Contaminant mobility as a result of sediment inundation : literature review and laboratory scale pilot study on mining contaminated sediments

This report presents a literature review of soil and sediment inundation methodologies and describes a pilot scale laboratory inundation study. Changing weather conditions, subsequent flooding events, and the increased frequency of such events both in the UK and worldwide is highlighting the need to research the area of contaminant mobility from soils and sediments under inundated conditions. The findings of such investigations impact on a wide variety of sectors, including human and ecological health, agriculture, building, transport, world economy and climate change. Standardised methodologies for the investigation of contaminant mobility resulting from soil/sediment inundation episodes are not available. Most research has been conducted in the agricultural sector for nutrient transport, as part of soil fertility and plant nutrition studies. Only recently has work been undertaken for studying potentially harmful element transport in inundated sediments/soils. A pilot scale laboratory study was undertaken using contaminated bank sediment samples collected from the Rookhope Burn catchment, Northern England, UK, with the aim to examine the extent of contaminant mobilisation from flooded sediments. The catchment has been affected by historical mining and processing of lead and zinc ore and is representative of several catchments affected by the environmental legacy related to mining in the Northern Pennine Orefield. Bank sediment Pb and Zn concentrations were found significantly above both the TEL and PEL sediment quality criteria, posing potentially a significant hazard to aquatic organisms. The source of the Pb and Zn in the sediments is related to the underlying mineralisation, mining activities and mine water discharges in the catchment. Abundances of original sulphide ore and authigenic metal-bearing phases were expected to vary through the catchment. The study design simulated rising flood water, a slow saturation of the sediment in order to induce a slow change in physico-chemical properties, followed by a 3 month (88 day) stagnation period. Natural day-night cycles were simulated by undertaking the study on the bench top during the winter of 2009/2010 (November to February). The chemical changes in the inundation water during the experiment were monitored and the sediment pore water at the end of the inundation period analysed. The inundation water pH remained alkaline to neutral, while redox measurements indicated oxic conditions in the water column throughout the inundation period. The pilot study showed that inundation of river bank sediments from the Rookhope Burn may be a significant pathway for contaminants in the catchment and that mobilisation from the sediments may pose a hazard to environmental receptors in the area, particularly with respect to Pb and Zn contamination. The different degrees and different rates of metal losses to the overlying water column observed during the flooding of the Rookhope Burn bank sediments demonstrated that the significance of metal mobilisation was dictated by the sediment composition. The inundation water composition monitored during the sediment flooding was used to indirectly infer possible processes that control contaminant fluxes from the sediments to the overlying water. Dissolved Pb concentration in the inundation water reflected the original concentration in the solid material and in sediments that had XRD-detectable galena and cerussite the dissolved Pb concentration reached a maximum value of 395 μg l-1. Cerussite, which is commonly formed as coatings on galena during the sulphide weathering, was close or supersaturated in those solutions, suggesting that the lead carbonate mineral phase provided a continuous source of Pb to these solutions. The initial dissolved Zn in the inundation waters was independent of the original concentration in the sediments. Sediments downstream a mine water discharge showed a greater availability of easily mobilised Zn, producing high initial Zn concentration in the inundation water, despite the relatively low Zn concentration in the inundated sediment. The Zn/SO4 and Cd/Zn molar ratios were both consistent with sphalerite mineral oxidation. The final inundation water solutions had the highest Zn concentrations for those sediment samples where sphalerite was detected by XRD. Redox sensitive elements such as Fe and Mn could not unequivocally indicate the presence of reducing conditions within the flooded sediments and the redox measurements were carried out only in the overlying water column (ORP above 200-350 mV). Low organic matter content and sandy texture would not have favoured the rapid formation of an anoxic layer. Yet, only extending the ORP measurements to the submerged sediment would determine the presence of flooding-induced reducing conditions. Reductive dissolution of Mn oxyhydroxides would result in release of Mn into solution, along with other trace metals, such as Pb and Zn. Mn increased in the inundation water throughout most or all the inundation period for some of the studied sediments. Their final pore water composition was significantly enriched in Mn (1300- 6500 μg l-1). Saturation indices indicated both rhodocrosite (MnCO3) and Mn oxides reached saturation. Therefore, it was not possible to preclude either the role of rhodocrosite as solubility controlling solid phase or the reductive dissolution of Mn oxides for accounting the enhanced Mn concentrations in the pore water and overlying water column without a better characterisation of the solid phase and monitoring of the sediment redox conditions. Amendments to the inundation test design have been recommended, which comprise: set-up to allow for the continuous monitoring of pore water dynamics and allow for the collection of pore water at the different times and measurement of pore water pH and Eh; inclusion of a blank test cell, to test the influence of the properties and the volume of the inundation water; inclusion of flow-cell tests to assess the influence of moving or stagnant inundation water; the inclusion of abiotic blanks to identify the role microbes play in the solubilisation of contaminants. complementary characterisation of the solid phase material and metal distribution in the sediment before and after the inundation experiment

Double Ionisation in R-Matrix Theory Using a 2-electron Outer Region

We have developed a two-electron outer region for use within R-matrix theory to describe double ionisation processes. The capability of this method is demonstrated for single-photon double ionisation of He in the photon energy region between 80 eV to 180 eV. The cross sections are in agreement with established data. The extended RMT method also provides information on higher-order processes, as demonstrated by the identification of signatures for sequential double ionisation processes involving an intermediate He$^{+}$ state with $n=2$.Comment: 5 pages, 4 figure

Anthropogenic and geogenic impacts on arsenic bioaccessibility in UK topsoils

Predictive linear regression (LR) modelling between bioaccessible arsenic (B-As) and a range of total elemental compositions and soil properties was executed in order to assess the potential for developing a national B-As dataset for the UK. LR indicates that total arsenic (As) is the only highly significant independent variable for estimating B-As in urban areas where it explains 75–92% of the variance. The broad compatibility of the London, Glasgow and Swansea regression models suggests that application of these models to estimate bioaccessible As in UK soils impacted by diffuse anthropogenic urban contamination and non-ferrous metal processing should be relatively accurate. In areas dominated by Jurassic ironstones and associated clays and limestones, total As, P and pH are significant, accounting for 53, 14 and 5%, respectively, of the B-As variance. Models based on total As as the sole predictor in the combined Jurassic and Cretaceous sedimentary ironstones datasets explain about 40% of the B-As variance. The median As bioaccessible fraction (%As-BAF) is 19 to 28% in the anthropogenic contamination impacted urban domains, but much lower (5–9%) in geogenic terrains dominated by ironstones. Results of this study can be used as part of a lines of evidence approach to localised risk assessment but should not be used to replace bioaccessibility testing at individual sites where local conditions may vary considerably from the broad overview presented in this study

Agent based modelling : initial assessment for use on soil bioaccessibility

This report describes the testing of Agent Based Modelling implementations in three different software packages: Repast-simphony, NetLogo and Insight-maker. These software have been evaluated against their capability to simulate the exposure of people as agents moving across Arsenic contaminated soils. Two of the three tested software (Repast-simphony and NetLogo) are recommended for assessment on more complex problems. An outline work plan is presented for future work

Heavy metal bioavailability and bioaccessibility in soil

This chapter considers the use of a variety of approaches to assess either the bioavailability or the bioaccessibility of metals in soil. The bioavailability of metals from soils is considered with respect to a series of single-extraction methods, including the use of ethylenediaminetetraacetic acid (EDTA), acetic acid, diethylenetriaminepentaacetic acid (DTPA), ammonium nitrate, calcium chloride and sodium nitrate. Then, a procedure for the recovery of metals using a three-stage sequential extraction protocol is described. Two alternate approaches for assessing the environmental health risk to humans by undertaking in vitro gastrointestinal extraction (also known as the physiologically based extraction test, PBET) are considered. Finally, two acid digestion protocols that allow the pseudo-total metal content of samples to be assessed are provided. In all cases details of how the different approaches can be performed are provided, including the specific reagents required (and their preparation), details of the different extraction and acid digestion protocols to be followed and suitable analytical details to allow the measurement of metals by inductively coupled plasma mass spectrometry (ICP-MS) with/without a collision/reaction cell. A detailed Notes section provides experimental details to guide the reader through some of the practical aspects of the procedures. Finally, some experimental results are provided as evidence of the suitability of the approaches described including single-extraction data, using EDTA and acetic acid, for metals in CRM BCR 700. In addition, in vitro gastrointestinal extraction data are provided for metals in CRM SRM 1570A (spinach leaves). The influence of time on the intestinal fluid phase on the recovery of metals in CRM SRM 1570A (spinach leaves) and CRM INCT-TL-1 (tea leaves) is investigated, as well as the repeatability in terms of recovery of metals from soil over a 3-week period by in vitro gastrointestinal extraction

Sources, mobility and bioaccessibility of potentially harmful elements in UK soils

Potentially harmful elements (PHE) occur both naturally from geogenic sources and from anthropogenic derived pollution. Anthropogenic sources can be further categorised into those derived from point sources. A point source is a single identifiable source which is confined to a very small area such as that arising from disposal of waste material or from an industrial plant. Diffuse pollution arises where substances are widely used and dispersed over an area as a result of land use activities, often associated with urban development. Examples of diffuse pollution include atmospheric deposition of contaminants arising from industry, domestic coal fires and traffic exhaust, and disposal of domestic coal ash. The total concentration and the chemical form and hence the mobility of the PHE in a soil is highly dependent on the source

Preclinical musculoskeletal junction testbed: Optimisation of a reproducible skeletal muscle construct [Abstract]

Preclinical musculoskeletal junction testbed: Optimisation of a reproducible skeletal muscle construct [Abstract

Small-scale skeletal muscle constructs for in-vitro musculoskeletal junction preclinical testbed [Abstract]

Small-scale skeletal muscle constructs for in-vitro musculoskeletal junction preclinical testbed [Abstract

A review of the current state of the art of physiologically-based tests for measuring human dermal in vitro bioavailability of polycyclic aromatic hydrocarbons (PAH) in soil

Polycyclic Aromatic Hydrocarbons are classed as Persistent Organic Pollutants, a large group of compounds that share similar characteristics. They are lipophilic, resistant to degradation in the environment and harmful to human and environmental health. Soil has been identified as the primary reservoir for Polycyclic Aromatic Hydrocarbons in the United Kingdom. This study reviews the literature associated with, or is relevant to, the measurement and modelling of dermal absorption of Polycyclic Aromatic Hydrocarbons from soils. The literature illustrates the use of in vivo, in vitro and in silico methods from a wide variety of scientific disciplines including occupational and environmental exposure, medical, pharmaceutical and cosmetic research and associated mathematical modelling. The review identifies a number of practical shortcomings which must be addressed if dermal bioavailability tests are to be applied to laboratory analysis of contaminated soils for human health risk assessment