Correlation analysis as a tool to investigate the bioaccessibility of nickel, vanadium and zinc in Northern Ireland soils

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 gastro-intestinal 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 Al2O3 resulting in the highest number of significant negative correlations followed by Fe2O3. 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 importance of solid-phase distribution on the oral bioaccessibility of Ni and Cr in soils overlying Palaeogene basalt lavas, Northern Ireland

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 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 (1.4–43.8 %), 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, aluminium 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.

Investigating local relationships between trace elements in soils and cancer data

Medical geology research has recognised a number of potentially toxic elements (PTEs), such as arsenic, cobalt, chromium, copper, nickel, lead, vanadium, uranium and zinc, known to influence human disease by their respective deficiency or toxicity. As the impact of infectious diseases has decreased and the population ages, so cancer has become the most common cause of death in developed countries including Northern Ireland. This research explores the relationship between environmental exposure to potentially toxic elements in soil and cancer disease data across Northern Ireland. The incidence of twelve different cancer types (lung, stomach, leukaemia, oesophagus, colorectal, bladder, kidney, breast, mesothelioma, melanoma and non melanoma(NM) both basal and squamous, were examined in the form of twenty-five coded datasets comprising aggregates over the 12 year period from 1993 to 2006. A local modelling technique,geographically weighted regression (GWR) is usedto explore the relationship between environmental exposure and cancer disease data. The results show comparisons of the geographical incidence of certain cancers (stomach and NM squamous skin cancer) in relation to concentrations of certain PTEs (arsenic levels in soils and radon were identified). Findings from the research have implications for regional human health risk assessments.

SPHERE: Stormont Parliamentary Hansards: Embedded in Research and Education

SPHERE (Stormont Parliamentary Hansards: Embedded in Research and Education) was a JISC-funded project based at King’s College, London and Queen’s University, Belfast, working in Partnership with the Northern Ireland Assembly Library, and the NIA Official Report (Hansard). Its purpose was to assess the use, value and impact of The Stormont Papers digital resource, and to use the results of this assessment to make recommendations for a series of practical approaches to embed the resource within teaching, learning and research among the wider user community. The project began in November 2010 and was concluded in April 2010.

A series of formal reports on the project are published by JISC online at http://www.jisc.ac.uk/whatwedo/programmes/digitisation/impactembedding/sphere.aspx

SPHERE Impact analysis summary
Portable Document Format
SPHERE interviews report
SPHERE Outreach use case
SPHERE research use case
SPHERE teaching use_case
SPHERE web survey report
SPHERE web analysis

Application of factor analysis and geostatistics to identify processes controlling the distribution and bioaccessibility of trace elements in Northern Ireland soils

Geologic and environmental factors acting over varying spatial scales can control
trace element distribution and mobility in soils. In turn, the mobility of an element in soil will affect its oral bioaccessibility. Geostatistics, kriging and principal component analysis (PCA) were used to explore factors and spatial ranges of influence over a suite of 8 element oxides, soil organic carbon (SOC), pH, and the trace elements nickel (Ni), vanadium (V) and zinc (Zn). Bioaccessibility testing was carried out previously using the Unified BARGE Method on a sub-set of 91 soil samples from the Northern Ireland Tellus1 soil archive. Initial spatial mapping of total Ni, V and Zn concentrations shows their distributions are correlated spatially with local geologic formations, and prior correlation analyses showed that statistically significant controls were exerted over trace element bioaccessibility by the 8 oxides, SOC and pH. PCA applied to the geochemistry parameters of the bioaccessibility sample set yielded three principal components accounting for 77% of cumulative variance in the data
set. Geostatistical analysis of oxide, trace element, SOC and pH distributions using 6862 sample locations also identified distinct spatial ranges of influence for these variables, concluded to arise from geologic forming processes, weathering processes, and localised soil chemistry factors. Kriging was used to conduct a spatial PCA of Ni, V and Zn distributions which identified two factors comprising the majority of distribution variance. This was spatially accounted for firstly by basalt rock types, with the second component associated with sandstone and limestone in the region. The results suggest trace element bioaccessibility and distribution is controlled by chemical and geologic processes which occur over variable spatial ranges of influence.

Numerical assessment of potential impacts of hydraulically fractured Bowland Shale on overlying aquifers

Natural gas extracted from hydraulically fractured shale formations potentially has a big impact on the global energy landscape. However, there are concerns of potential environmental impacts of hydraulic fracturing of the shale formations, particularly those related to water quality. To evaluate the potential impact of hydraulically fractured shale on overlying aquifers, we conduct realizations of numerical modeling simulations to assess fluid flow and chloride transport from a synthetic Bowland Shale over a period of 11,000 years. The synthetic fractured shale was represented by a three-dimensional discrete fracture model that was developed by using the data from a Bowland Shale gas exploration in Lancashire, UK. Chloride mass exchange between fractures and the rock matrix was fully accounted for in the model. The assessment was carried out to investigate fluid and chloride mass fluxes before, during, and after hydraulic fracturing of the Bowland Shale. Impacts of the upward fracture height and aperture, as well as hydraulic conductivity of the multilayered bedrock system, are also included this assessment. This modeling revealed that the hydraulically fractured Bowland Shale is unlikely to pose a risk to its overlying groundwater quality when the induced fracture aperture is ≤200 µm. With the fracture aperture ≥1000 µm, the upward chloride flux becomes very sensitive to the upward fracture height growth and hydraulic conductivity of the multilayered bedrock system. In the extremely unlikely event of the upward fracture growth directly connecting the shale formation to the overlying Sherwood Sandstone aquifer with the fracture aperture ≥1000 µm, the upward chloride mass flux could potentially pose risks to the overlying aquifer in 100 years. The model study also revealed that the upward mass flux is significantly intercepted by the horizontal mass flux within a high permeable layer between the Bowland Shale and its overlying aquifers, reducing further upward flux toward the overlying aquifers.

Comparison of methods used to calculate typical threshold values for potentially toxic elements in soil

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.

Integrating geophysical data and upscaling techniques to support regional groundwater flow modelling: A practical example of the Lagan Valley, Northern Ireland

When studying heterogeneous aquifer systems, especially at regional scale, a degree of generalization is anticipated. This can be due to sparse sampling regimes, complex depositional environments or lack of accessibility to measure the subsurface. This can lead to an inaccurate conceptualization which can be detrimental when applied to groundwater flow models. It is important that numerical models are based on observed and accurate geological information and do not rely on the distribution of artificial aquifer properties. This can still be problematic as data will be modelled at a different scale to which it was collected. It is proposed here that integrating geophysics and upscaling techniques can assist in a more realistic and deterministic groundwater flow model. In this study, the sedimentary aquifer of the Lagan Valley in Northern Ireland is chosen due to intruding sub-vertical dolerite dykes. These dykes are of a lower permeability than the sandstone aquifer. The use of airborne magnetics allows the delineation of heterogeneities, confirmed by field analysis. Permeability measured at the field scale is then upscaled to different levels using a correlation with the geophysical data, creating equivalent parameters that can be directly imported into numerical groundwater flow models. These parameters include directional equivalent permeabilities and anisotropy. Several stages of upscaling are modelled in finite element. Initial modelling is providing promising results, especially at the intermediate scale, suggesting an accurate distribution of aquifer properties. This deterministic based methodology is being expanded to include stochastic methods of obtaining heterogeneity location based on airborne geophysical data. This is through the Direct Sample method of Multiple-Point Statistics (MPS). This method uses the magnetics as a training image to computationally determine a probabilistic occurrence of heterogeneity. There is also a need to apply the method to alternate geological contexts where the heterogeneity is of a higher permeability than the host rock.

The development of Temporal Cognition

Time features in two key ways in cognition, each of which is discussed in turn in this chapter: time is processed as a dimension of stimuli or events, and time is represented as a framework in which events can be located. Section 1 examines the first of these from a developmental perspective, by reviewing research on age-related changes in the accuracy of duration processing. The Piagetian approach linked changes in duration processing to the development of a concept of time as a dimension of events separable from other event dimensions. This is contrasted with recent research conducted within the framework of Scalar Expectancy Theory, which models development in terms of changes in components of specialized timing mechanisms. Section 2 discusses developmental changes in the temporal frameworks that children use to represent the locations of events. Although as adults, we represent times as locations on a linear framework stretching from the past, to the present, and into the future, this way of representing time is not developmentally basic. A model is proposed of developmental stages in the acquisition of a mature temporal framework. The chapter concludes by considering two themes that cut across Section 1 and 2: the issue of whether there are both qualitative and quantitative change in children’s temporal abilities, and the link between temporal and spatial cognition.

Combining multi-scale geophysical techniques for robust hydro-structural characterisation in catchments underlain by hard rock in post-glacial regions

Accurate conceptual models of groundwater systems are essential for correct interpretation of monitoring data in catchment studies. In surface-water dominated hard rock regions, modern ground and surface water monitoring programmes often have very high resolution chemical, meteorological and hydrological observations but lack an equivalent emphasis on the subsurface environment, the properties of which exert a strong control on flow pathways and interactions with surface waters. The reasons for this disparity are the complexity of the system and the difficulty in accurately characterising the subsurface, except locally at outcrops or in boreholes. This is particularly the case in maritime north-western Europe, where a legacy of glacial activity, combined with large areas underlain by heterogeneous igneous and metamorphic bedrock, make the structure and weathering of bedrock difficult to map or model. Traditional approaches which seek to extrapolate information from borehole to field-scale are of limited application in these environments due to the high degree of spatial heterogeneity. Here we apply an integrative and multi-scale approach, optimising and combining standard geophysical techniques to generate a three-dimensional geological conceptual model of the subsurface in a catchment in NE Ireland. Available airborne LiDAR, electromagnetic and magnetic data sets were analysed for the region. At field-scale surface geophysical methods, including electrical resistivity tomography, seismic refraction, ground penetrating radar and magnetic surveys, were used and combined with field mapping of outcrops and borehole testing. The study demonstrates how combined interpretation of multiple methods at a range of scales produces robust three-dimensional conceptual models and a stronger basis for interpreting groundwater and surface water monitoring data.

Trace Element Abundance and Renal Disease

This research investigates the relationship between elevated trace elements in soils, stream sediments and stream water and the prevalence of Chronic Kidney Disease (CKD). The study uses a collaboration of datasets provided from the UK Renal Registry Report (UKRR) on patients with renal diseases requiring treatment including Renal Replacement Therapy (RRT), the soil geochemical dataset for Northern Ireland provided by the Tellus Survey, Geological Survey of Northern Ireland (GSNI) and the bioaccessibility of Potentially Toxic Elements (PTEs) from soil samples which were obtained from the Unified Barge Method (UBM). The relationship between these factors derives from the UKRR report which highlights incidence rates of renal impaired patients showing regional variation with cases of unknown aetiology. Studies suggest a potential cause of the large variation and uncertain aetiology is associated with underlying environmental factors such as the oral bioaccessibility of trace elements in the gastrointestinal tract.
As previous research indicates that long term exposure is related to environmental factors, Northern Ireland is ideally placed for this research as people traditionally live in the same location for long periods of time. Exploratory data analysis and multivariate analyses are used to examine the soil, stream sediments and stream water geochemistry data for a range of key elements including arsenic, lead, cadmium and mercury identified from a review of previous renal disease literature. The spatial prevalence of patients with long term CKD is analysed on an area basis. Further work includes cluster analysis to detect areas of low or high incidences of CKD that are significantly correlated in space, Geographical Weighted Regression (GWR) and Poisson kriging to examine locally varying relationship between elevated concentrations of PTEs and the prevalence of CKD.