James J. Rothwell

A spatial and seasonal assessment of river water chemistry across North West England

This paper presents information on the spatial and seasonal patterns of river water chemistry at approximately 800 sites in North West England based on data from the Environment Agency regional monitoring programme. Within a GIS framework, the linkages between average water chemistry (pH, sulphate, base cations, nutrients and metals) catchment characteristics (topography, land cover, soil hydrology, base flow index and geology), rainfall, deposition chemistry and geo-spatial information on discharge consents (point sources) are examined. Water quality maps reveal that there is a clear distinction between the uplands and lowlands. Upland waters are acidic and have low concentrations of base cations, explained by background geological sources and land cover. Localised high concentrations of metals occur in areas of the Cumbrian Fells which are subjected to mining effluent inputs. Nutrient concentrations are low in the uplands with the exception sites receiving effluent inputs from rural point sources. In the lowlands, both past and present human activities have a major impact on river water chemistry, especially in the urban and industrial heartlands of Greater Manchester, south Lancashire and Merseyside. Over 40% of the sites have average orthophosphate concentrations >0.1mg-Pl(-1). Results suggest that the dominant control on orthophosphate concentrations is point source contributions from sewage effluent inputs. Diffuse agricultural sources are also important, although this influence is masked by the impact of point sources. Average nitrate concentrations are linked to the coverage of arable land, although sewage effluent inputs have a significant effect on nitrate concentrations. Metal concentrations in the lowlands are linked to diffuse and point sources. The study demonstrates that point sources, as well as diffuse sources, need to be considered when targeting measures for the effective reduction in river nutrient concentrations. This issue is clearly important with regards to the European Union Water Framework Directive, eutrophication and river water quality.

Arsenic retention and release in ombrotrophic peatlands.

Organic matter can play an important role in the mobility and fate of As in the environment, but there is a lack of data on As biogeochemistry in ombrotrophic peatlands. The aim of this study was to investigate As retention and release in atmospherically contaminated ombrotrophic peat soils in the Peak District National Park (UK). Solid phase As concentrations in the peat soils exceed 25 mg kg(-1). Solid phase As and Fe concentrations are closely correlated at sites where the peat is subjected to drying and oxic conditions. In a wetter zone of the bog, solid phase As and Fe distributions are decoupled, suggesting that As retention in these systems is not solely controlled by the presence of Fe oxides. Comparison of solid phase As and Pb distributions reveals that As has been subjected to post-depositional mobility in areas of water table fluctuation. Conversely, at permanently waterlogged locations As is immobile. Detailed stream water sampling reveals that As is released from the organic-rich uplands soils into the fluvial system. Dissolved As concentrations are highly variable, with values ranging from 0.20 to 7.28 microg l(-1). Stream water As concentrations are elevated during late summer stormflow periods when there has been re-wetting of the peat after significant water table draw-down. Dissolved As is strongly correlated to dissolved organic carbon under stormflow and baseflow. The results of this study suggest that organic matter plays an important role in As dynamics in ombrotrophic peatlands, but further work is needed to identify the exact As binding and release mechanisms. Drying and re-wetting of ombrotrophic peat soils and associated changes in redox status has the potential to lead to increased As mobility. Further work is needed to provide information on how predicted climate change will influence As cycling at sites containing a legacy of atmospheric contamination.

Rainwater runoff retention on an aged intensive green roof

Urban areas are characterised by large proportions of impervious surfaces which increases rainwater runoff and the potential for surface water flooding. Increased precipitation is predicted under current climate change projections, which will put further pressure on urban populations and infrastructure. Roof greening can be used within flood mitigation schemes to restore the urban hydrological balance of cities. Intensive green roofs, with their deeper substrates and higher plant biomass, are able to retain greater quantities of runoff, and there is a need for more studies on this less common type of green roof which also investigate the effect of factors such as age and vegetation composition. Runoff quantities from an aged intensive green roof in Manchester, UK, were analysed for 69 rainfall events, and compared to those on an adjacent paved roof. Average retention was 65.7% on the green roof and 33.6% on the bare roof. A comprehensive soil classification revealed the substrate, a mineral soil, to be in good general condition and also high in organic matter content which can increase the water holding capacity of soils. Large variation in the retention data made the use of predictive regression models unfeasible. This variation arose from complex interactions between Antecedant Dry Weather Period (ADWP), season, monthly weather trends, and rainfall duration, quantity and peak intensity. However, significantly lower retention was seen for high rainfall events, and in autumn, which had above average rainfall. The study period only covers one unusually wet year, so a longer study may uncover relationships to factors which can be applied to intensive roofs elsewhere. Annual rainfall retention for Manchester city centre could be increased by 2.3% by a 10% increase in intensive green roof construction. The results of this study will be of particular interest to practitioners implementing greenspace adaptation in temperate and cool maritime climates.

A classification and regression tree model of controls on dissolved inorganic nitrogen leaching from European forests

Often, there is a non-linear relationship between atmospheric dissolved inorganic nitrogen (DIN) input and DIN leaching that is poorly captured by existing models. We present the first application of the non-parametric classification and regression tree approach to evaluate the key environmental drivers controlling DIN leaching from European forests. DIN leaching was classified as low (<3), medium (3-15) or high (>15kg N ha(-1) year(-1)) at 215 sites across Europe. The analysis identified throughfall NO(3)(-) deposition, acid deposition, hydrology, soil type, the carbon content of the soil, and the legacy of historic N deposition as the dominant drivers of DIN leaching for these forests. Ninety four percent of sites were successfully classified into the appropriate leaching category. This approach shows promise for understanding complex ecosystem responses to a wide range of anthropogenic stressors as well as an improved method for identifying risk and targeting pollution mitigation strategies in forest ecosystems.

Metal and nutrient dynamics on an aged intensive green roof

Runoff and rainfall quality was compared between an aged intensive green roof and an adjacent conventional roof surface. Nutrient concentrations in the runoff were generally below Environmental Quality Standard (EQS) values and the green roof exhibited NO3(-) retention. Cu, Pb and Zn concentrations were in excess of EQS values for the protection of surface water. Green roof runoff was also significantly higher in Fe and Pb than on the bare roof and in rainfall. Input-output fluxes revealed the green roof to be a potential source of Pb. High concentrations of Pb within the green roof soil and bare roof dusts provide a potential source of Pb in runoff. The origin of the Pb is likely from historic urban atmospheric deposition. Aged green roofs may therefore act as a source of legacy metal pollution. This needs to be considered when constructing green roofs with the aim of improving pollution remediation.

Storage and behavior of As, Sb, Pb, and Cu in ombrotrophic peat bogs under contrasting water table conditions.

Concentration depth profiles and inventories of solid-phase As, Sb, Pb, and Cu were determined in ²¹⁰Pb-dated cores from an ombrotrophic peat bog in northwest England. Cores were collected from the peat dome and adjacent to an eroding gully. Down-core distributions of As, Sb, Pb, and Cu in the dome core are almost identical. The water table is close to the dome surface with only short-term draw-down. Under these conditions, As, Sb, Pb, and Cu are immobile, allowing the reconstruction of trends in historical contaminant deposition. The peak in atmospheric deposition of As, Sb, Pb, and Cu (4.59, 2.78, 147, and 26.7 mg m⁻² y⁻¹, respectively) occurred during the late 19th century. Stable Pb isotope ratios reveal that Pb deposition during this period was from indigenous and foreign sources. The mean water table is much lower at the gully edge, and there are pronounced interannual fluctuations. These conditions have not affected the integrity of the Pb and Cu records but have caused postdepositional mobilization and redistribution of As and Sb. Cumulative inventories show significant loss of As and Sb at the gully edge site. Long-term water table draw-down in ombrotrophic peat bogs has the potential to alter the geochemistry and fate of previously deposited As and Sb.

Dynamic modelling of atmospherically-deposited Ni, Cu, Zn, Cd and Pb in Pennine catchments (Northern England)

Simulation modelling with CHUM-AM was carried out to investigate the accumulation and release of atmospherically-deposited heavy metals (Ni, Cu, Zn, Cd and Pb) in six moorland catchments, five with organic-rich soils, one with calcareous brown earths, in the Pennine chain of northern England. The model considers two soil layers and a third layer of weathering mineral matter, and operates on a yearly timestep, driven by deposition scenarios covering the period 1400-2010. The principal processes controlling heavy metals are competitive solid-solution partitioning of solutes, chemical interactions in solution, and chemical weathering. Agreement between observed and simulated soil metal pools and surface water concentrations for recent years was generally satisfactory, the results confirming that most contemporary soil metal is from atmospheric pollution. Metals in catchments with organic-rich soils show some mobility, especially under more acid conditions, but the calcareous mineral soils have retained nearly all anthropogenic metal inputs. Complexation by dissolved organic matter and co-transport accounts for up to 80% of the Cu in surface waters.

Adsorption behavior of arsenic relating to different natural solids: Soils, stream sediments and peats

The sorption of anthropogenically derived arsenic to natural solids plays an important role in the mobility and fate of this toxic metalloid in the environment. The adsorption affinity of dissolved As(V) and As(III) to contrasting natural solids was investigated using model solutions of As(V)/As(III) and homogenized samples of soils, stream sediments and peat cores. The adsorption of As(III) and As(V) on investigated sorbents ran mostly according to the Langmuir model, with high correlation factors (>0.7). Sorption capacities varied from 3.5×10(-3) to 2.0×10(-1) mmol/g of As, whereas As(III) achieved a higher adsorption affinity due to the presence of Fe ions in the model solution. The lower horizons of soils and the intact peat, characterized by high enrichment factors of As content (R>1), represented a more stable system with decreased adsorption/desorption dynamics of As transport. A higher surface activity of solids associated with R<1, and an increased As mobility in the solid-water interface, prevailed in upper horizons of the soil and intact peat, where the contact with atmospheric deposition was expected. Stream sediments proved to be a well-balanced system with R≈1. A strong As-Fe correlation in the natural solids confirmed As affinity to Fe particles.

Assessment of Lead contamination in Peatlands using field portable XRF

Ombrotrophic peatlands are highly sensitive to atmospheric heavy metal deposition. Previous attempts to quantify peatland lead pollution have been undertaken using the inventory approach. However, there can be significant within-site spatial heterogeneity in lead concentrations, highlighting the need for multiple samples to properly quantify lead storage. Field portable x-ray fluorescence (FPXRF) continues to gain acceptance in the study of contaminated soil, but has not thus far been used to assess peatland lead contamination. This study compares lead concentrations in surface peat samples from the South Pennines (UK) derived using (a) FPXRF in the field, (b) FPXRF in the lab on dried samples and (c) ICP-OES analysis. FPXRF field and lab data are directly comparable when field measurements are corrected for water content, both can be easily used to estimate acid extractable lead using regression equations. This study is a successful demonstration of FPXRF as a tool for a time- and cost-effective means of determining the lead content of contaminated peatlands, which will allow rapid landscape scale reconnaissance, core logging, surface surveys and sediment tracing.

Contrasting controls on arsenic and lead budgets for a degraded peatland catchment in Northern England

Atmospheric deposition of trace metals and metalloids from anthropogenic sources has led to the contamination of many European peatlands. To assess the fate and behaviour of previously deposited arsenic and lead, we constructed catchment-scale mass budgets for a degraded peatland in Northern England. Our results show a large net export of both lead and arsenic via runoff (282 ± 21.3 gPb ha(-1) y(-1) and 60.4 ± 10.5 gAs ha(-1) y(-1)), but contrasting controls on this release. Suspended particulates account for the majority of lead export, whereas the aqueous phase dominates arsenic export. Lead release is driven by geomorphological processes and is a primary effect of erosion. Arsenic release is driven by the formation of a redox-dynamic zone in the peat associated with water table drawdown, a secondary effect of gully erosion. Degradation of peatland environments by natural and anthropogenic processes has the potential to release the accumulated pool of legacy contaminants to surface waters.