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.

Soil-Geochemical Factors controlling the Distribution and Oral Bioaccessibility of Nickel, Vanadium and Chromium in Northern Ireland Soils

Geogenic nickel (Ni), vanadium (V) and chromium (Cr) are present at elevated levels in soils in Northern Ireland. Whilst Ni, V and Cr total soil concentrations share common geological origins, their respective levels of oral bioaccessibility are influenced by different soil-geochemical factors. Oral bioaccessibility extractions were carried out on 145 soil samples overlying 9 different bedrock types to measure the bioaccessible portions of Ni, V and Cr. Principal component analysis identified two components (PC1 and PC2) accounting for 69% of variance across 13 variables from the Northern Ireland Tellus Survey geochemical data. PC1 was associated with underlying basalt bedrock, higher bioaccessible Cr concentrations and lower Ni bioaccessibility. PC2 was associated with regional variance in soil chemistry and hosted factors accounting for higher Ni and V bioaccessibility. Eight per cent of total V was solubilised by gastric extraction on average across the study area. High median proportions of bioaccessible Ni were observed in soils overlying sedimentary rock types. Whilst Cr bioaccessible fractions were low (max = 5.4%), the highest measured bioaccessible Cr concentration reached 10.0 mg kg-1, explained by factors linked to PC1 including high total Cr concentrations in soils overlying basalt bedrock.

Metals in the Exosphere of the Highly Irradiated Planet WASP-12b

We present near-UV transmission spectroscopy of the highly irradiated transiting exoplanet WASP-12b, obtained with the Cosmic Origins Spectrograph on the Hubble Space Telescope. The spectra cover three distinct wavelength ranges: NUVA (2539-2580 Å), NUVB (2655-2696 Å), and NUVC (2770-2811 Å). Three independent methods all reveal enhanced transit depths attributable to absorption by resonance lines of metals in the exosphere of WASP-12b. Light curves of total counts in the NUVA and NUVC wavelength ranges show a detection at a 2.5s level. We detect extra absorption in the Mg II ??2800 resonance line cores at the 2.8s level. The NUVA, NUVB, and NUVC light curves imply effective radii of 2.69 ± 0.24 R J , 2.18 ± 0.18 R J , and 2.66 ± 0.22 R J respectively, suggesting the planet is surrounded by an absorbing cloud which overfills the Roche lobe. We detect enhanced transit depths at the wavelengths of resonance lines of neutral sodium, tin, and manganese, and at singly ionized ytterbium, scandium, manganese, aluminum, vanadium, and magnesium. We also find the statistically expected number of anomalous transit depths at wavelengths not associated with any known resonance line. Our data are limited by photon noise, but taken as a whole the results are strong evidence for an extended absorbing exosphere surrounding the planet. The NUVA data exhibit an early ingress, contrary to model expectations; we speculate this could be due to the presence of a disk of previously stripped material.

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.

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.

Hybrid Organic–Inorganic Polyoxometalates: Functionalization of VIV/ VV Nanosized Clusters to Produce Molecular Capsules

Functionalization of polyoxovanadate clusters using phosphonate and arsonate ligands results in molecular capsules (see structure; green V, purple P, red O, black C). Through the use of extended homologous ligands, these hybrid organic-inorganic capsules can be successively elongated into tubular molecules.

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.

Investigation of the solid-liquid phase transition of carbon at 150 GPa with spectrally resolved X-ray scattering

We have resolved the solid-liquid phase transition of carbon at pressures around 150GPa. High-pressure samples of different temperatures were created by laser-driven shock compression of graphite and varying the initial density from 1.30g/cm³ to 2.25g/cm³. In this way, temperatures from 5700K to 14,500K could be achieved for relatively constant pressure according to hydrodynamic simulations. From measuring the elastic X-ray scattering intensity of vanadium K-alpha radiation at 4.95keVat a scattering angle of 126°, which is very sensitive to the solid-liquid transition, we can determine whether the sample had transitioned to the fluid phase. We find that samples of initial density 1.3g/cm³ and 1.85g/cm³ are liquid in the compressed states, whereas samples close to the ideal graphite crystal density of 2.25g/cm³ remain solid, probably in a diamond-like state.

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

The peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO4{WO(O-2)(2)}(4)]@PIILP has been prepared by anion exchange of ring opening metathesis-derived pyrrolidinium-decorated norbornene/ cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO4{WO(O-2)(2)}(4)]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46 428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst.

Enhancement of Wear and Corrosion Resistance of Beta Titanium Alloy by Laser Gas Alloying with Nitrogen

The relatively high elastic modulus coupled with the presence of toxic vanadium (V) in Ti6Al4 V alloy has long been a concern in orthopaedic applications. To solve the problem, a variety of non-toxic and low modulus beta-titanium (beta-Ti) alloys have been developed. Among the beta-Ti alloy family, the quaternary Ti-Nb-Zr-Ta (TNZT) alloys have received the highest attention as a promising replacement for Ti6Al4 V due to their lower elastic modulus and outstanding long term stability against corrosion in biological environments. However, the inferior wear resistance of TNZT is still a problem that must be resolved before commercialising in the orthopaedic market. In this work, a newly-developed laser surface treatment technique was employed to improve the surface properties of Ti-35.3Nb-7.3Zr-5.7Ta alloy. The surface structure and composition of the laser-treated TNZT surface were examined by grazing incidence x-ray diffraction (GI-XRD) and x-ray photoelectron spectroscopy (XPS). The wear and corrosion resistance were evaluated by pin-on-plate sliding test and anodic polarisation test in Hanks’ solution. The experimental results were compared with the untreated (or base) TNZT material. The research findings showed that the laser surface treatment technique reported in this work can effectively improve the wear and corrosion resistance of TNZT.