Partitioning of trace metals in sediments: Relationships with bioavailability

As a result of complex physical, chemical and biological processes, a major fraction of the trace metals introduced into the aquatic environment is found associated with the bottom sediments, distributed among a variety of physico-chemical forms. As these different metal forms will generally exhibit different chemical reactivities, the measurement of the total concentration of a particular metal provides little indication of potential interactions with the abiotic or biotic components present in the environment. In principle, the partitioning of sediment-bound metals could be determined both by thermodynamic calculations (provided equilibrium conditions prevail) and by experimental techniques. The modelling of sediment-bound metals is far less advanced than is that of dissolved species, primarily because the thermodynamic data needed for handling sediment-interstitial water systems are not yet available. The partitioning of a metal among various fractions obtained by experimental techniques (e.g., sequential extraction procedures) is necessarily operationally defined. These methods have, however, provided significant insight into the physico-chemical factors influencing the bioavailability of particulate trace metals; some of these factors are discussed.     

Quantification of changing Pseudomonas aeruginosa sodA, htpX and mt gene abundance in response to trace metal toxicity: a potential in situ biomarker of environmental health

Sediment-dwelling prokaryotes play a vital role in determining the fate and speciation of metals, yet are also susceptible to the biological effects of trace metals. In this article, optimized DNA extraction and purification techniques and species-specific primers are used to assess the genetic incidence and abundance of metal detoxification and general stress genes of Pseudomonas aeruginosa to complement chemical analysis in inferring the severity of metal-contaminated sites along the Clark Fork River, Montana. Results show the highest incidence of candidate genes related to bacterial stress at the most polluted site, while multiple regression analysis demonstrated significant correlations (P<0.05, r(2)=0.9) between in situ metal concentrations (As, Cu and Zn), total gene incidence, and the incidence of metal detoxification genes. Furthermore, principal components plotting the incidence of genes related to metal resistance show clear separation of sites giving clear clusters on the basis of contamination. Quantification of three genes (sodA, htpX and mt) from surveyed sites found significantly higher (anova, P<0.05) copy numbers at the more contaminated sites compared with reference sites. The development of rapid microbial biomarker tools represents a significant advance in the field of environmental biomonitoring and the prediction of metal bioavailability.     

Sorption of hydrophobic organic contaminants and trace metals on phytoplankton and implications for toxicity assessment

The partitioning of trace metals and hydrophobic organic contaminants to phytoplankton determines their toxicity as well as their fate and transport in aquatic ecosystems. Accurate impact assessments, therefore, depend on a good understanding of the factors regulating the sorption of these compounds to biotic particles. The accumulation of chlorinated organic compounds in phytoplankton is generally considered as being due solely to physical sorption, described by reversible equilibrium models based on Langmuir or Freundlich isotherms. On the other hand, the uptake of trace metals is a two phase process: a fast sorption component viewed as an ionexchange or a covalent bonding process with cell surface ligands, followed by an intracellular transport phase that is dependent on cellular metabolic activity. The uptake of inorganic and hydrophobic organic pollutants and their bioaccumulation are influenced in a complex manner by duration of exposure and cell density, by environmental factors such as pH, the concentration of cations and of dissolved and colloidal organic matter, as well as by phytoplankton physiological condition. High concentrations of H⁺, Ca²⁺, and Mg²⁺ ions will reduce trace metal sorption by directly competing for uptake sites on the cell's surface, whereas the presence of dissolved organic carbon such as natural and synthetic chelators and phytoplankton exudates will reduce the bioavailability of both trace metals and hydrophobic organic contaminants. Thus, the impact of toxic contaminants on phytoplankton may be determined as much by the factors influencing uptake and partitioning as by the potency of the toxicants and interspecies differences in sensitivity. Recommendations for improving toxicity assessments are presented.     

Trace elements in agroecosystems and impacts on the environment.

Trace elements mean elements present at low concentrations (mg kg-1 or less) in agroecosystems. Some trace elements, including copper (Cu), zinc (Zn), manganese (Mn), iron (Fe), molybdenum (Mo), and boron (B) are essential to plant growth and are called micronutrients. Except for B, these elements are also heavy metals, and are toxic to plants at high concentrations. Some trace elements, such as cobalt (Co) and selenium (Se), are not essential to plant growth but are required by animals and human beings. Other trace elements such as cadmium (Cd), lead (Pb), chromium (Cr), nickel (Ni), mercury (Hg), and arsenic (As) have toxic effects on living organisms and are often considered as contaminants. Trace elements in an agroecosystem are either inherited from soil parent materials or inputs through human activities. Soil contamination with heavy metals and toxic elements due to parent materials or point sources often occurs in a limited area and is easy to identify. Repeated use of metal-enriched chemicals, fertilizers, and organic amendments such as sewage sludge as well as wastewater may cause contamination at a large scale. A good example is the increased concentration of Cu and Zn in soils under long-term production of citrus and other fruit crops. Many chemical processes are involved in the transformation of trace elements in soils, but precipitation-dissolution, adsorption-desorption, and complexation are the most important processes controlling bioavailability and mobility of trace elements in soils. Both deficiency and toxicity of trace elements occur in agroecosystems. Application of trace elements in fertilizers is effective in correcting micronutrient deficiencies for crop production, whereas remediation of soils contaminated with metals is still costly and difficult although phytoremediation appears promising as a cost-effective approach. Soil microorganisms are the first living organisms subjected to the impacts of metal contamination. Being responsive and sensitive, changes in microbial biomass, activity, and community structure as a result of increased metal concentration in soil may be used as indicators of soil contamination or soil environmental quality. Future research needs to focus on the balance of trace elements in an agroecosystem, elaboration of soil chemical and biochemical parameters that can be used to diagnose soil contamination with or deficiency in trace elements, and quantification of trace metal transport from an agroecosystem to the environment.     

Influence of Soil Chemistry and Plant Physiology in the Phytoremediation of Cu,Mn, and Zn

Different anthropogenic sources of metals can result from agricultural, industrial, military, mining and urban activities that contribute to environmental pollution. Plants can be grown for phytoremediation to remove or stabilize contaminants in water and soil. Copper (Cu), manganese (Mn) and zinc (Zn) are trace essential metals for plants, although their role in homeostasis in plants must be strictly regulated to avoid toxicity. In this review, we summarize the processes involved in the bioavailability, uptake, transport and storage of Cu, Mn and Zn in plants. The efficiency of phytoremediation depends on several factors including metal bioavailability and plant uptake, translocation and tolerance mechanisms. Soil parameters, such as clay fraction, organic matter content, oxidation state, pH, redox potential, aeration, and the presence of specific organisms, play fundamental roles in the uptake of trace essential metals. Key processes in the metal homeostasis network in plants have been identified. Membrane transporters involved in the acquisition, transport and storage of trace essential metals are reviewed. Recent advances in understanding the biochemical and molecular mechanisms of Cu, Mn and Zn hyperaccumulation are described. The use of plant-bacteria associations, plant-fungi associations and genetic engineering has opened a new range of opportunities to improve the efficiency of phytoremediation. The main directions for future research are proposed from the investigation of published results.     

Bioremediation of metal‐contaminated surface and groundwaters

Microorganisms immobilize, mobilize, or transform metals by extracellular precipitation reactions, intracellular accumulation, oxidation and reduction reactions, methylation and demethylation, and extracellular binding and complexation. Nearly all of these microbe/metal interactions occur within the wetlands approach to acid mine drainage treatment, a process that is rapidly gaining support as a low‐maintenance, cost‐effective approach to solving an important environmental problem. Several proprietary processes, which employ nonliving microorganisms that are immobilized in polymer matrixes, are entering the water treatment market. These processes take advantage of negatively charged functional groups on cell walls and exopolymers of microorganisms that bind cationic metals. These biosorbents effectively remove low concentrations (<1 to about 20 mg/L) of heavy metal cations in the presence of high concentrations of alkaline earth metals (Ca²⁺ and Mg²⁺) and organic contaminants to levels lower than the U.S. National Drinking Water Standards. Immobilization of the biomass in polymer matrixes yields products that have substantial chemical and mechanical integrity. These immobilized products lend themselves to application in conventionally engineered systems such as up‐flow and down‐flow columns, expanded‐bed systems, dispersed‐bed systems, and low‐maintenance trough systems. Biosorption will probably play an important role in achieving the strict environmental standards now being enforced.     

Can we determine the biological availability of sediment-bound trace elements?

It is clear from available data that the susceptibility of biological communities to trace element contamination differs among aquatic environments. One important reason is that the bioavailability of metals in sediments appears to be altered by variations in sediment geochemistry. However, methods for explaining or predicting the effect of sediment geochemistry upon metal bioavailability are poorly developed. Experimental studies demonstrate that ingestion of sediments and uptake from solution may both be important pathways of metal bioaccumulation in deposit/detritus feeding species. Relative importance between the two is geochemistry dependent. Geochemical characteristics of sediments also affect metal concentrations in the tissues of organisms collected from nature, but the specific mechanisms by which these characteristics influence metal bioavailability have not been rigorously demonstrated. Several prerequisites are necessary to better understand the processes that control metal bioavailability from sediments. 1) improved computational or analytical methods for analyzing distribution of metals among components of the sediments; 2) improved computational methods for assessing the influences of metal form in sediments on sediment-water metal exchange; and 3) a better understanding of the processes controlling bioaccumulation of metals from solution and food by metazoan species directly exposed to the sediments. Such capabilities would allow mechanistic explanations essential to the development of practical tools sought for determining sediment quality criteria for metals.     

Models of regulation and accumulation of trace metals in marine invertebrates

1. General principles governing trace metal uptake and accumulation in marine invertebrates are identified.2. Key determinants of trace metal body concentrations are bioavailability from seawater and from food. However, the nature of the trace metal (essential vs non-essential, chemical properties, etc.) and the physiological state of the organism, strongly influence subsequent handling, distribution, tissue accumulation and excretion.3. The roles of metal-binding proteins (metallothioneins, transferrin-like proteins, etc.) and haemolymph cellular elements in metal transport and storage are described.4. Uptake of many trace metals from seawater generally conforms to Fick's Law of Diffusion, but is also influenced by non-specific binding to ligands in body fluids and cells, potential differences across body surfaces and, in some instances, by active transport processes involving ionic pumps and pinocytosis.5. Potential mechanisms underlying regulation of whole organism and tissue metal loads are outlined and compared with accumulation strategies. The significance of trace metal levels is discussed with regard to the well-being of marine invertebrates and their use in biomonitoring studies of trace metal pollution.     

Modeling speciation effects on biodegradation in mixed metal/chelate systems

A new model, CCBATCH, comprehensively couples microbially catalyzed reactions to aqueous geochemistry. The effect of aqueous speciation on biodegradation reactions and the effect of biological reactions on the concentration of chemical species (e.g. H₂CO₃, NH ₄ ⁺ , O₂) are explicitly included in CCBATCH, allowing systematic investigation of kinetically controlled biological reactions. Bulk-phase chemical speciation reactions including acid/base and complexation are modeled as thermodynamically controlled, while biological reactions are modeled as kinetically controlled. A dual-Monod kinetic formulation for biological degradation reactions is coupled with stoichiometry for the degradation reaction to predict the rate of change of all biological and chemical species affected by the biological reactions. The capability of CCBATCH to capture pH and speciation effects on biological reactions is demonstrated by a series of modeling examples for the citrate/Fe(III) system. pH controls the concentration of potentially biologically available forms of citrate. When the percentage of the degradable substrate is low due to complexation or acid/base speciation, degradation rates may be slow despite high concentrations of substrate Complexation reactions that sequester substratein non-degradable forms may prevent degradation or stopdegradation reactions prior to complete substrate utilization. The capability of CCBATCH to couple aqueous speciation changes to biodegradation reaction kinetics and stoichiometry allows prediction of these key behaviors in mixed metal/chelate systems.     

The SET and ERITME indices: Integrative tools for the management of polluted sites

To address the lack of biological methods for assessing soil quality and its contaminant retention capacity and to provide a tool with which stakeholders can assess the risk of transfer of trace elements in the soil to the soil fauna, the Sum of the Excess of Transfers (SET) index from soil to the snail Cantareus aspersus has been broadened to include the internal concentrations of reference (CIRef) for 14 metals and metalloids (As, Cd, Co, Cu, Cr, Hg, Mo, Ni, Pb, Sb, Sn, Sr, Tl and Zn). Weighting the transfer of these elements by a risk coefficient (i.e., their toxicity point) provides a new assessment tool for stakeholders: the ERITME (Evaluation of the Risk of the Transferred Metal Elements) tool. This upgraded tool has been used to highlight unsuspected risks and revise management priorities at an industrial site. Moreover, using the tool to determine the risk from metal trace elements allows for improved environmental risk assessment, as ERITME is an integrative tool based on the real bioavailability of metals rather than chemical measures that often lead to unsatisfactory assessments of transfer. The SET and ERITME integrative tools, using snails as indicators of trace element zooavailability, can be used in environmental risk assessment.     

Role of Marine Cyanobacteria in Trace Metal Bioavailability in Seawater

In seawater, several trace metals with biological significance are highly complexed with organic matter. Marine cyanobacteria are an important phytoplanktonic group, with the ability to release trace metal-binding compounds to the seawater medium, which in turn modulates their bioavailability and influences their biogeochemical cycles. Such interactions may allow cyanobacteria to more easily access less available trace metals essential for their metabolic processes, or, conversely, keep the toxic forms of the trace metals from reaching intolerable levels. In this minireview, Cu and Fe interactions with cyanobacteria received special attention, although other trace metals (Co, Pb, Zn, and Cd) are also covered. Recent research has shed light on many aspects of trace metal–cyanobacteria ecology in seawater; nevertheless, the biochemical processes behind this dynamics and the structure of the vast majority of the metal binding compounds remain unclear.     

Metal mobilization from soils by phytosiderophores – experiment and equilibrium modeling

Aims

To test if multi–surface models can provide a soil-specific prediction of metal mobilization by phytosiderophores (PS) based on the characteristics of individual soils.

Methods

Mechanistic multi-surface chemical equilibrium modeling was applied for obtaining soil-specific predictions of metal and PS speciation upon interaction of the PS 2’-deoxymugineic acid (DMA) with 6 soils differing in availability of Fe and other metals. Results from multi-surface modeling were compared with empirical data from soil interaction experiments.

Results

For soils in which equilibrium was reached during the interaction experiment, multi-surface models could well predict PS equilibrium speciation. However, in uncontaminated calcareous soils, equilibrium was not reached within a week, and experimental and modeled DMA speciation differed considerably. In soils with circum-neutral pH, on which Fe deficiency is likely to occur, no substantial Fe mobilization by DMA was predicted. However, in all but the contaminated soils, Fe mobilization by DMA was observed experimentally. Cu and Ni were the quantitatively most important metals competing with Fe for complexation and mobilization by DMA.

Conclusion

Thermodynamics are unable to explain the role of PS as Fe carrier in calcareous soils, and the kinetic aspects of metal mobilization by PS need to be closer examined in order to understand the mechanisms underlying strategy II Fe acquisition.     

Trace metals accumulation in the eco-system water – soil – vegetation (Agropyron cristatum) – common voles (Microtus arvalis) – parasites (Hymenolepis diminuta) in Radnevo region,Bulgaria

BackgroundCoal and coal processing industries provoke trace metal pollution, which has a negative effect on the water – soil – vegetation – small mammals eco-system, constituting part of the food chain and exerting a serious impact on human health.ObjectivesAssessment of the environmental impact of Maritza iztok coal complex, situated east of Radnevo town, Bulgaria, by tracking the dynamics and accumulation of trace metals in the eco-system water – soil – vegetation – common voles – parasites.MethodsSamples from surface waters, their nearby uncultivated soils, meadow uncultivated vegetation (Agropyron cristatum) and field common voles (Microtus arvalis) were collected. In situ measurements and laboratory extraction procedures and analyses were performed. Accumulation and mobility indices were calculated. The distribution of dissolved Mn, Ni, Cu, Zn and Pb chemical species in water-soil extracts was calculated using a thermodynamic approach. Two thermodynamic models were applied – the classical ion-association model for calculating the inorganic trace metal species and the Stockholm Humic Model (SHM) accounting for the complexation reactions of trace metals with organic matter. Visual Minteq computer program, Version 3.1 was used. The relationship chemical species - bioaccumulation was discussed.ResultsPb and Mn, together with SO₄²⁻ and PO₄^3- were found to be the main pollutants of waters in the region. The soils studied exhibited low concentrations of trace metals, not exceeding the specified MACs. The content of Mn was the highest, followed by Zn, Pb, Cu and Ni. The highest phytoaccumulation coefficients in the studied uncultivated grass vegetation were calculated for Cu and Zn, being 1–2 orders of magnitude higher than those of Mn and Ni. The accumulation of trace metals was explained on the basis of ions mobility and chemical species distribution. In the case of the host-parasite system Microtus alvaris - Hymenolepis diminuta, Zn displays the highest accumulation coefficient, followed by those of Cu and Pb. The parasite showed a higher bioaccumulation compared to infected common voles, with the highest bioaccumulation found for Ni.ConclusionsThe bioaccumulation of trace metals depends on their mobility, concentration and chemical forms in water-soil solutions. Metal-organic species stimulate the phytoaccumulation of trace metals while inorganic ones suppress it. The sequence of trace metals bioaccumulation in common voles is analogous to that of soil contamination. The parasite exhibited higher bioaccumulation levels compared to infected common voles.     

Trace Metal Mixture Toxicity in Aquatic Organism Reviewed from a Biotoxicity Perspective

Biotoxicity of individual metals is well investigated but that of metal mixture, an environmental reality, in the developing metal mixture, is relatively obscure. Experimental evidences had shown that this mixture could give rise to combined effects that were different from the effect of metals one by one. This review provides an overview of recent research on metal mixture toxicity and the methods employed to predict their toxic combined effects. The two established reference models, the concentration-addition model and the independent-addition model, were used for evaluating the combined effect from the biological activities of the metal mixtures. While the reference models had provided reasonable tools for analyzing the combined effects, the actual predictions for binary metal mixtures showed often somewhat less than additive combined effects compared to what has been observed. As the metal bioavailability is oriented by several environmental factors as well as the toxicodynamics of metals is highly compound-specific, the non-interactive combined effects may be confused with different processes of the interactions. Thus, for improving the predictability of combined effects in metal mixture toxicity, numerous qualitative and quantitative analysis are required for the processes governing the toxicokinetics and dynamics of metals in aquatic organisms.     

BMRI-2, Rossendorf/Dresden, Germany (30 August - 1 September 2000)

Clearly, there is much left to be understood about microbial processes and interactions with metals, but much progress has been made, and the multidisciplinary approach of groups who are studying both the microbial populations and the chemistry of biotransformations of metals by bacteria will ensure rapid progress in our understanding of these issues. Several major points from different speakers summarize this meeting and are usefully reiterated at this point: Toxic metal ions, unlike organic pollutants, are immutable, and their bioavailability is a critical feature of their toxicity. The mobility, transport and fate of toxic metals and radionuclides in the environment are dependent on chemical and geochemical processes in which micro-organisms are intimately involved. Metals can be mobilized as well as immobilized by microorganisms. Metal/radionuclide valencies and chemical properties are critical to their environmental mobility. Bacterial- or fungal-metal interactions will be complicated by the presence of other pollutants. The identification of bacteria from environmental samples should not rely on one methodology, as these have been shown to be biased. Sonja Selenska-Pobell organized both BMRI-1 in 1998 and BMRI-2, which had well over 100 participants from Europe, Russia, USA and Japan in attendance. Thirty-one oral presentations were given, and over 30 posters were displayed over two poster sessions. BMRI-3 is provisionally planned for 2002 at GBF, Braunschweig, Germany.     

Towards a model of non-equilibrium binding of metal ions in biological systems

We have used a systems biology approach to address the hitherto insoluble problem of the quantitative analysis of non-equilibrium binding of aqueous metal ions by competitive ligands in heterogeneous media. To-date, the relative proportions of different metal complexes in aqueous media has only been modelled at chemical equilibrium and there are no quantitative analyses of the approach to equilibrium. While these models have improved our understanding of how metals are used in biological systems they cannot account for the influence of kinetic factors in metal binding, transport and fate. Here we have modelled the binding of aluminium, Al(III), in blood serum by the iron transport protein transferrin (Tf) as it is widely accepted that the biological fate of this non-essential metal is not adequately described by experiments, invitro and insilico, which have consistently demonstrated that at equilibrium 90% of serum Al(III) is bound by Tf. We have coined this paradox ‘the blood-aluminium problem’ and herein applied a systems biology approach which utilised well-found assumptions to pare away the complexities of the problem such that it was defined by a comparatively simple set of computational rules and, importantly, its solution assumed significant predictive capabilities. Here we show that our novel computational model successfully described the binding of Al(III) by Tf both at equilibrium and as equilibrium for Al_Tf was approached. The model predicted significant non-equilibrium binding of Al by ligands in competition with Tf and, thereby, provided an explanation of why the distribution of Al(III) in the body cannot be adequately described by its binding and transport by Tf alone. Generically the model highlighted the significance of kinetic in addition to thermodynamic constraints in defining the fate of metal ions in biological systems.     

Recognition of metal cations by biological systems.

Recognition of metal cations by biological systems can be compared with the geochemical criteria for isomorphous replacement. Biological systems are more highly selective and much more rapid. Methods of maintaining an optimum concentration, including storage and transfer for the essential trace elements, copper and iron, used in some organisms are in part reproducible by coordination chemists while other features have not been reporduced in models. Poisoning can result from a foreign metal taking part in a reaction irreversibly so that the recognition site or molecule is not released. For major nutrients, sodium, potassium, magnesium and calcium, there are similarities to the trace metals in selective uptake but differences qualitatively and quantitatively in biological activity. Compounds selective for potassium replace all the solvation sphere with a symmetrical arrangement of oxygen atoms; those selective for sodium give an asymmetrical environment with retention of a solvent molecule. Experiments with naturally occurring antibiotics and synthetic model compounds have shown that flexibility is an important feature of selectivity and that for transfer or carrier properties there is an optimum (as opposed to a maximum) metal-ligand stability constant. Thallium is taken up instead of potassium and will activate some enzymes; it is suggested that the poisonous characteristics arise because the thallium ion may bind more strongly than potassium to part of a site and then fail to bind additional atoms as required for the biological activity. Criteria for the design of selective complexing agents are given with indications of those which might transfer more than one metal at once.     

Rhizoremediation of metals: harnessing microbial communities

With the increasing successful stories of decontamination, different strategies for metal remediation are gaining importance and popularization in developing countries. Rhizoremediation, is one such promising option that harnesses the impressive capabilities of microorganisms associated with roots to degrade organic pollutants and transform toxic metals. Since it is a plant based in-situ phytorestoration technique it is proven to be economical, efficient and easy to implement under field conditions. Plants grown in metal contaminated sites harbor unique metal tolerant and resistant microbial communities in their rhizosphere. These rhizo-microflora secrete plant growth promoting substances, siderophores, phytochelators to alleviate metal toxicity, enhance the bioavailability of metals (phytoremediation) and complexation of metals (phytostabilisation). Selection of right bacteria/consortia and inoculation to seed/ roots of suitable plant species will widen the perspectives of rhizoremediation.     

Trace metals in the benthic habitat of the Maarsseveen Lakes system,The Netherlands

The cadmium, zinc, lead and copper concentrations in benthic invertebrates and sediment were determined during two consecutive winters in the Maarsseveen Lakes system. A sequential extraction procedure was applied to estimate the bioavailability of the trace metals in the sediment. Based on the trace metal analyses of organisms and sediment, it is concluded that the Maarsseveen Lakes system has background levels of cadmium, zinc, lead and copper. As the majority of metals was present in geochemically more stable sediment phases, the sequential extractions provided limited additional information on trace metal bioavailability.     

Quantitative imaging of metals in tissues

Metals and other trace elements play an important role in many physiological processes in all biological systems. Characterization of precise metal concentrations, their spatial distribution, and chemical speciation in individual cells and cell compartments will provide much needed information to explore the metallome in health and disease. Synchrotron-based X-ray fluorescent microscopy (SXRF) is the ideal tool to quantitatively measure trace elements with high sensitivity at high resolution. SXRF is based on the intrinsic fluorescent properties of each element and is therefore element specific. Recent advances in synchrotron technology and optimization of sample preparation have made it possible to image metals in mammalian tissue with submicron resolution. In combination with correlative methods, SXRF can now, for example, determine the amount and oxidation state of trace elements in intra-cellular compartments and identify cell-specific changes in the metal ion content during development or disease progression.