The time it takes for rainfall to travel through a catchment and reach the stream is a fundamental hydraulic parameter that controls the retention of soluble contaminants and thus the downstream consequences of pollution episodes. Catchments with short flushing times will deliver brief, intense contaminant pulses to downstream waters, whereas catchments with longer flushing times will deliver less intense but more sustained contaminant fluxes. Here we analyse detailed time series of chloride, a natural tracer, in both rainfall and runoff from headwater catchments at Plynlimon, Wales. We show that, although the chloride concentrations in rainfall have a white noise spectrum, the chloride concentrations in streamflow exhibit fractal 1/f scaling over three orders of magnitude. The fractal fluctuations in tracer concentrations indicate that these catchments do not have characteristic flushing times. Instead, their travel times follow an approximate power-law distribution implying that they will retain a long chemical memory of past inputs. Contaminants will initially be flushed rapidly, but then low-level contamination will be delivered to streams for a surprisingly long time.

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The chemical dynamics of lakes and streams affect their suitability as aquatic habitats and as water supplies for human needs. Because water quality is typically monitored only weekly or monthly, however, the higher-frequency dynamics of stream chemistry have remained largely invisible. To illuminate a wider spectrum of water quality dynamics, rainfall and streamflow were sampled in two headwater catchments at Plynlimon, Wales, at 7-h intervals for 1-2 y and weekly for over two decades, and were analyzed for 45 solutes spanning the periodic table from H + to U. Here we show that in streamflow, all 45 of these solutes, including nutrients, trace elements, and toxic metals, exhibit fractal 1/f α scaling on time scales from hours to decades (α = 1.05 ± 0.15, mean ± SD). We show that this fractal scaling can arise through dispersion of random chemical inputs distributed across a catchment. These 1/f time series are non-self-averaging: monthly, yearly, or decadal averages are approximately as variable, one from the next, as individual measurements taken hours or days apart, defying naive statistical expectations. (By contrast, stream discharge itself is nonfractal, and self-averaging on time scales of months and longer.) In the solute time series, statistically significant trends arise much more frequently, on all time scales, than one would expect from conventional t statistics. However, these same trends are poor predictors of future trends-much poorer than one would expect from their calculated uncertainties. Our results illustrate how 1/f time series pose fundamental challenges to trend analysis and change detection in environmental systems.aquatic chemistry | watershed hydrology | environmental monitoring | pink noise | flicker noise

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Abstract:The eutrophication of surface waters has become an endemic global problem. Nutrient loadings from agriculture are a major driver, but it remains very unclear what level of on-farm controls are necessary or can be justified to achieve water quality improvements. In this review article, we use the UK as an example of societies' multiple stressors on water quality to explore the uncertainties and challenges in achieving a sustainable balance between useable water resources, diverse aquatic ecosystems and a viable agriculture. Our analysis shows that nutrient loss from agriculture is a challenging issue if farm productivity and profitability is to be maintained and increased. Legacy stores of nitrogen (N) and phosphorus (P) in catchments may be sufficient to sustain algal blooms and murky waters for decades to come and more innovation is needed to drawdown and recover these nutrients. Agriculture's impact on eutrophication risk may also be overestimated in many catchments, and more accurate accounting of sources, their bioavailabilities and lag times is needed to direct proportioned mitigation efforts more effectively. Best practice farms may still be leaky and incompatible with good water quality in high-risk areas requiring some prioritization of society goals. All sectors of society must clearly use N and P more efficiently to develop long-term sustainable solutions to this complex issue and nutrient reduction strategies should take account of the whole catchment-to-coast continuum. However, the right balance of local interventions OPEN ACCESS Sustainability 2014, 6 5854 (including additional biophysical controls) will need to be highly site specific and better informed by research that unravels the linkages between sustainable farming practices, patterns of nutrient delivery, biological response and recovery trajectories in different types of waterbodies.

Th is commentary examines an "inconvenient truth" that phosphorus (P)-based nutrient mitigation, long regarded as the key tool in eutrophication management, in many cases has not yet yielded the desired reductions in water quality and nuisance algal growth in rivers and their associated downstream ecosystems. We examine why the water quality and aquatic ecology have not recovered, in some case aft er two decades or more of reduced P inputs, including (i) legacies of past land-use management, (ii) decoupling of algal growth responses to river P loading in eutrophically impaired rivers; and (iii) recovery trajectories, which may be nonlinear and characterized by thresholds and alternative stable states. It is possible that baselines have shift ed and that some disturbed river environments may never return to predisturbance conditions or may require P reductions below those that originally triggered ecological degradation. We discuss the practical implications of setting P-based nutrient criteria to protect and improve river water quality and ecology, drawing on a case study from the Red River Basin in the United States. We conclude that the challenges facing nutrient management and eutrophication control bear the hallmarks of "postnormal" science, where uncertainties are large, management intervention is urgently required, and decision stakes are high. We argue a case for a more holistic approach to eutrophication management that includes more sophisticated regime-based nutrient criteria and considers other nutrient and pollutant controls and river restoration (e.g., physical habitat and functional food web interactions) to promote more resilient water quality and ecosystem functioning along the land-freshwater continuum.

Abstract. This paper introduces new insights into the hydrochemical functioning of lowland river systems using fieldbased spectrophotometric and electrode technologies. The streamwater concentrations of nitrogen species and phosphorus fractions were measured at hourly intervals on a continuous basis at two contrasting sites on tributaries of the River Thames -one draining a rural catchment, the River Enborne, and one draining a more urban system, The Cut. The measurements complement those from an existing network of multi-parameter water quality sondes maintained across the Thames catchment and weekly monitoring based on grab samples. The results of the sub-daily monitoring show that streamwater phosphorus concentrations display highly complex dynamics under storm conditions dependent on the antecedent catchment wetness, and that diurnal phosphorus and nitrogen cycles occur under low flow conditions. The diurnal patterns highlight the dominance of sewage inputs in controlling the streamwater phosphorus and nitrogen concentrations at low flows, even at a distance of 7 km from the nearest sewage treatment works in the rural River Enborne. The time of sample collection is important when judging water quality against ecological thresholds or standards. An exhaustion of the supply of phosphorus from diffuse and multiple septic tank sources during storm events was evident and load estimation was not improved by sub-daily monitoring beyond that achieved by daily sampling because of the eventual reduction in the phosphorus mass entering the stream during events. The results highlight the utility of sub-daily water quality measurements and the discussion considers the practicalities and challenges of in situ, sub-daily monitoring.