Richard A. Skeffington

Characterising phosphorus and nitrate inputs to a rural river using high-frequency concentration-flow relationships

The total reactive phosphorus (TRP) and nitrate concentrations of the River Enborne, southern England, were monitored at hourly interval between January 2010 and December 2011. The relationships between these high-frequency nutrient concentration signals and flow were used to infer changes in nutrient source and dynamics through the annual cycle and each individual storm event, by studying hysteresis patterns. TRP concentrations exhibited strong dilution patterns with increasing flow, and predominantly clockwise hysteresis through storm events. Despite the Enborne catchment being relatively rural for southern England, TRP inputs were dominated by constant, non-rain-related inputs from sewage treatment works (STW) for the majority of the year, producing the highest phosphorus concentrations through the spring-summer growing season. At higher river flows, the majority of the TRP load was derived from within-channel remobilisation of phosphorus from the bed sediment, much of which was also derived from STW inputs. Therefore, future phosphorus mitigation measures should focus on STW improvements. Agricultural diffuse TRP inputs were only evident during storms in the May of each year, probably relating to manure application to land. The nitrate concentration-flow relationship produced a series of dilution curves, indicating major inputs from groundwater and to a lesser extent STW. Significant diffuse agricultural inputs with anticlockwise hysteresis trajectories were observed during the first major storms of the winter period. The simultaneous investigation of high-frequency time series data, concentration-flow relationships and hysteresis behaviour through multiple storms for both phosphorus and nitrate offers a simple and innovative approach for providing new insights into nutrient sources and dynamics.

An analysis of long-term trends, seasonality and short-term dynamics in water quality data from Plynlimon, Wales

This paper examines two hydrochemical time-series derived from stream samples taken in the Upper Hafren catchment, Plynlimon, Wales. One time-series comprises data collected at 7-hour intervals over 22 months (Neal et al., 2012-this issue), while the other is based on weekly sampling over 20 years. A subset of determinands: aluminium, calcium, chloride, conductivity, dissolved organic carbon, iron, nitrate, pH, silicon and sulphate are examined within a framework of non-stationary time-series analysis to identify determinand trends, seasonality and short-term dynamics. The results demonstrate that both long-term and high-frequency monitoring provide valuable and unique insights into the hydrochemistry of a catchment. The long-term data allowed analysis of long-term trends, demonstrating continued increases in DOC concentrations accompanied by declining SO(4) concentrations within the stream, and provided new insights into the changing amplitude and phase of the seasonality of the determinands such as DOC and Al. Additionally, these data proved invaluable for placing the short-term variability demonstrated within the high-frequency data within context. The 7-hour data highlighted complex diurnal cycles for NO(3), Ca and Fe with cycles displaying changes in phase and amplitude on a seasonal basis. The high-frequency data also demonstrated the need to consider the impact that the time of sample collection can have on the summary statistics of the data and also that sampling during the hours of darkness provides additional hydrochemical information for determinands which exhibit pronounced diurnal variability. Moving forward, this research demonstrates the need for both long-term and high-frequency monitoring to facilitate a full and accurate understanding of catchment hydrochemical dynamics.

How well can we model stream phosphorus concentrations in agricultural catchments

Mechanistic catchment-scale phosphorus models appear to perform poorly where diffuse sources dominate. We investigate the reasons for this for one model, INCA-P, testing model output against 18 months of daily data in a small Scottish catchment. We examine key model processes and provide recommendations for model improvement and simplification. Improvements to the particulate phosphorus simulation are especially needed. The model evaluation procedure is then generalised to provide a checklist for identifying why model performance may be poor or unreliable, incorporating calibration, data, structural and conceptual challenges. There needs to be greater recognition that current models struggle to produce positive Nash-Sutcliffe statistics in agricultural catchments when evaluated against daily data. Phosphorus modelling is difficult, but models are not as useless as this might suggest. We found a combination of correlation coefficients, bias, a comparison of distributions and a visual assessment of time series a better means of identifying realistic simulations. We use daily data to test a mechanistic phosphorus model in an agricultural area.The model reproduces dissolved phosphorus dynamics but struggles with particulates.A number of potential model simplifications and improvements are highlighted.Nash-Sutcliffe is of limited use for measuring phosphorus model performance.We present a checklist for assessing why environmental models may underperform.

Recovery from acidification in the Tillingbourne catchment, southern England: catchment description and preliminary results

Measurements of acid deposition and streamwater chemistry made in 1979-1982 and 1999-2000 are compared for a small, acid-sensitive catchment in Southeast England. The location, geology, soils, vegetation and hydrology of the catchment are described. The catchment is located on an acidic cretaceous sandstone with a low permeability clay sub-stratum. Soils are predominantly podzol and gley, with some mesotrophic peat. The catchment is forested. Mean volume-weighted concentrations in precipitation have changed approximately in proportion to emission changes. SO4(2-) has declined by 61%, H+ by 75%, both NO- and NH4+ by 37% and Cl- by 26%. Changes in wet deposition are greater, sulfate deposition declined by 69%, non-marine SO4(2-) by 73%, H+ deposition by 75%, NO3- and NH4+ by 50% and Cl- by 41%. Sulfate deposition in throughfall, a surrogate for total deposition measurement, has declined by 82% and non-marine SO4(2-) by 86%. Some of these changes are due to alterations in the tree cover and location of the collectors. In 1979-1982, the flux of NO3- and NH4+ in throughfall was less than in rainfall, 7.5 compared with 11.3 kg N ha(-1) year(-1), showing that N uptake by the canopy was greater than dry deposition of these species. However, in 1999-2000, the throughfall flux of N was greater than rainfall, 19.6 compared to 5.7 kg N ha year(-1), indicating that canopy uptake is not occurring to the same extent. Surface water was sampled at the same locations in the catchment during the two periods. At the catchment exit, mean pH increased, from 3.93 to 4.21 mg l(-1), and SO4(2-) declined from 20.2 to 16.7 mg l(-1) (18%). The decrease in SO4(2-) is much less than the reduction in deposition, suggesting that the predicted recovery is being delayed by release of sulfur from the soil. In contrast, NO3- concentrations in the catchment waters increased from 0.22 to 0.52 mg N l(-1) (133%) despite the reduction in N deposition. NH4+ concentrations were low during both study periods. It is concluded that recovery from acidification is probably occurring, but is possibly being delayed by desorption of soil S. The catchment is also showing signs of increasing N saturation, despite a reduction in N inputs.

The implications of climate change for the water environment in England

This paper reviews the implications of climate change for the water environment and its management in England. There is a large literature, but most studies have looked at flow volumes or nutrients and none have considered explicitly the implications of climate change for the delivery of water management objectives. Studies have been undertaken in a small number of locations. Studies have used observations from the past to infer future changes, and have used numerical simulation models with climate change scenarios. The literature indicates that climate change poses risks to the delivery of water management objectives, but that these risks depend on local catchment and water body conditions. Climate change affects the status of water bodies, and it affects the effectiveness of measures to manage the water environment and meet policy objectives. The future impact of climate change on the water environment and its management is uncertain. Impacts are dependent on changes in the duration of dry spells and frequency of ‘flushing’ events, which are highly uncertain and not included in current climate scenarios. There is a good qualitative understanding of ways in which systems may change, but interactions between components of the water environment are poorly understood. Predictive models are only available for some components, and model parametric and structural uncertainty has not been evaluated. The impacts of climate change depend on other pressures on the water environment in a catchment, and also on the management interventions that are undertaken to achieve water management objectives. The paper has also developed a series of consistent conceptual models describing the implications of climate change for pressures on the water environment, based around the source-pathway-receptor concept. They provide a framework for a systematic assessment across catchments and pressures of the implications of climate change for the water environment and its management.

The effects of a changing pollution climate on throughfall deposition and cycling in a forested area in southern England

This study compares two sets of measurements of the composition of bulk precipitation and throughfall at a site in southern England with a 20-year gap between them. During this time, SO(2) emissions from the UK fell by 82%, NO(x) emissions by 35% and NH(3) emissions by 7%. These reductions were partly reflected in bulk precipitation, with deposition reductions of 56% in SO(4)(2-), 38% in NO(3)(-), 32% in NH(4)(+), and 73% in H(+). In throughfall under Scots pine, the effects were more dramatic, with an 89% reduction in SO(4)(2-) deposition and a 98% reduction in H(+) deposition. The mean pH under these trees increased from 2.85 to 4.30. Nitrate and ammonium deposition in throughfall increased slightly, however. In the earlier period, the Scots pines were unable to neutralise the high flux of acidity associated with sulphur deposition, even though this was not a highly polluted part of the UK, and deciduous trees (oak and birch) were only able to neutralise it in summer when the leaves were present. In the later period, the sulphur flux had reduced to the point where the acidity could be neutralised by all species - the neutralisation mechanism is thus likely to be largely leaching of base cations and buffering substances from the foliage. The high fluxes are partly due to the fact that these are 60-80 year old trees growing in an open forest structure. The increase in NO(3)(-) and NH(4)(+) in throughfall in spite of decreased deposition seems likely due to a decrease in foliar uptake, perhaps due to the increasing nitrogen saturation of the catchment soils. These changes may increase the rate of soil microbial activity as nitrogen increases and acidity declines, with consequent effects on water quality of the catchment drainage stream.

Are our dynamic water quality models too complex? A comparison of a new parsimonious phosphorus model, SimplyP, and INCA‐P

This is an Published Version of an article published by American Geophysical Union in Water Resources Research, available online: https://sites.agu.org/

Selective environmental stress caused by magmatic sulfur emissions from continental flood basalt eruptions

Several biotic crises during the past 300 million years have been linked to episodes of continental flood basalt volcanism, and in particular to the release of massive quantities of magmatic sulphur gas species. Flood basalt provinces were typically formed by numerous individual eruptions, each lasting years to decades. However, the environmental impact of these eruptions may have been limited by the occurrence of quiescent periods that lasted hundreds to thousands of years. Here we use a global aerosol model to quantify the sulphur-induced environmental effects of individual, decade-long flood basalt eruptions representative of the Columbia River Basalt Group, 16.5–14.5 million years ago, and the Deccan Traps, 65 million years ago. For a decade-long eruption of Deccan scale, we calculate a decadal-mean reduction in global surface temperature of 4.5 K, which would recover within 50 years after an eruption ceased unless climate feedbacks were very different in deep-time climates. Acid mists and fogs could have caused immediate damage to vegetation in some regions, but acid-sensitive land and marine ecosystems were well-buffered against volcanic sulphur deposition effects even during century-long eruptions. We conclude that magmatic sulphur from flood basalt eruptions would have caused a biotic crisis only if eruption frequencies and lava discharge rates had been high and sustained for several centuries at a time.

Long-term predictions of ecosystem acidification and recovery

This paper considers the long-term (500year) consequences of continued acid deposition, using a small forested catchment in S. England as an example. The MAGIC acidification model was calibrated to the catchment using data for the year 2000, and run backwards in time for 200years, and forwards for 500. Validation data for model predictions were provided by various stream and soil measurements made between 1977 and 2013. The model hindcast suggests that pre-industrial stream conditions were very different from those measured in 2000. Acid Neutralising Capacity (ANC) was +150μeqL(-1) and pH7.1: there was little nitrate (NO3). By the year 2000, acid deposition had reduced the pH to 4.2 and ANC to c. -100μeqL(-1), and NO3 was increasing in the stream. The future state of the catchment was modelled using actual deposition reductions up to 2013, and then based on current emission reduction commitments. This leads to substantial recovery, to pH6.1, ANC +43μeqL(-1), though it takes c. 250years. Then, however, steady acidification resumes, due to continued N accumulation in the catchment and leaching of NO3. Soil data collected using identical methods in 1978 and 2013 show that MAGIC correctly predicts the direction of change, but the observed data show more extreme changes - reasons for this are discussed. Three cycles of forest growth were modelled - this reduces NO3 output substantially during the active growth phase, and increases stream pH and ANC, but acidifies the soil which continues to accumulate nitrogen. The assumptions behind these results are discussed, and it is concluded that unmanaged ecosystems will not return to a pre-industrial state in the foreseeable future.

Dedication of the special issue to Colin Neal

This Special Issue, “Climate change and coupling of macronutrient cycles along the atmospheric, terrestrial, freshwater and estuarine continuum” is dedicated to the career of Colin Neal, whose work over the years has generated so many concepts and so much data to support on-going research in this important research area. This note is concerned with Colin and his contributions to the scientific literature.