Influence of urban river restoration on nitrogen dynamics at the sediment-water interface.

River restoration projects focused on altering flow regimes through use of in-channel structures can facilitate ecosystem services, such as promoting nitrogen (N) storage to reduce eutrophication. In this study we use small flux chambers to examine ammonium (NH4+) and nitrate (NO3-) cycling across the sediment-water interface. Paired restored and unrestored study sites in 5 urban tributaries of the River Thames in Greater London were used to examine N dynamics following physical disturbances (0-3 min exposures) and subsequent biogeochemical activity (3-10 min exposures). Average ambient NH4+ concentrations were significantly different amongst all sites and ranged from 28.0 to 731.7 µg L-1, with the highest concentrations measured at restored sites. Average NO3- concentrations ranged from 9.6 to 26.4 mg L-1, but did not significantly differ between restored and unrestored sites. Average NH4+ fluxes at restored sites ranged from -8.9 to 5.0 µg N m-2 sec-1, however restoration did not significantly influence NH4+ uptake or regeneration (i.e., a measure of release to surface water) between 0-3 minutes and 3-10 minutes. Further, average NO3- fluxes amongst sites responded significantly between 0-3 minutes ranging from -33.6 to 97.7 µg N m-2 sec-1. Neither NH4+ nor NO3- fluxes correlated to sediment chlorophyll-a, total organic matter, or grain size. We attributed variations in overall N fluxes to N-specific sediment storage capacity, biogeochemical transformations, potential legacy effects associated with urban pollution, and variations in river-specific restoration actions.

The contaminant legacy from historic coastal landfills and their potential as sources of diffuse pollution.

Prior to modern environmental regulation landfills in low-lying coastal environments were frequently constructed without leachate control, relying on natural attenuation within inter-tidal sediments to dilute and disperse contaminants reducing environmental impact. With sea level rise and coastal erosion these sites may now pose a pollution risk, yet have received little investigation. This work examines the extent of metal contamination in saltmarsh sediments surrounding a historic landfill in the UK. Patterns of sediment metal data suggest typical anthropogenic pollution chronologies for saltmarsh sediments in industrialised nations. However, many metals were also enriched at depth in close proximity to the landfill boundary and are indicative of a historical leachate plume. Though this total metal load is low, e.g., c. 1200 and 1650kg Pb and Zn respectively, with >1000 historic landfills on flood risk or eroding coastlines in the UK this could represent a significant, yet under-investigated, source of diffuse pollution.

Unravelling metal mobility under complex contaminant signatures.

Metals are concerning pollutants in estuaries, where contamination can undergo significant remobilisation driven by physico-chemical forcing. Environmental concentrations of metals in estuarine sediments are often higher than natural backgrounds, but show no contiguity to potential sources. Thus, better understanding the metal mobility in estuaries is essential to improve identification of pollution sources and their accountability for environmental effects. This study aims to identify the key biogeochemical drivers of metal mobilisation on contaminated estuarine sediments through (1) evaluation of the potential mobilisation under controlled conditions, and (2) investigation of the relevance of metal mobilisation for in situ pollution levels in an area with multiple contaminant sources. Sediments from a saltmarsh adjacent to a coastal landfill, a marina, and a shipyard on the Thames Estuary (Essex, UK) were exposed in the laboratory (24h, N=96, 20°C) to water under various salinity, pH, and redox potential. Major cations, Fe(II), and trace metal concentrations were analysed in the leachate and sediment. Salinity, pH and redox had a significant effect on metal mobilisation (p<0.001), e.g. under certain conditions Fe(II) leaching was increased ~1000-fold. Measurements in situ of surface and subsurface sediment cores revealed that landfill proximity poorly explained metal spatial distribution. However, physicochemical parameters explained up to 97% of geochemically normalized metal concentrations in sediments. Organic matter and pH were dominant factors for most of the metal concentrations at the sediment surface. At subsurface, major cations (Ca, Na, Mg and K) were determinant predictors of metal concentrations. Applying the empirical model obtained in the laboratory to geochemical conditions of the studied saltmarsh it was possible to demonstrate that Fe mobilisation regulates the fate of this (and other) metal in that area. Thus, present results highlight the importance of metal mobility to control sediment pollution and estuarine fate of metals.