Interactions of land use and dynamic river conditions on sorption equilibria between benthic sediments and river soluble reactive phosphorus concentrations.

Within-river cycling of P is a crucial link between catchment pollution sources and the resulting ecological impacts and integrates the biogeochemistry and hydrodynamics of river systems. This study investigates benthic sediment P sorption in relation to river soluble reactive phosphorus (SRP) concentrations during high- to low-flow changes in a major mixed land use river system in NE Scotland. We hypothesised that sediments comprised P sinks during moderate to higher flows but became P saturated with loss of buffering function during prolonged baseflow. Sediment characteristics were evaluated and equilibrium P concentrations (EPC(0)) calculated using a standardised batch adsorption method (EPC(0) values 0.04-1.75 micromol Pl(-1)). Pollution-impacted tributaries (32-69% catchment agricultural land cover) had increased SRP concentrations (0.19-2.62 micromol Pl(-1)) and maintained EPC(0)SRP values during summer baseflow so that sediments were indicated as P sources. This deviation from a geochemical sediment-water P equilibrium was attributed to biological accumulation of P from the water column into the sediments. In particular, large stores of sediment P accumulated in main stem reaches below agricultural tributaries and this may be consequential for sensitive downstream ecosystems. Hence, biogeochemical processes at the river bed may strongly influence river SRP cycling between geochemical and biotic pools. The nature of this internal reservoir of river P and its ecosystem interactions needs better understanding to enable best results to be attained from catchment mitigation actions designed to maintain/improve ecological status under the Water Framework Directive.

Hydrogarnet: a host phase for Cr(VI) in chromite ore processing residue (COPR) and other high pH wastes.

For understanding both the environmental behavior and developing remediation treatments for chromium ore processing residue (COPR) it is important to identify all the potentially soluble sources of Cr(VI). Hydrogarnet has been identified as a major phase in COPR and it has been previously speculated that it has a capacity to host Cr(VI). Here we provide direct evidence of this capacity by demonstrating the incorporation of Cr(VI) into laboratory synthesized hydrogarnet. Electron microscopy and energy dispersive X-ray microanalysis show incorporation of approximately 17000-22000 mg Cr(VI) kg(-1) hydrogarnet. X-ray powder diffraction data show that peak intensities are altered by chromium substitution and that chromium substituted hydrogarnets have a smaller unit cell than the pure Ca-Al end member. This is consistent with substitution of hydroxyl tetrahedra by smaller chromate tetrahedra. Electron energy loss spectroscopy confirms the tetrahedral coordination and hexavalent oxidation state of chromium in the hydrogarnets. The maximum amount of hexavalent chromium that can be introduced synthetically corresponds to a replacement of about one out of every eight hydroxyl tetrahedral per unit cell by a CrO4(2-) tetrahedra and tallies closely with the amount of chromium measured in hydrogarnets from COPR. Chromium-bearing hydrogarnet is the most abundant crystalline phase in millions of tons of COPR contaminating land around Glasgow, Scotland, and was recently identified in COPR from sites in North America. Calculations based on its abundance and its Cr(VI) content indicate that hydrogarnet can host as much as 50% of the Cr(VI) found in some COPR samples.

The implications of integrated assessment and modelling studies for the future remediation of chromite ore processing residue disposal sites.

Chromite ore processing residue (COPR) waste from a former chromium chemical works (1830-1968) is still contaminating groundwater in Glasgow, Scotland, with carcinogenic hexavalent chromium, Cr(VI). An integrated analytical, experimental and modelling approach has identified and accounted for mineral phases and processes responsible for the retention and release of Cr(VI) under prevailing field conditions. Both the nature of mineral phase retention and the buffered high pH of the sites, however, militate against direct remediative treatment of the source material, for example by the application of generic methods (e.g. FeSO4) that have been successfully employed elsewhere for the reduction of Cr(VI) to Cr(III) in other matrices. The interception and treatment of groundwater to remove Cr(VI) and the capping of sites to reduce human exposure to airborne Cr(VI)-contaminated dust may well be more realistic and effective, at least in the short to medium term.

The effect of EDTA and fulvic acid on Cd, Zn, and Cu toxicity to a bioluminescent construct (pUCD607) of Escherichia coli.

The hypothesis, that metal toxicity is dominated by free ion activity, was tested by comparing calculated metal activities with measured toxic responses to a genetically modified, luminescent bacterium, Escherichia coli. The toxicity of Cd, Cu, and Zn sulphate salts in the presence of EDTA and fulvic acid in well-defined solutions was measured. Good agreement between free metal activity and toxicity was found for Cu but not for Zn and Cd. The toxicity relationships were altered by glucose addition to the organism. Stable chloride complexes may have contributed to the toxicity of Cd under the test conditions. The results suggest that there is not always a simple relationship between toxicity and free-ion metal concentration and that further account should be taken of competitive interactions between living cells and ligands and the physiological status of the organism.