Demonstration test catchments : the role of hydrogeological conceptual modelling

Agricultural diffuse pollution, particularly from nitrate and phosphate, is a significant problem in the UK and is the focus of the national Demonstration Test Catchments (DTC) study — a UK Government initiative. The DTC programme is providing evidence for investigating how on-farm mitigation measures can reduce the impact of agricultural diffuse water pollution on ecological function. This will involve studying how such measures affect pollutant concentrations in so-called receptors, such as the streams which drain the catchments. It is therefore important to investigate how water moves from the land surface to the receptors and in particular to quantify the amounts and timescales involved in the different water flow routes. The DTC catchments are the Eden, the Avon and the Wensum and groundwater flow is a significant component of main river flow in all of the catchments, ranging in overall terms from around 50% of river flow in the Eden to 90% in the Avon. It is therefore important that robust conceptual models of the groundwater flow systems of the catchments — and in particular of the monitored sub-catchments — are developed. BGS is contributing to the creation of DTC groundwater conceptual models in all three study catchments. The BGS work is funded principally by NERC and by DEFRA

A field study to assess the degradation and transport of diuron and its metabolites in a calcareous soil

An experimental plot has been established on a calcareous soil in southern England to investigate the fate and transport of diuron (N'-[3,4-dichlorophenyl]-NN-dimethylurea), a commonly used phenylurea herbicide. An agricultural grade of diuron was applied to the soil surface at a rate of 6.7 kg/ha along with a potassium bromide conservative tracer applied at 200 kg/ha, in early January, 2001. Hand augured samples were taken at regular intervals over the next 50 days, with samples collected down to 54 cm. Porewaters were extracted from the soil cores by using high speed centrifugation and the supernatant fluids were retained for analysis by HPLC, for diuron and three of its metabolites, N'-[3,4-dichlorophenyl]-N,N-methylurea (DCPMU), N'-3,4-dichlorophenylurea (DCPU) and 3,4-dichloroaniline (DCA). The centrifuged soil was retained and then extracted with methanol prior to HPLC analysis for the same suite of phenylureas. A mass balance approach showed large variations in diuron distribution, but on average accounted for 104% of the diuron applied. Concentrations of diuron and its metabolites were roughly five times higher in the soil than in the soil porewaters. After 50 days, metabolites comprised 10% of the total diuron present in the porewater and 20% of the total diuron sorbed to the soil matrix. After 36 days, a large pulse of diuron and DCPMU appeared in the porewaters and soil matrix at a depth of 54 cm, travelling an average of 0.15 cm/day faster than Br. A preferential route for diuron transport is suggested. There is evidence to suggest that degradation occurs at depth as well as at the soil surface. Metabolites generally appear to move more slowly than the parent compound. All metabolites were encountered, but interpreting transport and degradation processes simultaneously proved beyond the scope of the study. Diuron was detected once in a shallow (5 m) observation well, situated on the experimental plot. High concentrations of diuron and metabolites were still present in the soil and soil solutions after 50 days and remain as a source of potential groundwater contaminatio

Phosphate oxygen isotopes within aquatic ecosystems:global data synthesis and future research priorities

The oxygen isotope ratio of dissolved inorganic phosphate (δ18Op) represents a novel and potentially powerful stable isotope tracer for biogeochemical research. Analysis of δ18Op may offer new insights into the relative importance of different sources of phosphorus within natural ecosystems. Due to the isotope fractionations that occur alongside the metabolism of phosphorus, δ18Op could also be used to better understand the intracellular and extracellular reaction mechanisms that control phosphorus cycling. In this review focussed on aquatic ecosystems, we examine the theoretical basis to using stable oxygen isotopes within phosphorus research.We consider the methodological challenges involved in accurately determining δ18Op, given aquatic matrices in which potential sources of contaminant oxygen are ubiquitous. Finally,we synthesise the existing global data regarding δ18Op in aquatic ecosystems, concluding by identifying four key areas for future development of δ18Op research. Through this synthesis, we seek to stimulate broader interest in the use of δ18Op to address the significant research and management challenges that continue to surround the stewardship of phosphorus

Public water supply is responsible for significant fluxes of inorganic nitrogen in the environment

Understanding anthropogenic disturbance of macronutrient cycles is essential for assessing risks facing ecosystems. For the first time, we quantified inorganic nitrogen (N) fluxes associated with abstraction, mains water leakage and transfers of treated water related to public water supply. In England, the mass of nitrate-N removed from aquatic environments by abstraction (ABS-NO3-N) was estimated to be 24.2 kt N/yr. This is equal to six times estimates of organic N removal by abstraction, 15 times in-channel storage of organic N and 30 times floodplain storage of organic N. ABS-NO3-N is also between 3-39% of N removal by denitrification in the hydrosphere. Mains water leakage of nitrate-N (MWL-NO3-N) returns 3.62 kt N/yr to the environment, equating to approximately 15% of ABS-NO3-N . In urban areas, MWL-NO3-N can represent up to 20% of total N inputs. MWL-NO3-N is predicted to increase by up to 66% by 2020 following implementation of treated water transfers. ABS-NO3-N and MWL-NO3-N should be considered in future assessments of N fluxes, in order to accurately quantify anthropogenic disturbances to N cycles. The methodology we developed is transferable, using widely-available datasets and could be used to quantify N fluxes associated with public water supply across the world

Long-term Holocene groundwater fluctuations in a chalk catchment: evidence from Rock-Eval pyrolysis of riparian peats

he depositional history of peat-dominated wetlands can be used to understand palaeoclimate and palaeohydrology and also constrain the impacts of future climate change. However, in chalkland valleys, seasonal water table fluctuations and a high alkalinity have diminished key environment indicators such as pollen, and there is a need for alternative investigative techniques. The method of Rock-Eval pyrolysis can track changes in organic matter source and degradation, potentially relating to historic changes in vegetation cover. This is the first Rock-Eval on cores from a groundwater-dependent riparian chalk valley wetland combined with radiocarbon dating. The dating showed that the cores represented approximately 4000 years of depositional history. Changes in hydrocarbon chemistry including normal alkane composition of the peat indicated shifts of around 500 to 1000 years between terrestrial and more aquatic species, relating to periods of climate wetness. These climatic shifts are broadly consistent with other evidence from ombrotrophic peatland and lacustrine sediments across northwest Europe. However, the connection between climate wetness and groundwater dependent chalkland wetlands is complicated by external anthropogenically driven factors relating to land use and vegetation cover changes in the catchment. Nonetheless, this study suggests that Rock-Eval pyrolysis is a useful and cost-effective tool that can provide evidence for long-term Holocene groundwater fluctuation

A combined geochemical and hydrological approach for understanding macronutrient sources

This study employed complementary geochemical techniques and distributed hydrological modelling to investigate multiple sources of catchment macronutrients and characterise their changes in contrasting storm and baseflow conditions. This approach was demonstrated for the Beult catchment in the county of Kent (England), a designated Site of Special Scientific Interest (SSSI) indentified as failing to meet water quality standards for key nutrients under the Water Framework Directive. Significant changes in nutrient stoichiometry and bioavailability are observed for surface waters under contrasting flow regimes. Soluble reactive phosphorus (SRP) concentrations are approximately twice as high during baseflow compared to high flow, while the inverse is true for particulate, colloidal and dissolved hydrolysable phosphorus, dissolved organic carbon and nitrate. Nitrogen (N):phosphorus (P) ratios are lower during baseflow for most surface waters impacted by diffuse sources of pollution. Fluorescence indices of dissolved organic matter (DOM) show that waste water inputs may be locally important sources of more complex low molecular weight DOM, particularly during baseflow. Nitrate N and O isotope signatures, combined with other dissolved chemical tracers, confirm the dominance of wastewater N inputs at sites downsteam of sewerage treatment works during baseflow, with a shift towards the soil N pool in surface waters across the catchment during high flow. Distributed hydrological modelling using the Grid-to-Grid model reveal areas with the greatest runoff also export higher N and P concentrations, and hence deliver a greater flux of macronutrients, while forested areas with low nutrient concentrations reduce runoff and nutrient fluxes. During periods of high runoff, nested sampling indicates that nutrient fluxes scale with catchment area. This combined approach enables a more thorough assessment of the macronutrient sources and dynamics, better informing management options in nutrient impacted catchments

Coupling of groundwater, river level and rainfall in an upland floodplain

Upland floodplains provide an important function in regulating river flows and controlling the coupling of hillslope runoff with rivers. To investigate the responses of floodplain groundwater to river flows and rainfall events, a small floodplain in an upland area of the River Tweed catchment, Scotland, was characterised using geophysics, 3D geological mapping and hydrogeological testing; and monitoring undertaken from September 2011 to February 2013 of: groundwater levels in five pairs of piezometers; river stage and flow at the upstream and downstream limits of the study site; soil moisture on the adjacent hillslope; and meteorological parameters. Periodical groundwater chemistry and residence data were also collected. The floodplain aquifer is permeable throughout but partially stratified, comprising dominantly alluvial and glaciofluvial sandy gravels between 8 and 15m interspersed with thin, intermittent layers of low permeability silts, clays and peats. Overlying the gravel aquifer is a partial thin cover of low permeability alluvial silts, and it is underlain dominantly by low permeability glaciolacustrine silts and clays. High permeability solifluction deposits mantle much of the adjacent hillslope and provide a rapid connection to the floodplain aquifer. The unusually wet year of 2012 provides a good example of how a temperate upland floodplain responds to consistently high rainfall. Statistical analysis and graphical interpretation of groundwater level, rainfall, soil moisture and river stage demonstrates that: 1) dominant groundwater flow within the floodplain is in the same direction as the river, from up-valley to down-valley; 2) soil moisture in the hillslope is strongly correlated with local rainfall, but groundwater across much of the floodplain is more strongly influenced by river stage; except 3) groundwater near the edge of floodplain, which responds more slowly to local rainfall and river stage changes ; and 4) subsurface flow from the hillslope to the floodplain occurs during high rainfall events. A detailed investigation of three flood events, when the river rose above bank level and flooded adjacent fields and groundwater became artesian in parts of the floodplain, suggests that antecedent moisture conditions can partly explain the differences in groundwater response during different flood events, where high intensity or long duration rainfall can cause saturated soil conditions, reducing soil water storage capacity and hence promoting flood conditions. A conceptual model based on field data of groundwater flow after storm events during antecedent unsaturated and saturated soil conditions is presented

Development and initial application of δ18Op to understand phosphorus cycling in river, lake and groundwater ecosystems.

Variation in the stable isotope composition of oxygen within dissolved phosphate (δ18Op) represents a novel and potentially powerful environmental tracer. In freshwater, marine and terrestrial ecosystems, δ18Op can act as an inherent label for the sources of phosphorus and the extent to which phosphorus from different sources is metabolised. This paper focuses on the methodological development and initial application of δ18Op across a range of freshwater ecosystems. Initially, we report modifications to the analytical protocol for δ18Op that are designed to minimise incorporation of contaminant oxygen in the final silver phosphate precipitate prior to pyrolysis. This is critical given the range of possible sources of contaminant oxygen within freshwater matrices. Subsequently, we consider the potential utility of δ18Op through application of the technique within a range of freshwater ecosystems in England, UK. Firstly, we characterise δ18Op in river water and effluents from Sewage Treatment Works (STW), and examine the opportunity to use the 18Op of STW effluents to trace the entry and downstream fate of phosphorus from these point sources in rivers. Secondly, we analyse δ18Op to gain insights into variations in the sources and biological cycling of phosphorus in a seasonally stratified lake ecosystem. Thirdly, we characterise δ18Op in shallow and deep groundwater samples, considering whether δ18Op might provide evidence for variation in source and extent of metabolism for phosphorus in groundwater ecosystems. Taken together, these data extend the catalogue of δ18Op in freshwater ecosystems, and further the scope of δ18Op as a tool to better understand phosphorus biogeochemistry

A New Technique to Determine the Phosphate Oxygen Isotope Composition of Freshwater Samples at Low Ambient Phosphate Concentration

The oxygen isotope composition of dissolved inorganic phosphate (d18Op) offers new opportunities to understand the sources and the fate of phosphorus (P) in freshwater ecosystems. However, current analytical protocols for determining d18Op are unable to generate reliable data for samples in which ambient P concentrations are extremely low, precisely the systems in which d18Op may provide new and important insights into the biogeochemistry of P. In this paper, we report the development, testing and initial application of a new technique that enables d18Op analysis to be extended into such ecosystems. The Twist Spinning Mode (TSM) protocol described here enables >1000 L of sample with a P concentration <0.016 mg P L-1 to be initially processed within the field in approximately 24 hours. Combined with a new freeze-drying method to maximise the yield and minimise the contamination of silver phosphate generated for isotope ratio mass spectrometry, the TSM protocol is able to generate accurate and precise d18Op data. We evaluated the TSM protocol using synthetic test solutions and subsequently applied the protocol to samples from locations around the Saint-Lawrence River in Montreal, Canada. We believe that the novel technique reported here offers the methodological basis for researchers to extend the application of d18Op into a much wider range of freshwater ecosystems than has been possible to date