沉积物重金属污染达到轻度等级;所有养殖区均可发生由Cu偶尔引起的不利生物毒性效应,个别养殖区可发生由Hg频繁引发的不利生物毒性效应。乐清湾养殖区表层沉积物重金属主要来源于沿岸电镀企业废水排放及农药化肥造成的农业面源污染。开展Cu、Hg污染治理修复是实现乐清湾养殖环境安全的迫切需求。