Urban geochemistry: research strategies to assist risk assessment and remediation of brownfield sites in urban areas

Urban geochemical maps of Wolverhampton and Nottingham, based on multielement analysis of surface soils, have shown distribution patterns of “total” metals concentrations relating to past and present industrial and domestic land use and transport systems. Several methods have been used to estimate the solubility and potential bioavailability of metals, their mineral forms and potential risks to urban population groups. These include sequential chemical extraction, soil pore water extraction and analysis, mineralogical analysis by scanning electron microscopy, source apportionment by lead isotope analysis and the development of models to predict metal uptake by homegrown vegetables to provide an estimate of risk from metal consumption and exposure. The results from these research strategies have been integrated with a geographical information system (GIS) to provide data for future land-use planning.     

A Petrographic Investigation of two Sequential Extraction Techniques Applied to Anaerobic Canal Bed Mud

The application of sequential extraction procedures to determine metal speciation in sediments is fraught with uncertainty regarding what is actually dissolving or re-precipitating at each stage. In order to choose an appropriate scheme for the investigation of contaminated anaerobic mud two different sequential extraction procedures (Kersten and Förstner, 1986; Quevauviller, 1998) were investigated using a Cryogenic SEM (CryoSEM) technique coupled with energy dispersive X-ray analysis (EDXA). This enabled assessment of the degree of reagent selectivity and any re-precipitation associated with the respective methods. Analysis of the non-leached sediment revealed the most abundant authigenic minerals in order of decreasing abundance to be Fe²⁺-phosphate vivianite (Fe₃(PO₄)₂·8H₂O), mixed Fe, Zn, Cu sulphides, pyrite and calcite. After each stage of the sequential extraction the sediment residue was examined using CryoSEM. After extraction of the exchangeable fraction no obvious evidence of mineral dissolution was observed. Calcite was not completely dissolved during the carbonate extraction stage of either procedure. Vivianite began to dissolve in the carbonate extraction stage of both procedures and was completely dissolved by oxide extraction stage of both procedures. The sediment leached by acidified ammonium oxalate, contained abundant Fe oxalate crystals, suggesting that a large proportion of the Fe released from the vivianite has been re-precipitated. The Fe oxalate was then dissolved with the subsequent sulphide fraction. The technique used to extract the sulphide and organic fraction is the same in both schemes and no sulphide or metal rich organic matter was found in either residue.     

Contaminant source apportionment by PIMMS lead isotope analysis and SEM-image analysis

By combining scanning electron microscopy (SEM) image analysis and laser ablation plasma ionisation multi-collector mass spectrometry (LA-PIMMS), high precision lead isotope analyses can be obtained from individual metal-rich particles. Soils from Wolverhampton and Nottingham were sampled on the basis of high Pb concentrations or brownfield location. Pressed powder pellets of each were rastered by LA-PIMMS to obtain a bulk Pb-isotope signature. The results plot along an apparent mixing line between the major sources of lead contamination in the UK, that is UK ore deposits and alkyl-lead from petrol additives (Australian ore). Two particularly lead-rich soils were chosen to investigate the lead distribution and isotope variability between size and density fractions. The fine-grained and low-density fractions contained most of the lead and have Pb-isotope ratios comparable with the bulk soils. By contrast, the small, lead-enriched denser fractions contained only a minor proportion of the total lead but Pb-isotope signatures indicating relative enrichment in one or other of the end-members from the mixing line. Further characterisation of individual Pb-rich grains is in progress.