A large proportion of nutrients and sediment is mobilised in catchments during storm events. Therefore understanding a catchment's hydrological behaviour during storms and how this acts to mobilise and transport nutrients and sediment to nearby watercourses is extremely important for effective catchment management. The expansion of available in-situ sensors is allowing a wider range of water quality parameters to be monitored and at higher temporal resolution, meaning that the investigation of hydrochemical behaviours during storms is increasingly feasible. Studying the relationship between discharge and water quality parameters in storm events can provide a valuable research tool to infer the likely source areas and flow pathways contributing to nutrient and sediment transport. Therefore, this paper uses 2 years of high temporal resolution (15/30 min) discharge and water quality (nitrate-N, total phosphorus (TP) and turbidity) data to examine hysteretic behaviour during storm events in two contrasting catchments, in the Hampshire Avon catchment, UK. This paper provides one of the first examples of a study which comprehensively examines storm behaviours for up to 76 storm events and three water quality parameters. It also examines the observational uncertainties using a non-parametric approach. A range of metrics was used, such as loop direction, loop area and a hysteresis index (HI) to characterise and quantify the storm behaviour. With two years of high resolution information it was possible to see how transport mechanisms varied between parameters and through time. This study has also clearly shown the different transport regimes operating between a groundwater dominated chalk catchment versus a surface-water dominated clay catchment. This information, set within an uncertainty framework, means that confidence can be derived that the patterns and relationships thus identified are statistically robust. These insights can thus be used to provide information regarding transport processes and biogeochemical processing within river catchments.

Abstract. Analysis of hydrochemical behaviour during storm events can provide new insights into the process controls on nutrient transport in catchments. The examination of storm behaviours using hysteresis analysis has increased in recent years, partly due to the increased availability of high temporal resolution data sets for discharge and water quality parameters. A number of these analyses involve the use of an index to describe the characteristics of a hysteresis loop in order to compare storm behaviours both within and between catchments. This technical note reviews the methods for calculation of the hysteresis index (HI) and explores a new more effective methodology. Each method is systematically tested and the impact of the chosen calculation on the results is examined. Recommendations are made regarding the most effective method of calculating a HI which can be used for comparing data between storms and between different water quality parameters and catchments.

This paper uses high-frequency bankside measurements from three catchments selected as part of the UK government-funded Demonstration Test Catchments (DTC) project. We compare the hydrological and hydrochemical patterns during the water year 2011–2012 from the Wylye tributary of the River Avon with mixed land use, the Blackwater tributary of the River Wensum with arable land use and the Newby Beck tributary of the River Eden with grassland land use. The beginning of the hydrological year was unusually dry and all three catchments were in states of drought. A sudden change to a wet summer occurred in April 2012 when a heavy rainfall event affected all three catchments. The year-long time series and the individual storm responses captured by in situ nutrient measurements of nitrate and phosphorus (total phosphorus and total reactive phosphorus) concentrations at each site reveal different pollutant sources and pathways operating in each catchment. Large storm-induced nutrient transfers of nitrogen and or phosphorus to each stream were recorded at all three sites during the late April rainfall event. Hysteresis loops suggested transport-limited delivery of nitrate in the Blackwater and of total phosphorus in the Wylye and Newby Beck, which was thought to be exacerbated by the dry antecedent conditions prior to the storm. The high rate of nutrient transport in each system highlights the scale of the challenges faced by environmental managers when designing mitigation measures to reduce the flux of nutrients to rivers from diffuse agricultural sources. It also highlights the scale of the challenge in adapting to future extreme weather events under a changing climate

Storm events can drive highly variable behavior in catchment nutrient and water fluxes, yet short‐term event dynamics are frequently missed by low‐resolution sampling regimes. In addition, nutrient source zone contributions can vary significantly within and between storm events. Our inability to identify and characterize time‐dynamic source zone contributions severely hampers the adequate design of land use management practices in order to control nutrient exports from agricultural landscapes. Here we utilize an 8 month high‐frequency (hourly) time series of streamflow, nitrate (NO3‐N), dissolved organic carbon (DOC), and hydroclimatic variables for a headwater agricultural catchment. We identified 29 distinct storm events across the monitoring period. These events represented 31% of the time series and contributed disproportionately to nutrient loads (42% of NO3‐N and 43% of DOC) relative to their duration. Regression analysis identified a small subset of hydroclimatological variables (notably precipitation intensity and antecedent conditions) as key drivers of nutrient dynamics during storm events. Hysteresis analysis of nutrient concentration‐discharge relationships highlighted the dynamic activation of discrete NO3‐N and DOC source zones, which varied on an event‐specific basis. Our results highlight the benefits of high‐frequency in situ monitoring for characterizing short‐term nutrient fluxes and unraveling connections between hydroclimatological variability and river nutrient export and source zone activation under extreme flow conditions. These new process‐based insights, which we summarize in a conceptual model, are fundamental to underpinning targeted management measures to reduce nutrient loading of surface waters.

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Dissolved organic matter (DOM) plays an important role in freshwater biogeochemistry. To investigate the influence of catchment character on the quality and quantity of DOM in freshwaters, 45 sampling sites draining subcatchments of contrasting soil type, hydrology, and land cover within one large upland‐dominated and one large lowland‐dominated catchment were sampled over a 1‐yr period. Dominant land cover in each subcatchment included: arable and horticultural, blanket peatland, coniferous woodland, and improved, unimproved, acid, and calcareous grasslands. The composition of the C, N, and P pool was determined as a function of the inorganic nutrient species (NO3−, NO2−, NH4+, and PO43−) and dissolved organic nutrient (dissolved organic carbon [DOC], dissolved organic nitrogen [DON], and dissolved organic phosphorus [DOP]) concentrations. DOM quality was assessed by calculation of the molar DOC : DON and DOC : DOP ratios and specific ultraviolet absorbance (SUVA254). In catchments with little anthropogenic nutrient inputs, DON and DOP typically composed > 80% of the total dissolved nitrogen (TDN) and total dissolved phosphorus (TDP) concentrations. By contrast, in heavily impacted agricultural catchments DON and DOP typically comprised 5–15% of TDN and 10–25% of TDP concentrations. Significant differences in DOC : DON and DOC : DOP ratios were observed between land cover class with significant correlations observed between both the DOC : DON and DOC : DOP molar ratios and SUVA254 (rs = 0.88 and 0.84, respectively). Analysis also demonstrated a significant correlation between soil C : N ratio and instream DOC : DON/DOP (rs = 0.79 and 0.71, respectively). We infer from this that soil properties, specifically the C : N ratio of the soil organic matter pool, has a significant influence on the composition of DOM in streams draining through these landscapes.

13The measurement of discharge is fundamental in nutrient load estimation. Due to our ability to 14 monitor discharge routinely, it is generally assumed that the associated uncertainty is low. This paper 15 challenges this preconception, arguing that discharge uncertainty should be explicitly taken into 16 account to produce robust statistical analyses. In many studies, paired discharge and chemical 17 datasets are used to calculate 'true' loads and used as the benchmark to compare with other load 18 estimates. 19This paper uses two years of high frequency (daily and sub-hourly) discharge and nutrient 20 concentration data (nitrate-N and total phosphorus (TP)) collected at four field sites as part of the 21Hampshire Avon Demonstration Test Catchment (DTC) programme. A framework for estimating 22 observational nutrient load uncertainty was used which combined a flexible non-parametric approach 23 to characterising discharge uncertainty, with error modelling that allowed the incorporation of errors 24 which were heteroscedastic and temporally correlated. 25The results showed that the stage-discharge relationships were non-stationary, and observational 26 uncertainties from ±2-25% were recorded when the velocity-area method was used. The variability in 27 nutrient load estimates ranged from 1.1-9.9% for nitrate-N and from 3.3-10% for TP when daily 28 laboratory data were used, rising to a maximum of 9% for nitrate-N and 83% for TP when the sensor 29 data were used. However, the sensor data provided a better representation of the 'true' load as storm 30 events are better represented temporally, posing the question: is it more beneficial to have high 31 frequency, lower precision data or lower frequency but higher precision data streams to estimate 32 nutrient flux responses in headwater catchments? 33 34

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