Estimation of p,p'-DDT degradation in soil by modeling and constraining hydrological and biogeochemical controls.

Despite not being used for decades in most countries, DDT remains ubiquitous in soils due to its persistence and intense past usage. Because of this it is still a pollutant of high global concern. Assessing long term dissipation of DDT from this reservoir is fundamental to understand future environmental and human exposure. Despite a large research effort, key properties controlling fate in soil (in particular, the degradation half-life (τsoil)) are far from being fully quantified. This paper describes a case study in a large central European catchment where hundreds of measurements of p,p'-DDT concentrations in air, soil, river water and sediment are available for the last two decades. The goal was to deliver an integrated estimation of τsoil by constraining a state-of-the-art hydrobiogeochemical-multimedia fate model of the catchment against the full body of empirical data available for this area. The INCA-Contaminants model was used for this scope. Good predictive performance against an (external) dataset of water and sediment concentrations was achieved with partitioning properties taken from the literature and τsoil estimates obtained from forcing the model against empirical historical data of p,p'-DDT in the catchment multicompartments. This approach allowed estimation of p,p'-DDT degradation in soil after taking adequate consideration of losses due to runoff and volatilization. Estimated τsoil ranged over 3000-3800 days. Degradation was the most important loss process, accounting on a yearly basis for more than 90% of the total dissipation. The total dissipation flux from the catchment soils was one order of magnitude higher than the total current atmospheric input estimated from atmospheric concentrations, suggesting that the bulk of p,p'-DDT currently being remobilized or lost is essentially that accumulated over two decades ago.

A theoretical assessment of microplastic transport in river catchments and their retention by soils and river sediments.

The presence of microplastics (MPs) in the environment is a problem of growing concern. While research has focused on MP occurrence and impacts in the marine environment, very little is known about their release on land, storage in soils and sediments and transport by run-off and rivers. This study describes a first theoretical assessment of these processes. A mathematical model of catchment hydrology, soil erosion and sediment budgets was upgraded to enable description of MP fate. The Thames River in the UK was used as a case study. A general lack of data on MP emissions to soils and rivers and the mass of MPs in agricultural soils, limits the present work to serve as a purely theoretical, nevertheless rigorous, assessment that can be used to guide future monitoring and impact evaluations. The fundamental assumption on which modelling is based is that the same physical controls on soil erosion and natural sediment transport (for which model calibration and validation are possible), also control MP transport and storage. Depending on sub-catchment soil characteristics and precipitation patterns, approximately 16-38% of the heavier-than-water MPs hypothetically added to soils (e.g. through routine applications of sewage sludge) are predicted to be stored locally. In the stream, MPs < 0.2 mm are generally not retained, regardless of their density. Larger MPs with densities marginally higher than water can instead be retained in the sediment. It is, however, anticipated that high flow periods can remobilize this pool. Sediments of river sections experiencing low stream power are likely hotspots for deposition of MPs. Exposure and impact assessments should prioritize these environments.

Perfluoroalkyl substances (PFAS) in river and ground/drinking water of the Ganges River basin: Emissions and implications for human exposure.

Many perfluoroalkyl substances (PFAS) are ubiquitous environmental contaminants. They have been widely used in production processes and daily-use products or may result from degradation of precursor compounds in products or the environment. India, with its developing industrialization and population moving from traditional to contemporary lifestyles, represents an interesting case study to investigate PFAS emission and exposure along steep environmental and socioeconomic gradients. This study assesses PFAS concentrations in river and groundwater (used in this region as drinking water) from several locations along the Ganges River and estimates direct emissions, specifically for PFOS and PFOA. 15 PFAS were frequently detected in the river with the highest concentrations observed for PFHxA (0.4-4.7 ng L(-1)) and PFBS (

Assessment of contaminant fate in catchments using a novel integrated hydrobiogeochemical-multimedia fate model.

Models for pollution exposure assessment typically adopt an overly simplistic representation of geography, climate and biogeochemical processes. This strategy is unsatisfactory when high temporal resolution simulations for sub-regional spatial domains are performed, in which parameters defining scenarios can vary interdependently in space and time. This is, for example, the case when assessing the influence of biogeochemical processing on contaminant fate. Here we present INCA-Contaminants, the Integrated Catchments model for Contaminants; a new model that simultaneously and realistically solves mass balances of water, carbon, sediments and contaminants in the soil-stream-sediment system of catchments and their river networks as a function of climate, land use/management and contaminant properties. When forced with realistic climate and contaminant input data, the model was able to predict polychlorinated biphenyls (PCBs) concentrations in multiple segments of a river network in a complex landscape. We analyzed model output sensitivity to a number of hydro-biogeochemical parameters. The rate of soil organic matter mineralization was the most sensitive parameter controlling PCBs levels in river water, supporting the hypothesis that organic matter turnover rates will influence re-mobilization of previously deposited PCBs which had accumulated in soil organic matrix. The model was also used to project the long term fate of PCB 101 under two climate scenarios. Catchment diffuse run-off and riverine transport were the major pathways of contaminant re-mobilization. Simulations show that during the next decade the investigated boreal catchment will shift from being a net atmospheric PCB sink to a net source for air and water, with future climate perturbation having little influence on this trend. Our results highlight the importance of using credible hydro-biogeochemical simulations when modeling the fate of hydrophobic contaminants.

An assessment of the fine sediment dynamics in an upland river system: INCA-Sed modifications and implications for fisheries.

There is a need for better links between hydrology and ecology, specifically between landscapes and riverscapes to understand how processes and factors controlling the transport and storage of environmental pollution have affected or will affect the freshwater biota. Here we show how the INCA modelling framework, specifically INCA-Sed (the Integrated Catchments model for Sediments) can be used to link sediment delivery from the landscape to sediment changes in-stream. INCA-Sed is a dynamic, process-based, daily time step model. The first complete description of the equations used in the INCA-Sed software (version 1.9.11) is presented. This is followed by an application of INCA-Sed made to the River Lugg (1077 km(2)) in Wales. Excess suspended sediment can negatively affect salmonid health. The Lugg has a large and potentially threatened population of both Atlantic salmon (Salmo salar) and Brown Trout (Salmo trutta). With the exception of the extreme sediment transport processes, the model satisfactorily simulated both the hydrology and the sediment dynamics in the catchment. Model results indicate that diffuse soil loss is the most important sediment generation process in the catchment. In the River Lugg, the mean annual Guideline Standard for suspended sediment concentration, proposed by UKTAG, of 25 mg l(-1) is only slightly exceeded during the simulation period (1995-2000), indicating only minimal effect on the Atlantic salmon population. However, the daily time step simulation of INCA-Sed also allows the investigation of the critical spawning period. It shows that the sediment may have a significant negative effect on the fish population in years with high sediment runoff. It is proposed that the fine settled particles probably do not affect the salmonid egg incubation process, though suspended particles may damage the gills of fish and make the area unfavourable for spawning if the conditions do not improve.

An application of the GLUE methodology for estimating the parameters of the INCA-N model.

The conceptual and parameter uncertainty of the semi-distributed INCA-N (Integrated Nutrients in Catchments-Nitrogen) model was studied using the GLUE (Generalized Likelihood Uncertainty Estimation) methodology combined with quantitative experimental knowledge, the concept known as 'soft data'. Cumulative inorganic N leaching, annual plant N uptake and annual mineralization proved to be useful soft data to constrain the parameter space. The INCA-N model was able to simulate the seasonal and inter-annual variations in the stream-water nitrate concentrations, although the lowest concentrations during the growing season were not reproduced. This suggested that there were some retention processes or losses either in peatland/wetland areas or in the river which were not included in the INCA-N model. The results of the study suggested that soft data was a way to reduce parameter equifinality, and that the calibration and testing of distributed hydrological and nutrient leaching models should be based both on runoff and/or nutrient concentration data and the qualitative knowledge of experimentalist.