Potentially toxic elements (PTEs) including nickel and chromium are often present in soils overlying basalt at concentrations above regulatory guidance values due to the presence of these elements in underlying geology. Oral bioaccessibility testing allows the risk posed by PTEs to human health to be assessed, however bioaccessibility is controlled by factors including mineralogy, particle size, solid phase speciation and encapsulation. X-ray diffraction (XRD) was used to characterise the mineralogy of 12 soil samples overlying Palaeogene basalt lavas in Northern Ireland and non specific sequential extraction coupled with chemometric analysis was used to determine the distribution of elements amongst soil components in 3 of these samples. The data obtained were related to total concentration and oral bioaccessible concentration to determine whether a relationship exists between the overall concentrations of PTEs, their bioaccessibility and the soils mineralogy and geochemistry.Gastric phase bioaccessible fraction (BAF%) ranged from 0.4% to 5.4% for chromium in soils overlying basalt and bioaccessible and total chromium concentrations are positively correlated. In contrast the range of gastric phase BAF for nickel was greater (1.4 to 43.8%), while no significant correlation was observed between bioaccessible and total nickel concentrations. However nickel BAF was inversely correlated with total concentration. Solid phase fractionation information showed that bioaccessible nickel was associated with calcium carbonate, aluminum oxide, iron oxide and clay related components, while bioaccessible chromium was associated with clay related components. This suggests that weathering significantly affects nickel bioaccessibility, but does not have the same effect on the bioaccessibility of chromium. Suggested keywordsoral bioaccessibility, nickel, chromium, basalt, sequential extraction, solid phase distribution 3

Correlation analyses were conducted on nickel (Ni), vanadium (V) and zinc (Zn) oral bioaccessible fractions (BAFs) and selected geochemistry parameters to identify specific controls exerted over trace element bioaccessibility. BAFs were determined by previous research using the Unified BARGE Method. Total trace element concentrations and soil geochemical parameters were analysed as part of the Geological Survey of Northern Ireland Tellus Project. Correlation analysis included Ni, V and Zn BAFs against their total concentrations, pH, estimated soil organic carbon (SOC) and a further eight element oxides. BAF data were divided into three separate generic bedrock classifications of basalt, lithic arenite and mudstone prior to analysis, resulting in an increase in average correlation coefficients between BAFs and geochemical parameters. Sulphur trioxide and SOC, spatially correlated with upland peat soils, exhibited significant positive correlations with all BAFs in gastric and gastrointestinal digestion phases, with such effects being strongest in the lithic arenite bedrock group. Significant negative relationships with bioaccessible Ni, V and Zn and their associated total concentrations were observed for the basalt group. Major element oxides were associated with reduced oral trace element bioaccessibility, with Al 2 O 3 resulting in the highest number of significant negative correlations followed by Fe 2 O 3. Spatial mapping showed that metal oxides were present at reduced levels in peat soils. The findings illustrate how specific geology and soil geochemistry exert controls over trace element bioaccessibility, with soil chemical factors having a stronger influence on BAF results than relative geogenic abundance. In general, higher Ni, V and Zn bioaccessibility is expected in peat soil types.

The environmental quality of land can be assessed by calculating relevant threshold values, which differentiate between concentrations of elements resulting from geogenic and diffuse anthropogenic sources and concentrations generated by point sources of elements. A simple process allowing the calculation of these typical threshold values (TTVs) was applied across a region of highly complex geology (Northern Ireland) to six elements of interest; arsenic, chromium, copper, lead, nickel and vanadium. Three methods for identifying domains (areas where a readily identifiable factor can be shown to control the concentration of an element) were used: k-means cluster analysis, boxplots and empirical cumulative distribution functions (ECDF). The ECDF method was most efficient at determining areas of both elevated and reduced concentrations and was used to identify domains in this investigation. Two statistical methods for calculating normal background concentrations (NBCs) and upper limits of geochemical baseline variation (ULBLs), currently used in conjunction with legislative regimes in the UK and Finland respectively, were applied within each domain. The NBC methodology was constructed to run within a specific legislative framework, and its use on this soil geochemical data set was influenced by the presence of skewed distributions and outliers. In contrast, the ULBL methodology was found to calculate more appropriate TTVs that were generally more conservative than the NBCs. TTVs indicate what a "typical" concentration of an element would be within a defined geographical area and should be considered alongside the risk that each of the elements pose in these areas to determine potential risk to receptors.

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The unknown aetiology of Chronic Kidney Disease (CKD) has attracted recent attention as a result of the increasing global prevalence and recent reviews of occupational and environmental exposure to nephrotoxins. The main focus of this research is to examine the potential relationship between environmental exposure to known nephrotoxins including arsenic, cadmium and lead and the potential health risk associated with the progressive dysfunction of the kidneys in renal impaired patients with CKD across Northern Ireland. In addition to these known nephrotoxins, co-abundance with several essential elements has been found to play a role as protecting mechanisms while others increase the uptake of nephrotoxic elements as a result of similar absorption mechanisms within the body. Key elements protecting the body from toxicity include selenium and zinc, whereas those which have been attributed to enhance the uptake of arsenic, cadmium and lead include iron and calcium. The compositional nature of the soil and stream geochemical data is explored to aid in the analysis of interactions between elements. Two approaches, one data-driven and the other knowledge-driven, are explored to investigate the associations between co-abundant elements. The bioaccessibility of these elements, which is the portion of the relevant toxin absorbed within the M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT2 body, is also investigated to identify areas across Northern Ireland with an increased environmental hazard and potential health risk. The study uses a combination of datasets from the United Kingdom Renal Registry (UKRR) unknown aetiology subset, the soil and stream geochemical dataset from the Tellus Survey (GSNI) with the addition of a bioaccessibility subset. Findings suggest a relationship between the presence of elevated arsenic in stream waters and impaired renal function of the kidneys.Interactions between essential elements and potentially toxic elements could explain the regional variation of CKD of uncertain aetiology across Northern Ireland.