The relationship between historical development and potentially toxic element concentrations in urban soils.

Increasing urbanisation has a direct impact on soil quality, resulting in elevated concentrations of potentially toxic elements (PTEs) in soils. This research aims to assess if soil PTE concentrations can be used as an 'urbanisation tracer' by investigating geogenic and anthropogenic source contributions and controls, and considering PTE enrichment across historical urban development zones. The UK cities of Belfast and Sheffield are chosen as study areas, where available shallow and deep concentrations of PTEs in soil are compared to identify geogenic and anthropogenic contributions to PTEs. Cluster analysis and principal component analysis are used to elucidate the main controls over PTE concentrations. Pollution indices indicate that different periods of historical development are linked to enrichment of different PTEs. Urban subdomains are identified and background values calculated using various methodologies and compared to generic site assessment criteria. Exceedances for a number of the PTEs considered suggest a potential human health risk could be posed across subdomains of both Belfast and Sheffield. This research suggests that airborne diffuse contamination from often historical sources such as traffic, domestic combustion and industrial processes contribute greatly to soil contamination within urban environments. The relationship between historical development and differing PTEs is a novel finding, suggesting that PTEs have the potential for use as 'urbanisation tracers'. The investigative methodology employed has potential applications for decision makers, urban planners, regulators and developers of urban areas.

When are total concentrations not total? Factors affecting geochemical analytical techniques for measuring element concentrations in soil.

Inductively coupled plasma (ICP) following aqua regia digestion and X-ray fluorescence (XRF) are both geochemical techniques used to determine 'total' concentrations of elements in soil. The aim of this study is to compare these techniques, identify elements for which inconsistencies occur and investigate why they arise. A study area (∼14,000 km(2)) with a variety of total concentration controls and a large geochemical dataset (n = 7950) was selected. Principal component analysis determined underlying variance in a dataset composed of both geogenic and anthropogenic elements. Where inconsistencies between the techniques were identified, further numerical and spatial analysis was completed. The techniques are more consistent for elements of geogenic sources and lead, whereas other elements of anthropogenic sources show less consistency within rural samples. XRF is affected by sample matrix, while the form of element affects ICP concentrations. Depending on their use in environmental studies, different outcomes would be expected from the techniques employed, suggesting the choice of analytical technique for geochemical analyses may be more critical than realised.

The effects of lead sources on oral bioaccessibility in soil and implications for contaminated land risk management.

Lead (Pb) is a non-threshold toxin capable of inducing toxic effects at any blood level but availability of soil screening criteria for assessing potential health risks is limited. The oral bioaccessibility of Pb in 163 soil samples was attributed to sources through solubility estimation and domain identification. Samples were extracted following the Unified BARGE Method. Urban, mineralisation, peat and granite domains accounted for elevated Pb concentrations compared to rural samples. High Pb solubility explained moderate-high gastric (G) bioaccessible fractions throughout the study area. Higher maximum G concentrations were measured in urban (97.6 mg kg(-1)) and mineralisation (199.8 mg kg(-1)) domains. Higher average G concentrations occurred in mineralisation (36.4 mg kg(-1)) and granite (36.0 mg kg(-1)) domains. Findings suggest diffuse anthropogenic and widespread geogenic contamination could be capable of presenting health risks, having implications for land management decisions in jurisdictions where guidance advises these forms of pollution should not be regarded as contaminated land.

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.