Determining patterns in the composition of dissolved organic matter in fresh waters according to land use and management

In fresh waters, the origins of dissolved organic matter (DOM) have been found to exert a fundamental control on its reactivity, and ultimately, its ecosystem functional role. A detailed understanding of landscape scale factors that control the export of DOM to aquatic ecosystems is, therefore, pivotal if the effects of DOM flux to fresh waters are to be fully understood. In this study we present data from a national sampling campaign across the United Kingdom in which we explore the variability in DOM composition in three broad landscape types defined by similar precipitation, geology, land use and management, hydrology, and nutrient enrichment status. We characterised samples from fifty-one sites, grouping them into one of three major underlying classifications: circumneutral streams underlain by clay and mudstone (referred to as ‘clay’), alkaline streams underlain by Cretaceous Chalk or by Carboniferous or Jurassic Limestone (‘limestone’), and acidic streams in peatland catchments underlain by a range of low permeability lithologies (‘peat’). DOM composition was assessed through organic matter stoichiometry (organic carbon: organic nitrogen; organic carbon: organic phosphorus; C/N(P)DOM) and metrics derived from ultra-violet (UV)/visible spectroscopic analysis of DOM such as specific UV absorption (a254 nm; SUVA254). We found similar SUVA254, C/NDOM and DOM/a254 relationships within classifications, demonstrating that despite a large degree of heterogeneity within environments, catchments with shared environmental character and anthropogenic disturbance export DOM with a similar composition and character. Improving our understanding of DOM characterisation is important to help predict shifts in stream ecosystem function, and ecological responses to enrichment or mitigation efforts and how these may result in species composition shifts and biodiversity loss in freshwater ecosystems

A geospatial framework to support integrated biogeochemical modelling in the United Kingdom

Anthropogenic impacts on the aquatic environment, especially in the context of nutrients, provide a major challenge for water resource management. The heterogeneous nature of policy relevant management units (e.g. catchments), in terms of environmental controls on nutrient source and transport, leads to the need for holistic management. However, current strategies are limited by current understanding and knowledge that is transferable between spatial scales and landscape typologies. This study presents a spatially-explicit framework to support the modelling of nutrients from land to water, encompassing environmental and spatial complexities. The framework recognises nine homogeneous landscape units, distinct in terms of sensitivity of nutrient losses to waterbodies. The functionality of the framework is demonstrated by supporting an exemplar nutrient model, applied within the Environmental Virtual Observatory pilot (EVOp) cloud cyber-infrastructure. We demonstrate scope for the use of the framework as a management decision support tool and for further development of integrated biogeochemical modelling

Dissolved organic nutrient uptake by riverine phytoplankton varies along a gradient of nutrient enrichment

The concentration of dissolved organic matter (DOM) in freshwaters is increasing in large areas of the world. In addition to carbon, DOM contains nitrogen and phosphorus and there is growing concern that these organic nutrients may be bioavailable and contribute to eutrophication. However, relatively few studies have assessed the potential for dissolved organic nitrogen (DON) or dissolved organic phosphorus (DOP) compounds to be bioavailable to natural river phytoplankton communities at different locations or times. Temporal and spatial variations in uptake, relative to environmental characteristics were examined at six riverine sites in two contrasting catchments in the UK. This study also examined how the uptake by riverine phytoplankton of four DON and four DOP compounds commonly found in rivers, varied with concentration. Total nitrogen (TN) and phosphorus (TP) concentrations, the proportion of inorganic nutrient species, and nutrient limitation varied temporally and spatially, as did the potential for DON and DOP uptake. All eight of the DOM compounds tested were bioavailable, but to different extents. Organic nutrient use depended on the concentration of the organic compound supplied, with simple compounds (urea and glucose-6-phosphate) supporting algal growth even at very low concentrations. DON use was negatively correlated with the TN and ammonia concentration and DOP use was negatively correlated with soluble reactive phosphorus (SRP) and dissolved organic carbon (DOC) concentration. The evidence indicates that DOM in rivers has been overlooked as a potential source of nutrients to phytoplankton and therefore as an agent of eutrophication

Characterisation of riverine dissolved organic matter using a complementary suite of chromatographic and mass spectrometric methods

Dissolved organic matter (DOM) plays a fundamental role in nutrient cycling dynamics in riverine systems. Recent research has confirmed that the concentration of riverine DOM is not the only factor regulating its functional significance; the need to define the chemical composition of DOM is a priority. Past studies of riverine DOM rested on bulk quantification, however technological advancements have meant there has been a shift towards analytical methods which allow the characterisation of DOM either at compound class or more recently molecular level. However, it is important to consider that all analytical methods only consider a defined analytical window. Thus, herein, we explore the use of a hierarchy of methods which can be used in combination for the investigation of a wide range of DOM chemistries. By using these methods to investigate the DOM composition of a range of streams draining catchments of contrasting environmental character, a wide range of compounds were identified across a range of polarities and molecular weight, thereby extending the analytical window. Through the elucidation of the DOM character in stream samples, information can be collected about likely the sources of DOM. The identification of individual key compounds within the DOM pool is a key step in the design of robust and informative bioassay experiments, used to understand in-stream ecosystem responses. This is critical if we are to assess the role of DOM as a bioavailable nutrient resource and/or ecotoxicological factor in freshwater

Projected impacts of increased uptake of source control mitigation measures on agricultural diffuse pollution emissions to water and air

The authors gratefully acknowledge the funding provided by Defra project LM0304; Phase 2 of the Avon Demonstration Test Catchment. The DTC farm survey data were collected in conjunction with the Avon (Defra project WQ0211), Wensum (Defra project WQ0212) and Eden (Defra project WQ02010) DTC programmes. The Environment Agency kindly provided access to national GIS layers. The authors thank the experts included in the elicitation exercise for current implementation of source control measures

The potential benefits of on-farm mitigation scenarios for reducing multiple pollutant loadings in prioritised agri-environment areas across England

The authors gratefully acknowledge the funding provided by the Department for Environment, Food and Rural Affairs (Defra) via project LM0304

Land use for England and Wales: evaluation of management options to support 'good ecological status' in surface freshwaters

This paper analyses historic records of agricultural land use and management for England and Wales from 1931 and 1991 and uses export coefficient modelling to hindcast the impact of these practices on the rates of diffuse nitrogen (N) and phosphorus (P) export to water bodies for each of the major geo-climatic regions of England and Wales. Key trends indicate the importance of animal agriculture as a contributor to the total diffuse agricultural nutrient loading on waters, and the need to bring these sources under control if conditions suitable for sustaining 'Good Ecological Status' under the Water Framework Directive are to be generated. The analysis highlights the importance of measuring changes in nutrient loading in relation to the catchment-specific baseline state for different water bodies. The approach is also used to forecast the likely impact of broad regional scale scenarios on nutrient export to waters and highlights the need to take sensitive land out of production, introduce ceilings on fertilizer use and stocking densities, and controls on agricultural practice in higher risk areas where intensive agriculture is combined with a low intrinsic nutrient retention capacity, although the uncertainties associated with the modelling applied at this scale should be taken into account in the interpretation of model output. The paper advocates the need for a two-tiered approach to nutrient management, combining broad regional policies with targeted management in high risk areas at the catchment and farm scale