Accumulated metal speciation in earthworm populations with multi-generational exposure to metalliferous soils: cell fractionation and high energy synchrotron analyses

Predicting metal bioaccumulation and toxicity in soil organisms is complicated by site-specific biotic and abiotic parameters. In this study we exploited tissue fractionation and digestion techniques, combined with X-ray absorption spectroscopy (XAS), to investigate the whole-body and subcellular distributions, ligand affinities, and coordination chemistry of accumulated Pb and Zn in field populations of the epigeic earthworm Lumbricus rubellus inhabiting three contrasting metalliferous and two unpolluted soils. Our main findings were (i) earthworms were resident in soils with concentrations of Pb and Zn ranging from 1200 to 27 000 mg kg(-1) and 200 to 34 000 mg kg(-1), respectively; (ii) Pb and Zn primarily accumulated in the posterior alimentary canal in nonsoluble subcellular fractions of earthworms; (iii) site-specific differences in the tissue and subcellular partitioning profiles of populations were observed, with earthworms from a calcareous site partitioning proportionally more Pb to their anterior body segments and Zn to the chloragosome-rich subcellular fraction than their acidic-soil inhabiting counterparts; (iv) XAS indicated that the interpopulation differences in metal partitioning between organs were not accompanied by qualitative differences in ligand-binding speciation, because crystalline phosphate-containing pyromorphite was a predominant chemical species in the whole-worm tissues of all mine soil residents. Differences in metal (Pb, Zn) partitioning at both organ and cellular levels displayed by field populations with protracted histories of metal exposures may reflect their innate ecophysiological responses to essential edaphic variables, such as Ca2+ status. These observations are highly significant in the challenging exercise of interpreting holistic biomarker data delivered by "omic" technologies.

Evidence of heavy metal movement down the profile of a heavily-sludged soil

Two sites in central England where sewage sludge has been deposited for decades were studied to measure the heavy metal distribution in the soil profiles. The first site (S 1) was a field receiving heavy loads sludge from a nearby wastewater treatment plant, and the second (S2) was a farm applying 'normal' sludge rates of 8 t ha(-1) y(-1) of the same sludge. Soil samples were also taken by a near-by untreated control site. In S I the movement of heavy metals was significant even down to 80 cm depth compared to the control. In S2, the concentrations of lead (Pb) and zinc (Zn) and the organic matter content were higher than the control down to 20 cm, while nickel (Ni) moved significantly down to 80 cm. This underlies. the possibility that the metals bound onto organic surfaces moved along with organic matter down to that depth. The movement of metals in S2 points out the potential risks of applying sewage sludge for a long time.

Strategic management of non-point source pollution from sewage sludge

In the UK, the recycling of sewage sludge to land is expected to double by 2006 but the security of this route is threatened by environmental concerns and health scares. Strategic investment is needed to ensure sustainable and secure sludge recycling outlets. At present, the security of this landbank for sludge recycling is determined by legislation relating to nutrient rather than potentially toxic elements (PTEs) applications to land - especially the environmental risk linked to soil phosphorus (P) saturation. We believe that not all land has an equal risk of contributing nutrients derived from applications to land to receiving waters. We are currently investigating whether it is possible to minimise nutrient loss by applying sludge to land outside Critical Source Areas (CSAs) regardless of soil P Index status. Research is underway to develop a predictive and spatially-sensitive, semi-distributed model of critical thresholds for sludge application that goes beyond traditional 'end-of-pipe" or "edge-of-field" modelling, to include hydrological flow paths and delivery mechanisms to receiving waters from non-point sources at the catchment scale.

Construction of a historical Water Pollution Index for the Mersey Basin

The Mersey Basin has been significantly polluted for over 200 years. However, there is a lack of quantitative historical water quality data as effective water quality monitoring and data recording only began 30-40 years ago. This paper assesses water pollution in the Mersey Basin using a Water Pollution Index constructed from social and economic data. Methodology, output and the difficulties involved with validation are discussed. With the limited data input available the index approximately reproduces historical water quality. The paper illustrates how historical studies of environmental water quality may provide valuable identification of factors responsible for pollution and a marker set for contemporary and future water quality issues in the context of the past. This is an issue of growing research interest.

Soil geochemical analyses as an indication of metal working at the excavation of a house in the Roman City at Silchester (UK)

Silchester is the site of a major late Iron Age and Roman town (Calleva Atrebatum), situated in northern Hampshire (England (UK)) and occupied between the late first century BC and the fifth or sixth century AD. Extensive evidence of the nature of the buildings and the plan of the town was obtained from excavations undertaken between 1890 and 1909. The purpose of this study was to use soil geochemical analyses to reinforce the archaeological evidence particularly with reference to potential metal working at the site. Soil analysis has been used previously to distinguish different functions or land use activity over a site and to aid identification and interpretation of settlement features (Entwistle et al., 2000). Samples were taken from two areas of the excavation on a 1-metre grid. Firstly from an area of some 500 square metres from contexts of late first/early second century AD date throughout the entirety of a large 'town house' (House 1) from which there was prima facie evidence of metalworking.

Sequential extraction and single-step cold-acid extraction: A feasibility study for use with freshwater-canal sediments

This investigation examines metal release from freshwater sediment using sequential extraction and single-step cold-acid leaching. The concentrations of Cd, Cr, Cu, Fe, Ni, Pb and Zn released using a standard 3-step sequential extraction (Rauret et al., 1999) are compared to those released using a 0.5 M HCl; leach. The results show that the three sediments behave in very different ways when subject to the same leaching experiments: the cold-acid extraction appears to remove higher relative concentrations of metals from the iron-rich sediment than from the other two sediments. Cold-acid extraction appears to be more effective at removing metals from sediments with crystalline iron oxides than the "reducible" step of the sequential extraction. The results show that a single-step acid leach can be just as effective as sequential extractions at removing metals from sediment and are a great deal less time-consuming.

The use of earth observation techniques to improve catchment-scale pollution predictions

Remote sensing can potentially provide information useful in improving pollution transport modelling in agricultural catchments. Realisation of this potential will depend on the availability of the raw data, development of information extraction techniques, and the impact of the assimilation of the derived information into models. High spatial resolution hyperspectral imagery of a farm near Hereford, UK is analysed. A technique is described to automatically identify the soil and vegetation endmembers within a field, enabling vegetation fractional cover estimation. The aerially-acquired laser altimetry is used to produce digital elevation models of the site. At the subfield scale the hypothesis that higher resolution topography will make a substantial difference to contaminant transport is tested using the AGricultural Non-Point Source (AGNPS) model. Slope aspect and direction information are extracted from the topography at different resolutions to study the effects on soil erosion, deposition, runoff and nutrient losses. Field-scale models are often used to model drainage water, nitrate and runoff/sediment loss, but the demanding input data requirements make scaling up to catchment level difficult. By determining the input range of spatial variables gathered from EO data, and comparing the response of models to the range of variation measured, the critical model inputs can be identified. Response surfaces to variation in these inputs constrain uncertainty in model predictions and are presented. Although optical earth observation analysis can provide fractional vegetation cover, cloud cover and semi-random weather patterns can hinder data acquisition in Northern Europe. A Spring and Autumn cloud cover analysis is carried out over seven UK sites close to agricultural districts, using historic satellite image metadata, climate modelling and historic ground weather observations. Results are assessed in terms of probability of acquisition probability and implications for future earth observation missions. (C) 2003 Elsevier Ltd. All rights reserved.

Is the OECD acute worm toxicity test environmentally relevant? The effect of mineral form on calculated lead toxicity

In a series of experiments the toxicity of lead to worms in soil was determined following the draft OECD earthworm reproduction toxicity protocol except that lead was added as solid lead nitrate, carbonate and sulphide rather than as lead nitrate solution as would normally be the case. The compounds were added to the test soil to give lead concentrations of 625-12500 pg Pb g-1 of soil. Calculated toxicities of the lead decreased in the order nitrate > carbonate > sulphide, the same order as the decrease in the solubility of the metal compounds used. The 7-day LC50 (lethal concentration when 50% of the population is killed) for the nitrate was 5321 +/- 275 mug Pb g(-1) of soil and this did not change with time. The LC50 values for carbonate and sulphide could not be determined at the concentration ranges used. The only parameter sensitive enough to distinguish the toxicities of the three compounds was cocoon (egg) production. The EC50S for cocoon production (the concentration to produce a 50% reduction in cocoon production) were 993, 8604 and 10 246 mug Pb g(-1) of soil for lead nitrate, carbonate and sulphide, respectively. Standard toxicity tests need to take into account the form in which the contaminant is present in the soil to be of environmental relevance. (C) 2002 Elsevier Science Ltd. All rights reserved.

Distribution of selected heavy metals in sediments of the Agueda river (Central Portugal)

The state of river water deterioration in the Agueda hydrographic basin, mostly in the western part, partly reflects the high rate of housing and industrial development in this area in recent years. The streams have acted as a sink for organic and inorganic loads from several origins: domestic and industrial sewage and agricultural waste. The contents of the heavy metals Cr, Cd, Ni, Cu, Pb, and Zn were studied by sequential chemical extraction of the principal geochemical phases of streambed sediments, in the <63 mum fraction, in order to assess their potential availability to the environment, investigating, the metal concentrations, assemblages, and trends. The granulometric and mineralogical characteristics of this sediment fraction were also studied. This study revealed clear pollution by Cr, Cd, Ni, Cu, Zn, and Pb, as a result from both natural and anthropogenic origins. The chemical transport of metals appears to be essentially by the following geochemical phases, in decreasing order of significance: (exchangeable + carbonates) much greater than (organics) much greater than (Mn and Fe oxides and hydroxides). The (exchangeable + carbonate) phase plays an important part in the fixation of Cu, Ni, Zn, and Cd. The organic phase is important in the fixation of Cr, Pb, and also Cu and Ni. Analyzing the metal contents in the residual fraction, we conclude that Zn and Cd are the most mobile, and Cr and Pb are less mobile than Cu and Ni. The proximity of the pollutant sources and the timing of the influx of contaminated material control the distribution of the contaminant-related sediments locally and on the network scale.

A multi-scale framework for strategic management of diffuse pollution

A multi-scale framework for decision support is presented that uses a combination of experiments, models, communication, education and decision support tools to arrive at a realistic strategy to minimise diffuse pollution. Effective partnerships between researchers and stakeholders play a key part in successful implementation of this strategy. The Decision Support Matrix (DSM) is introduced as a set of visualisations that can be used at all scales, both to inform decision making and as a communication tool in stakeholder workshops. A demonstration farm is presented and one of its fields is taken as a case study. Hydrological and nutrient flow path models are used for event based simulation (TOPCAT), catchment scale modelling (INCA) and field scale flow visualisation (TopManage). One of the DSMs; The Phosphorus Export Risk Matrix (PERM) is discussed in detail. The PERM was developed iteratively as a point of discussion in stakeholder workshops, as a decision support and education tool. The resulting interactive PERM contains a set of questions and proposed remediation measures that reflect both expert and local knowledge. Education and visualisation tools such as GIS, risk indicators, TopManage and the PERM are found to be invaluable in communicating improved farming practice to stakeholders. (C) 2008 Elsevier Ltd. All rights reserved.

Towards a nutrient export risk matrix approach to managing agricultural pollution at source

A generic Nutrient Export Risk Matrix (NERM) approach is presented. This provides advice to farmers and policy makers on good practice for reducing nutrient loss and is intended to persuade them to implement such measures. Combined with a range of nutrient transport modelling tools and field experiments, NERMs can play an important role in reducing nutrient export from agricultural land. The Phosphorus Export Risk Matrix (PERM) is presented as an example NERM. The PERM integrates hydrological understanding of runoff with a number of agronomic and policy factors into a clear problem-solving framework. This allows farmers and policy makers to visualise strategies for reducing phosphorus loss through proactive land management. The risk Of Pollution is assessed by a series of informed questions relating to farming intensity and practice. This information is combined with the concept of runoff management to point towards simple, practical remedial strategies which do not compromise farmers' ability to obtain sound economic returns from their crop and livestock.

Characterization and identification of mixed-metal phosphates in soils: the application, of Raman spectroscopy

The development of protocols for the identification of metal phosphates in phosphate-treated, metal-contaminated soils is a necessary yet problematical step in the validation of remediation schemes involving immobilization of metals as phosphate phases. The potential for Raman spectroscopy to be applied to the identification of these phosphates in soils has yet to be fully explored. With this in mind, a range of synthetic mixed-metal hydroxylapatites has been characterized and added to soils at known concentrations for analysis using both bulk X-ray powder diffraction (XRD) and Raman spectroscopy. Mixed-metal hydroxylapatites in the binary series Ca-Cd, Ca-Pb, Ca-Sr and Cd-Pb synthesized in the presence of acetate and carbonate ions, were characterized using a range of analytical techniques including XRD, analytical scanning electron microscopy (SEM), infrared spectroscopy (IR), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and Raman spectroscopy. Only the Ca-Cd series displays complete solid solution, although under the synthesis conditions of this study the Cd-5(PO4)(3)OH end member could not be synthesized as a pure phase. Within the Ca-Cd series the cell parameters, IR active modes and Raman active bands vary linearly as a function of Cd content. X-ray diffraction and extended X-ray absorption fine structure spectroscopy (EXAFS) suggest that the Cd is distributed across both the Ca(1) and Ca(2) sites, even at low Cd concentrations. In order to explore the likely detection limits for mixed-metal phosphates in soils for XRD and Raman spectroscopy, soils doped with mixed-metal hydroxylapatites at concentrations of 5, 1 and 0.5 wt.% were then studied. X-ray diffraction could not confirm unambiguously the presence or identity of mixed-metal phosphates in soils at concentrations below 5 wt.%. Raman spectroscopy proved a far more sensitive method for the identification of mixed-metal hydroxylapatites in soils, which could positively identify the presence of such phases in soils at all the dopant concentrations used in this study. Moreover, Raman spectroscopy could also provide an accurate assessment of the degree of chemical substitution in the hydroxylapatites even when present in soils at concentrations as low as 0.1%.

Interactions between earthworms and arsenic in the soil environment: a review

Chemical pollution of the environment has become a major source of concern. In particular, many studies have investigated the impact of pollution on biota in the environment. Studies on metalliferous contaminated mine spoil wastes have shown that some soil organisms have the capability to become resistant to metal/metalloid toxicity. Earthworms are known to inhabit arsenic-rich metalliferous soils and, due to their intimate contact with the soil, in both the solid and aqueous phases, are likely to accumulate contaminants present in mine spoil. Earthworms that inhabit metalliferous contaminated soils must have developed mechanisms of resistance to the toxins found in these soils. The mechanisms of resistance are not fully understood; they may involve physiological adaptation (acclimation) or be genetic. This review discusses the relationships between earthworms and arsenic-rich mine spoil wastes, looking critically at resistance and possible mechanisms of resistance, in relation to soil edaphic factors and possible trophic transfer routes. (C) 2003 Elsevier Science Ltd. All rights reserved.

Enhanced phytoextraction: II. Effect of EDTA and citric acid on heavy metal uptake by Helianthus annuus from a calcareous soil

High biomass producing plant species, such as Helianthus annuus, have potential for removing large amounts of trace metals by harvesting the aboveground biomass if sufficient metal concentrations in their biomass can be achieved. However, the low bioavailability of heavy metals in soils and the limited translocation of heavy metals to the shoots by mosthigh biomass producing plant species limit the efficiency of the phytoextraction process. Amendment of a contaminated soil with ethylene diamine letraacetic acid (EDTA) or citric acid increases soluble heavy metal concentrations, potentially rendering them more available for plant uptake. This article discusses the effects of EDTA and citric acid on the uptake of heavy metals and translocation to aboveground harvestable plant parts in Helianthus annuus. EDTA was included in the research for comparison purposes in our quest for less persistent alternatives, suitable for enhanced phytoextraction. Plants were grown in a calcareous soil moderately contaminated with Cu, Pb, Zn, and Cd and treated with increasing concentrations of EDTA (0. 1, 1, 3, 5, 7, and 10 mmol kg(-1) soil) or citric acid (0. 01, 0. 05, 0.25, 0.442, and 0.5 mol kg(-1) soil). Heavy metal concentrations in harvested shoots increased with EDTA concentration but the actual amount of phytoextracted heavy metals decreased at high EDTA concentrations, due to severe growth depression. Helianthus annuus suffered heavy metal stress due to the significantly increased bioavailable metal fraction in the soil. The rapid mineralization of citric acid and the high buffering capacity of the soil made citric acid inefficient in increasing the phytoextracted amounts of heavy metals. Treatments that did not exceed the buffering capacity of the soil (< 0.442 mol kg(-1) soil) did not result in any significant increase in shoot heavy metal concentrations. Treatments with high concentrations resulted in a dissolution of the carbonates and compaction of the soil. These physicochemical changes caused growth depression of Helianthus annuus. EDTA and citric acid added before sowing of Helianthus annuus did not appear to be efficient amendments when phytoextraction of heavy metals from calcareous soils is considered.