High frequency UV-Vis sensors estimate error in riverine dissolved organic carbon load estimates from grab sampling.

High frequency ultraviolet - visible (UV-VIS) sensors offer a way of improving dissolved organic carbon (DOC) load estimates in rivers as they can be calibrated to DOC concentration. This is an improvement on periodic grab sampling, or the use of pumped sampling systems which store samples in-field before collection. We hypothesised that the move to high frequency measurements would increase the load estimate based on grab sampling due to systemic under-sampling of high flows. To test our hypotheses, we calibrated two sensors in contrasting catchments (Exe and Bow Brook, UK) against weekly grab sampled DOC measurements and then created an hourly time series of DOC for the two sites. Taking this measurement as a 'true' value of DOC load, we simulated 1,000 grab sampling campaigns at weekly, fortnightly and monthly frequency to understand the likely distribution of load and error estimates. We also performed an analysis of daily grab samples collected using a pumped storage sampling system with weekly collection. Our results show that: a) grab sampling systemically underestimates DOC loads and gives positively skewed distributions of results, b) this under-estimation and positive skew decreases with increasing sampling frequency, c) commonly used estimates of error in the load value are also systemically lowered by the oversampling of low, stable flows due to their dependence on the variance in the flow-weighted mean concentration, and d) that pumped storage systems may lead to under-estimation of DOC and over estimation of specific ultra-violet absorbance (SUVA), a proxy for aromaticity, due to biodegradation during storage.

Sources of dissolved organic carbon (DOC) in a mixed land use catchment (Exe, UK).

Many catchment management schemes in the UK have focussed on peatland restoration to improve ecosystem services such as carbon sequestration, water quality and biodiversity. The effect of these schemes on dissolved organic carbon (DOC) flux is critical in understanding peatland carbon budgets as well as the implications for drinking water treatment. In many catchments, however, peatland areas are not the only source of DOC, meaning that their significance at the full catchment scale is unclear. In this paper we have evaluated the importance of different land uses as sources of DOC by combining three datasets obtained from the Exe catchment, UK. The first dataset comprises a weekly monitoring record at three sites for six years, the second, a monthly monitoring record of 25 sites in the same catchment for one year, and the third, an assessment of DOC export from litter and soil carbon stocks. Our results suggest that DOC concentration significantly increased from the peaty headwaters to the mixed land-use areas (ANOVA F = 12.52, p < 0.001, df = 2), leading to higher flux estimates at the downstream sites. We present evidence for three possible explanations: firstly, that poor sampling of high flows may lead to underestimation of DOC flux, second, that there are significant sources of DOC besides the peatland headwaters, and finally, that biological- and photo-degradation decreases the influence of upstream DOC sources. Our results provide evidence both for the targeting of catchment management in peatland areas as well as the need to consider DOC from agricultural and forested areas of the catchment.

Spatial variation in soil properties and diffuse losses between and within grassland fields with similar short-term management.

One of the major challenges for agriculture is to understand the effects of agricultural practices on soil properties and diffuse pollution, to support practical farm-scale land management. Three conventionally managed grassland fields with similar short-term management, but different ploughing histories, were studied on a long-term research platform: the North Wyke Farm Platform. The aims were to (i) quantify the between-field and within-field spatial variation in soil properties by geostatistical analysis, (ii) understand the effects of soil condition (in terms of nitrogen, phosphorus and carbon contents) on the quality of discharge water and (iii) establish robust baseline data before the implementation of various grassland management scenarios. Although the fields sampled had experienced the same land use and similar management for at least 6 years, there were differences in their mean soil properties. They showed different patterns of soil spatial variation and different rates of diffuse nutrient losses to water. The oldest permanent pasture field had the largest soil macronutrient concentrations and the greatest diffuse nutrient losses. We show that management histories affect soil properties and diffuse losses. Potential gains in herbage yield or benefits in water quality might be achieved by characterizing every field or by area-specific management within fields (a form of precision agriculture for grasslands). Permanent pasture per se cannot be considered a mitigation measure for diffuse pollution. The between- and within-field soil spatial variation emphasizes the importance of baseline characterization and will enable the reliable identification of any effects of future management change on the Farm Platform. HIGHLIGHTS: Quantification of soil and water quality in grassland fields with contrasting management histories.Considerable spatial variation in soil properties and diffuse losses between and within fields.Contrasting management histories within and between fields strongly affected soil and water quality.Careful pasture management needed: the oldest pasture transferred the most nutrients from soil to water.

New approaches to the restoration of shallow marginal peatlands.

Globally, the historic and recent exploitation of peatlands through management practices such as agricultural reclamation, peat harvesting or forestry, have caused extensive damage to these ecosystems. Their value is now increasingly recognised, and restoration and rehabilitation programmes are underway to improve some of the ecosystem services provided by peatlands: blocking drainage ditches in deep peat has been shown to improve the storage of water, decrease carbon losses in the long-term, and improve biodiversity. However, whilst the restoration process has benefitted from experience and technical advice gained from restoration of deep peatlands, shallow peatlands have received less attention in the literature, despite being extensive in both uplands and lowlands. Using the experience gained from the restoration of the shallow peatlands of Exmoor National Park (UK), and two test catchments in particular, this paper provides technical guidance which can be applied to the restoration of other shallow peatlands worldwide. Experience showed that integrating knowledge of the historical environment at the planning stage of restoration was essential, as it enabled the effective mitigation of any threat to archaeological features and sites. The use of bales, commonly employed in other upland ecosystems, was found to be problematic. Instead, 'leaky dams' or wood and peat combination dams were used, which are both more efficient at reducing and diverting the flow, and longer lasting than bale dams. Finally, an average restoration cost (£306 ha(-1)) for Exmoor, below the median national value across the whole of the UK, demonstrates the cost-effectiveness of these techniques. However, local differences in peat depth and ditch characteristics (i.e. length, depth and width) between sites affect both the feasibility and the cost of restoration. Overall, the restoration of shallow peatlands is shown to be technically viable; this paper provides a template for such process over analogous landscapes.

Antecedent conditions control carbon loss and downstream water quality from shallow, damaged peatlands.

Losses of dissolved organic carbon (DOC) from drained peatlands are of concern, due to the effects this has on the delivery of ecosystem services, and especially on the long-term store of carbon and the provision of drinking water. Most studies have looked at the effect of drainage in deep peat; comparatively, little is known about the behaviour of shallow, climatically marginal peatlands. This study examines water quality (DOC, Abs(400), pH, E4/E6 and C/C) during rainfall events from such environments in the south west UK, in order to both quantify DOC losses, and understand their potential for restoration. Water samples were taken over a 19 month period from a range of drains within two different experimental catchments in Exmoor National Park; data were analysed on an event basis. DOC concentrations ranging between 4 and 21 mg L(-1) are substantially lower than measurements in deep peat, but remain problematic for the water treatment process. Dryness plays a critical role in controlling DOC concentrations and water quality, as observed through spatial and seasonal differences. Long-term changes in depth to water table (30 days before the event) are likely to impact on DOC production, whereas discharge becomes the main control over DOC transport at the time scale of the rainfall/runoff event. The role of temperature during events is attributed to an increase in the diffusion of DOC, and therefore its transport. Humification ratios (E4/E6) consistently below 5 indicate a predominance of complex humic acids, but increased decomposition during warmer summer months leads to a comparatively higher losses of fulvic acids. This work represents a significant contribution to the scientific understanding of the behaviour and functioning of shallow damaged peatlands in climatically marginal locations. The findings also provide a sound baseline knowledge to support research into the effects of landscape restoration in the future.

Accelerated export of sediment and carbon from a landscape under intensive agriculture.

The export of total organic carbon (particulate and dissolved) from terrestrial to aquatic ecosystems has important implications for water quality and the global carbon cycle. However, most research to date has focused on DOC losses from either forested or peaty catchments, with only limited studies examining the controls and rates of total fluvial carbon losses from agricultural catchments, particularly during storm events. This study examined the controls and fluxes of total suspended sediment (SS), total particulate (TPC) and dissolved organic carbon (DOC) from two adjacent catchments with contrasting intensive agricultural and semi-natural land-use. Data from 35 individual storm events showed that the agricultural catchment exported significantly higher SS concentrations on a storm-by-storm basis than the semi-natural catchment, with peak discharge exerting a greater control over SS, TPC and DOC concentrations. Baseflow DOC concentrations in the agricultural catchment were significantly higher. DOC quality monitored during one simultaneous rainfall event differed between the two study catchments, with more humic, higher molecular weight compounds prevailing in the agricultural catchment and lower molecular weight compounds prevailing in the semi-natural catchment. During an eight month period for which a comparable continuous turbidity record was available, the estimated SS yields from the agricultural catchment were higher than from the semi-natural catchment. Further, the agricultural catchment exported proportionally more TPC and a comparable amount of DOC, despite a lower total soil carbon pool. These results suggest that altered hydrological and biogeochemical processes within the agricultural catchment, including accelerated soil erosion and soil organic matter turnover, contributed to an enhanced fluvial SS and carbon export. Thus, we argue that enhancing semi-natural vegetation within intensively farmed catchments could reduce sediment and carbon losses from these areas and increase their resilience to more extreme hydrological events, anticipated as a result of climate change.

A novel application of natural fluorescence to understand the sources and transport pathways of pollutants from livestock farming in small headwater catchments.

This paper demonstrates the application of a low-cost and rapid natural fluorescence technique for tracing and quantifying the transport of pollutants from livestock farming through a small headwater catchment. Fluorescence intensities of Dissolved Organic Matter (DOM) present in different pollutant sources and drainage waters in the Den Brook catchment (Devon, UK) were monitored through storm events occurring between January 2007 and June 2008. Contrasting fluorescence signals from different sources confirmed the technique's usefulness as a tracer of pollutants from livestock farming. Changes in fluorescence intensities of drainage waters throughout storm events were used to assess the dynamics of key pollutant sources. The farmyard area of the catchment studied was shown to contribute polluted runoff at the onset of storm events in response to only small amounts of rain, when flows in the Den Brook first-order channel were low. The application of slurry to a field within the catchment did not elevate the fluorescence of drainage waters during storm events suggesting that when slurry is applied to undrained fields the fluorescent DOM may become quickly adsorbed onto soil particles and/or immobilised through bacterial breakdown. Fluorescence intensities of drainage waters were successfully combined with discharge data in a two component mixing model to estimate pollutant fluxes from key sources during the January 2007 storm event. The farmyard was shown to be the dominant source of tryptophan-like material, contributing 61-81% of the total event flux at the catchment outlet. High spatial and temporal resolution measurements of fluorescence, possibly using novel in-situ fluorimeters, may thus have great potential in quickly identifying and quantifying the presence, dynamics and sources of pollutants from livestock farming in catchments.

Assessing catchment-scale erosion and yields of suspended solids from improved temperate grassland.

This paper quantifies the yields of suspended solids (SS) from a headwater catchment managed as improved temperate grassland, providing the first direct, catchment-scale evidence of the rates of erosion from this land-use in the UK and assessing the threat posed to aquatic ecosystems. High-resolution monitoring of catchment hydrology and the concentrations of SS and volatile organic matter (VOM) were carried out in the first-order channel of the Den Brook headwater catchment in Devon (UK) during the 2006-2007 hydrological season. The widely used 'rating curve' (discharge-concentration) approach was employed to estimate yields of SS, but as demonstrated by previous researchers, this study showed that discharge is a poor predictor of SS concentrations and therefore any yields estimated from this technique are likely to be highly uncertain. Nevertheless, for the purpose of providing estimates of yields that are comparable to previous studies on other land uses/sources, this technique was adopted albeit in an uncertainty-based framework. The findings suggest that contrary to the common perception, grasslands can be erosive landscapes with SS yields from this catchment estimated to be between 0.54 and 1.21 t ha(-1) y(-1). In terms of on-site erosion problems, this rate of erosion does not significantly exceed the commonly used 'tolerable' threshold in the UK ( approximately 1 t ha(-1) y(-1)). In terms of off-site erosion problems, it is argued here that the conventional expression of SS yield as a bulk annual figure has little relevance to the water quality and ecological status of surface waters and therefore an alternative technique (the concentration-frequency curve) is developed within this paper for the specific purpose of assessing the ecological threat posed by the delivery of SS into surface waters. This technique illustrates that concentrations of SS recorded at the catchment outlet frequently exceed the water quality guidelines, such as those of the EU Freshwater Fisheries Directive (78/659/EC), and pose a serious threat to aquatic organisms. It is suggested that failure to recognise improved temperate grasslands as a potential source of particulate material could result in the non-compliance of surface waters to water quality guidelines, deterioration of ecological status and failure of water quality remediation measures.

Understanding the influence of suspended solids on water quality and aquatic biota.

Over the last 50 years the effects of suspended solids (SS) on fish and aquatic life have been studied intensively throughout the world. It is now accepted that SS are an extremely important cause of water quality deterioration leading to aesthetic issues, higher costs of water treatment, a decline in the fisheries resource, and serious ecological degradation of aquatic environments. As such, government-led environmental bodies have set recommended water quality guidelines for concentrations of SS in freshwater systems. However, these reference values are often spurious or based on the concept of turbidity as a surrogate measure of the concentration of SS. The appropriateness of these recommended water quality values is evaluated given: (1) the large variability and uncertainty in data available from research describing the effects of SS on aquatic environments, (2) the diversity of environments that these values are expected to relate to, and (3) the range of conditions experienced within these environments. Furthermore, we suggest that reliance solely upon turbidity data as a surrogate for SS must be treated with caution, as turbidity readings respond to factors other than just concentrations of SS, as well as being influenced by the particle-size distribution and shape of SS particles. In addition, turbidity is a measure of only one of the many detrimental effects, reviewed in this paper, which high levels of SS can have in waterbodies. In order to improve the understanding of the effects of SS on aquatic organisms, this review suggests that: First, high-resolution turbidity monitoring should be supplemented with direct, measurements of SS (albeit at lower resolution due to resource issues). This would allow the turbidity record to be checked and calibrated against SS, effectively building a rating-relationship between SS and turbidity, which would in-turn provide a clearer picture of the exact magnitude of the SS problem. Second, SS should also be characterised in terms of their particle-size distribution and chemical composition. This would provide information to develop a more comprehensive understanding of the observed variable effects of a given concentration of SS in aquatic habitats. These two suggested improvements, combined with lower-resolution concurrent measures of aquatic ecological status, would improve our understanding of the effects of SS in aquatic environments and together with a more detailed classification of aquatic environments, would provide an environment-specific evidence base for the establishment of effective water quality guidelines for SS.

Rethinking the contribution of drained and undrained grasslands to sediment-related water quality problems.

Grass vegetation has been recommended for use in the prevention and control of soil erosion because of its dense sward characteristics and stabilizing effect on the soil. A general assumption is that grassland environments suffer from minimal soil erosion and therefore present little threat to the water quality of surface waters in terms of sediment and sorbed contaminant pollution. Our data question this assumption, reporting results from one hydrological year of observations on a field-experiment monitoring overland flow, drain flow, fluxes of suspended solids, total phosphorus (TP), and molybdate-reactive phosphorus (<0.45 mum) in response to natural rainfall events. During individual rainfall events, 1-ha grassland lysimeters yield up to 15 kg of suspended solids, with concentrations in runoff waters of up to 400 mg L(-1). These concentrations exceed the water quality standards recommended by the European Freshwater Fisheries Directive (25 mg L(-1)) and the USEPA (80 mg L(-1)) and are beyond those reported to have caused chronic effects on freshwater aquatic organisms. Furthermore, TP concentrations in runoff waters from these field lysimeters exceeded 800 mug L(-1). These concentrations are in excess of those reported to cause eutrophication problems in rivers and lakes and contravene the ecoregional nutrient criteria in all of the USA ecoregions. This paper also examines how subsurface drainage, a common agricultural practice in intensively managed grasslands, influences the hydrology and export of sediment and nutrients from grasslands. This dataset suggests that we need to rethink the conceptual understanding of grasslands as non-erosive landscapes. Failure to acknowledge this will result in the noncompliance of surface waters to water quality standards.

A tiered risk-based approach for predicting diffuse and point source phosphorus losses in agricultural areas.

Implementation of the European Union Water Framework Directive requires an assessment of the pressures from human activity, which, combined with information on the sensitivity of the receiving waterbody to the pressures, will identify those water bodies at risk of failing to meet the Directive's environmental objectives. Part of the process of undertaking the risk assessment for lakes is an assessment of diffuse agricultural phosphorus (P) pressures. Three approaches of increasing sophistication were developed for this purpose: a basic 'risk screening' approach (tier 1) applicable to all lakes in Great Britain (GB) and based on export coefficients for different land cover classes and animal types; the Pressure Delivery Risk Screening Matrix approach (tier 2) that differentiated between pressures in surface water and groundwater river basins; and the Phosphorus Indicators Tool (PIT), a simple model of locational risk and P delivery potential (tier 3). Application of the three approaches to a range of lake catchments in England demonstrated that a tiered risk assessment approach was appropriate which was tailored to the quality of the available data. A step-wise procedure was developed whereby if the tier 1 and 2 approaches showed a catchment to be at high risk of failing to meet the Directive's environmental objectives with regard to P, it was justifiable to undertake a more detailed assessment using the tier 3 approach. The tier 1 approach was applied to all lakes in GB greater than 1 ha in size on the assumption that the boundary between the good/moderate status classes under the Water Framework Directive guidelines represented a doubling of the total P (TP) reference conditions. The initial outputs suggested that 51% of lakes in GB are predicted to not meet the TP targets identified for high or good status and must, therefore, be considered at risk. There were regional differences in numbers of lakes at risk. Scotland appeared to have the fewest sites at risk (18%); England the most (88%), with Wales having an intermediate percentage (56%). A comparison of P pressures on freshwaters using the tier 2 approach with other pressures on waterbodies (e.g. nitrate, sediment) in GB is shown as risk maps on the Environment Agency website at: . The tier 3 approach was applied to data-rich catchments and identified at the 1 km(2) areas of relatively high risk of P delivery to water.