Mixing of arsenic-rich groundwater and surface water in drinking water distribution systems: Implications for contaminants, disinfection byproducts and organic components.

The utilization of groundwaters containing high levels of arsenic (As) for drinking water purposes presents major health and economic challenges for water utilities. One low-cost approach is to mix arsenic-rich groundwater (GW) with arsenic-free surface waters (SW) to achieve acceptable As levels. In this study we investigated the effect of different mixing ratios on water quality in an eastern Croatian water distribution system (WDS). To investigate the effects of mixing on drinking water quality, we measured the organic matter (OM) composition, disinfection byproduct (DBP) and metal concentrations in differently mixed ratios of GW and SW within the WDS. Fluorescence analysis revealed that the GW and SW had similar OM composition, with an almost equal ratio of humic- and protein-like OM throughout the WDS despite fluorescence indices revealing slightly different OM sources between the two water types. The tyrosine-like OM component was more variable, increasing during warmer months and towards the end of the WDS, most likely due to enhanced biofilm formation. Arsenic concentrations decreased to below 10 µg/L in the second half of the sampling campaign. Acceptable water quality was achieved after a period of destabilization and solubilization of loose deposits within the WDS resulting in their mobilization caused by water quality changes. Principal component and classification analysis, regression models and Spearman correlation coefficients revealed an association between As, OM and DBP concentrations with these correlations suggestive of their role in As mobilization in the WDS. Changing source waters, with different OM content and characteristics, corresponded to variable As release within the WDS.

What is the deal with the Green Deal: Will the new strategy help to improve European freshwater quality beyond the Water Framework Directive?

Agricultural land use covers almost half of the EU territory and reducing nutrient and pesticide losses to freshwaters is central to existing EU policy. However, the progress of improving freshwater quality and reducing eutrophication is slow and lags behind targets. The Green Deal is a key element of the EU plans to implement the United Nation's Sustainable Development Goals. Here, we discuss the opportunities that the Green Deal and associated strategies may provide for the achievement of the water quality goals of the Water Framework Directive in agricultural landscapes. We welcome Green Deal's aspirational stated goals. However, the reliance of mitigation of diffuse agricultural pollution on the reform of the Common Agricultural Policy represents grave risks for practical implementation and the achievement of the Green Deal objectives. We also argue that the new strategies should be targeted at tackling and understanding the sources of water quality problems along the full pollution continuum. To maximise the opportunities for tackling diffuse pollution from agricultural land use and achieving the delayed water quality targets, we stress that a range of targeted new instruments will be needed to close the gaps in the pollution continuum 'from source to impact'. These gaps include: (I) smart and standardised monitoring of the impacts of proposed eco-schemes and agri-environment-climate measures, (ii) active restoration of agricultural streams and ditches and their floodplains to reduce secondary pollution sources, (iii) options to draw down nutrient levels to or below the agronomic optimum that reduce legacy sources, (iv) integrating farm-scale and catchment-scale analysis of trade-offs in reducing different pollutants and their combined effects, and finally (v) accounting for emerging pressures to freshwater quality due to climate change. Incorporation of the pollution continuum framework into tackling diffuse agricultural pollution will ensure that the European water-related policy goals are achieved.

The concentration-discharge slope as a tool for water quality management.

Recent technological breakthroughs of optical sensors and analysers have enabled matching the water quality measurement interval to the time scales of stream flow changes and led to an improved understanding of spatially and temporally heterogeneous sources and delivery pathways for many solutes and particulates. This new ability to match the chemograph with the hydrograph has promoted renewed interest in the concentration-discharge (c-q) relationship and its value in characterizing catchment storage, time lags and legacy effects for both weathering products and anthropogenic pollutants. In this paper we evaluated the stream c-q relationships for a number of water quality determinands (phosphorus, suspended sediments, nitrogen) in intensively managed agricultural catchments based on both high-frequency (sub-hourly) and long-term low-frequency (fortnightly-monthly) routine monitoring data. We used resampled high-frequency data to test the uncertainty in water quality parameters (e.g. mean, 95th percentile and load) derived from low-frequency sub-datasets. We showed that the uncertainty in water quality parameters increases with reduced sampling frequency as a function of the c-q slope. We also showed that different sources and delivery pathways control c-q relationship for different solutes and particulates. Secondly, we evaluated the variation in c-q slopes derived from the long-term low-frequency data for different determinands and catchments and showed strong chemostatic behaviour for phosphorus and nitrogen due to saturation and agricultural legacy effects. The c-q slope analysis can provide an effective tool to evaluate the current monitoring networks and the effectiveness of water management interventions. This research highlights how improved understanding of solute and particulate dynamics obtained with optical sensors and analysers can be used to understand patterns in long-term water quality time series, reduce the uncertainty in the monitoring data and to manage eutrophication in agricultural catchments.

Unravelling organic matter and nutrient biogeochemistry in groundwater-fed rivers under baseflow conditions: Uncertainty in in situ high-frequency analysis.

In agricultural catchments, diffuse nutrient fluxes (mainly nitrogen N and phosphorus P), are observed to pollute receiving waters and cause eutrophication. Organic matter (OM) is important in mediating biogeochemical processes in freshwaters. Time series of the variation in nutrient and OM loads give insights into flux processes and their impact on biogeochemistry but are costly to maintain and challenging to analyse for elements that are highly reactive in the environment. We evaluated the capacity of the automated monitoring to capture typically low baseflow concentrations of the reactive forms of nutrients and OM: total reactive phosphorus (TRP), nitrate nitrogen (NO3-N) and tryptophan-like fluorescence (TLF). We compared the performance of in situ monitoring (wet chemistry analyser, UV-vis and fluorescence sensors) and automated grab sampling without instantaneous analysis using autosamplers. We found that automatic grab sampling shows storage transformations for TRP and TLF and do not reproduce the diurnal concentration pattern captured by the in situ analysers. The in situ TRP and fluorescence analysers respond to temperature variation and the relationship is concentration-dependent. Accurate detection of low P concentrations is particularly challenging due to large errors associated with both the in situ and autosampler measurements. Aquatic systems can be very sensitive to even low concentrations of P typical of baseflow conditions. Understanding transformations and measurement variability in reactive forms of nutrients and OM associated with in situ analysis is of great importance for understanding in-stream biogeochemical functioning and establishing robust monitoring protocols.

Understanding nutrient biogeochemistry in agricultural catchments: the challenge of appropriate monitoring frequencies.

We evaluate different frequencies of riverine nutrient concentration measurement to interpret diffuse pollution in agricultural catchments. We focus on three nutrient fractions, nitrate-nitrogen (NO3-N), total reactive phosphorus (TRP) and total phosphorus (TP) observed using conventional remote laboratory-based, low-frequency sampling and automated, in situ high-frequency monitoring. We demonstrate the value of low-frequency routine nutrient monitoring in providing long-term data on changes in surface water and groundwater nutrient concentrations. By contrast, automated high-frequency nutrient observations provide insight into the fine temporal structure of nutrient dynamics in response to a full spectrum of flow dynamics. We found good agreement between concurrent in situ and laboratory-based determinations for nitrate-nitrogen (Pearson's R = 0.93, p < 0.01). For phosphorus fractions: TP (R = 0.84, p < 0.01) and TRP (R = 0.79, p < 0.01) the relationships were poorer due to the underestimation of P fractions observed in situ and storage-related changes of grab samples. A detailed comparison between concurrent nutrient data obtained by the hourly in situ automated monitoring and weekly-to-fortnightly grab sampling reveals a significant information loss at the extreme range of nutrient concentration for low-frequency sampling.

Nitrate in United kingdom rivers: policy and its outcomes since 1970.

Modern conventional farming provides Western Europe and North America with reliable, high quality, and relatively cheap supplies of food and fiber, increasingly viewed as a potential source of fuel. One of the costs is continued widespread pollution of rivers and groundwater-predominantly by nutrients. In 1970, in both the United States and UK, farming was focused on maximizing yield and management practices were rapidly modernizing. Little attention was paid to the external impacts of farming. In 2010, diffuse pollution from agriculture is being seriously addressed by both voluntary and statutory means in an attempt to balance environmental costs with the continued benefits of agricultural production. In this paper we consider long-term changes in the concentration and flux of nitrate in five rural UK rivers to demonstrate the impact of agricultural intensification and subsequent policies to reduce diffuse pollution on river water quality between 1970 and 2010.