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Eighteen months of 7-hourly analyses of rainfall and stream water chemistry are presented, spanning a wide range of chemical determinands and building on over 20 years of weekly records for the moorland headwaters of the river Severn. The high-frequency time series data show that hydrochemical responses to major hydrological and biological drivers of short-term variability in rainfall and rivers are not captured by conventional low-frequency monitoring programmes. A wealth of flow related, flow independent, diurnal, seasonal and annual fluctuations indicate a cacophony of interactions within the catchment and stream. The complexity of the chemical dynamics is visually obvious, although there appears to be no clear way of translating this complexity into a simple algorithm. The work provides a proof of concept for the complex structure of catchment functioning revealed by extensive high-frequency measurements coupled with high analytical sensitivity and reproducibility. It provides new insights into hydrogeochemical functioning and a novel resource for catchment modelling.

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 SO4 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 NO3, 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.

Al is a critical ecotoxicant in surface waters impacted by acidic deposition. Apart from the most acidic surface waters, Al concentrations are often considered to be controlled by Al(OH)3 or aluminosilicate (clay) solubility for modelling studies. For many UK rivers there is no clear evidence for such solubility controls even though there is the potential under moderately acidic/alkaline conditions. Here, Al solubility in ground and river water is compared for acid sensitive catchments in mid-Wales. The results reveal that there may be a solubility control within the groundwater but a more complex state of affairs within the river. The groundwater is of high CO2 content and once in the river it degasses to raise pH. However, there is limited change in Al concentration and hence the solubility relationship is lost. The results flag the potential importance of groundwater solubility controls for Al and the potential for the groundwater zone to act as an Al filter. For positive alkalinity groundwaters, the high CO2 levels depress the pH to near the value for minimum Al solubility. However, there is no simple groundwater end-member. Examining Al solubility controls solely within the rivers provides cryptic and misleading clues to the hydrogeological controls for Al within catchments. Assessing the within-catchment processes requires direct measurement with full consideration of both inorganic and organic attenuation.

Operationally defined dissolved Titanium [Ti] (the b0.45 μm filtered fraction) in rivers draining rural, agricultural, urban and industrial land-use types in the UK averaged 2.1 μg/l with a range in average of 0.55 to 6.48 μg/l. The lowest averages occurred for the upland areas of mid-Wales the highest just downstream of major sewage treatment works (STWs). [Ti] in rainfall and cloud water in mid-Wales averaged 0.2 and 0.7 μg/l, respectively. Average, baseflow and stormflow [Ti] were compared with two markers of sewage effluent and thus human population: soluble reactive phosphorus (SRP) and boron (B). While B reflects chemically conservative mixing, SRP declined downstreamof STWinputs due to in-streamphysico-chemical and biological uptake. The results are related to colloidal and sub-colloidal Ti inputs from urban/industrial conurbations coupled with diffuse background (geological) sources and within-river removal/retention under low flows as a result of processes of aggregation and sedimentation. The urban/industrial inputs increased background [Ti] by up to eleven fold, but the total anthropogenic Ti input might well have been underestimated owing to withinriver retention. A baseline survey using cross-flow ultrafiltration revealed that up to 79% of the [Ti]was colloidal/nanoparticulate (N1 kDa i.e. Nc. 1–2 nm) for the rural areas, but as lowas 28% for the urban/industrial rivers. This raises fundamental issues of the pollutant inputs of Ti,with the possibility of significant complexation of Ti in the sewage effluents and subsequent breakdown within the rivers, as well as the physical dispersion of fine colloids down to the macro-molecular scale. Although not directly measured, the particulate Ti can make an important contribution to the net Ti flux.

Dissolved aluminium concentrations ([Al]) in the <0.45μm filtered fraction are described for 54 UK river sites covering rural, acidic/acid sensitive, agricultural and urban typologies, and wide pH range (4 to 11). High [Al] occurred under acidic conditions and for acid runoff neutralised by bicarbonate rich groundwater. Thermodynamic analysis indicates Al hydroxide/hydroxy-silicate oversaturation at circumneutral pH across the rivers, but undersaturation at lower/higher pH. The oversaturation reflects in part the presence of Al bearing colloids as indicated by (1) [Al] being correlated with components associated with both lithogenic (Fe, Ti and lanthanides) colloids and organic carbon, (2) baseflow studies using cross-flow ultrafiltration and (3) comparison of our data with Acid Waters Monitoring Network (AWMN) information on labile and non-labile Al. Tree harvesting and emission reductions of SOx in acidic and acid sensitive catchments in mid-Wales led to acidification reversal, lower [Al] and changing [H+] – [Al] relationships. The [Al] decline was confined to acidic conditions while [Al] increased during the later part of the monitoring period with a peak around 2002 for moorland and forested systems. Colloidal production across the flow range was indicated late in the record by comparison of our data with information collected by the AWMN for a site in mid-Wales. This production seems interlinked with organic carbon and with dissolved CO2 changes. In order for further understanding of Al hydrogeochemistry in river systems there is a need to integrate research that moves from equilibrium to kinetic and colloidal consideration including the critical issues of organic and inorganic controls within the context of bioavailability and aquatic stress. The colloidal Al may well be of low environmental concern to fish and other factors such as habitat may well be critical.

The fate of Ti was examined in an activated sludge plant serving over 200,000 people. These studies revealed a decrease of 30 to 3.2 µg/L of Ti<0.45 µm from influent to effluent and a calculated Ti presence of 305 mg/kg DW in wasted sludge. Thus, using sludge as a fertiliser would result in a predicted deposition of up to 250 mg/m2 of Ti to soil surfaces using a recommended maximal agricultural application rate. Given the major use of TiO2 in many industrial and domestic applications where loss to the sewer is possible, this measured Ti was presumed to have been largely TiO2, a proportion of which will be nanoparticle sized. To assess the behaviour of engineered nanoparticle (ENP) TiO2 in sewage and toxicology studies, Optisol (Oxonica Materials Ltd) and P25 (Evonik Industries AG), which are representative of forms used in sunscreen and cosmetic products, were used. These revealed a close association of TiO2 ENPs with activated sludge. Using commercial information on consumption, and removal rates for sewage treatment, predictions were made for river water concentrations for sunscreen TiO2 ENPs for the Anglian and Thames regions in Southern England. The highest predicted value from these exercises was 8.8 µg/L for the Thames region in which it was assumed one in four people used the recommended application of sunscreen during a low flow (Q95) period. Ecotoxicological studies using potentially vulnerable species indicated that 1,000 µg/L TiO2 ENP did not affect the viability of a mixed community of river bacteria in the presence of UV light. Direct exposure to TiO2 ENPs did not impair the immuno-effectiveness of earthworm coelomocyte cells at concentrations greatly above those predicted for sewage sludge.

This paper presents new information on the hydrology and water quality of the eroding peatland headwaters of the River Severn in mid-Wales and links it to the impact of plantation conifer forestry further down the catchment. The Upper Hafren is dominated by low-growing peatland vegetation, with an average annual precipitation of around 2650 mm with around 250 mm evaporation. With low catchment permeability, stream response to rainfall is “flashy” with the rising limb to peak stormflow typically under an hour. The water quality is characteristically “dilute”; stormflow is acidic and enriched in aluminium and iron from the acid organic soil inputs. Baseflow is circum-neutral and calcium and bicarbonate bearing due to the inputs of groundwater enriched from weathering of the underlying rocks. Annual cycling is observed for the nutrients reflecting uptake and decomposition processes linked to the vegetation and for arsenic implying seasonal waterlogging within the peat soils and underlying glacial drift. Over the decadal scale, sulphate and nitrate concentrations have declined while Gran alkalinity, dissolved organic carbon and iron have increased, indicating a reduction in stream acidification. Within the forested areas the water quality is slightly more concentrated and acidic, transgressing the boundary for acid neutralisation capacity as a threshold for biological damage. Annual sulphate and aluminium concentrations are double those observed in the Upper Hafren, reflecting the influence of forestry and the greater ability of trees to scavenge pollutant inputs from gaseous and mist/cloud-water sources compared to short vegetation. Acidification is decreasing more rapidly in the forest compared to the eroding peatland possibly due to the progressive harvesting of the mature forest reducing the scavenging of acidifying inputs. For the Lower Hafren, long-term average annual precipitation is slightly lower, with lower average altitude, at around 2520 mm and evaporation i

The changing patterns of riverine boron concentration are examined for the Thames catchment in southern southeastern England using data from 1997 to 2007. Boron concentrations are related to an independent 28 marker for sewage effluent, sodium. The results show that boron concentrations in the main river channels have declined with time especially under baseflow conditions when sewage effluent dilution potential is at its lowest. While boron concentrations have reduced, especially under low-flow conditions, this does not fully translate to a corresponding reduction in boron flux and it seems that the “within-catchment” supplies of boron to the river are contaminated by urban sources. The estimated boron reduction in the effluent input to the river based on the changes in river chemistry is typically around 60% and this figure matches with an initial survey of more limited data for the industrial north of England. Data for effluent concentrations at eight sewage treatment works within the Kennet also indicate substantial reductions in boron concentrations: 80% reduction occurred between 2001 and 2008. For the more contaminated rivers there are issues of localised rather than catchment-wide sources and uncertainties over the extent and nature of water/boron stores. Atmospheric sources average around 32 to 61% for the cleaner and 4 to 14% for the more polluted parts. The substantial decreases in the boron concentrations correspond extremely well with the timing and extent of European wide trends for reductions in the industrial and domestic usage of boron-bearing compounds. It clearly indicates that such reductions have translated into lower average and peak concentrations of boron in the river although the full extent of these reductions has probably not yet occurred due to localised stores that are still to deplete

Three field manipulation experiments were carried out during 1993–1995 on the Northern Pennines to investigate the influences of temperature, solar radiation and rainfall on the release of dissolved organic carbon (DOC) from vegetated soil cores using zero-tension lysimeters. The cores were manipulated by being translocated to four sites down a climatic gradient, by artificial soil heating or being exposed to double normal rainfall. In each experiment three soil types, a brown earth, a micropodzol and a peaty gley, with differing organic matter content and distribution within the profile, were studied. DOC data, expressed as mg C m−2 day−1, were analysed following log10 transformation, by a repeated measures analysis of variance procedure, using climatic variables measured concurrently with sampling, and 1 and 2 months before sampling. DOC release was dominated by rainfall but was also associated with solar radiation and temperature. With each of the three climatic variables, rainfall, solar radiation and temperature, both positive and negative effects on DOC release have been found significant, indicating that the concurrent and delayed effects of the same variable may be different. DOC release was positively related with all three soils to concurrent rainfall, indicating rainfall's primary leaching action. DOC release was also negatively related to rainfall of the previous month indicating that its action depletes the leachable pool of DOC in the soil. DOC release was positively associated with solar radiation 2 months earlier, indicating that DOC's main source is that of primary production; DOC peaks closely followed peaks of annual primary production. DOC release was linked with temperature, the strongest association being with temperature 2 months earlier, indicating that temperature effects both primary production and DOC regeneration via organic matter decomposition. A conceptual model, relating our findings to those processes known to govern DOC release from

Concentrations of seven metals were measured in over 1000 samples as part of an integrated survey. Sixteen metal pairs were significantly positively correlated. Cluster analysis identified two clusters. Metals from the largest (Cr, Cu, Ni, V, Zn), but not the smallest (Cd, Pb) cluster were significantly negatively correlated with spatial location and soil pH and organic matter content. Cd and Pb were not correlated with these parameters, due possibly to the masking effect of recent extensive release. Analysis of trends with soil properties in different habitats indicated that general trends may not necessarily be applicable to all areas. A risk assessment indicated that Zn poses the most widespread direct risk to soil fauna and Cd the least. Any risks associated with high metal concentrations are, however, likely to be greatest in habitats such as arable and horticultural, improved grassland and built up areas where soil metal concentrations are more frequently elevated.

In a field trial, oiled beach sand was buried in a coastal dune system in south Wales. A monitoring programme was designed to assess the rate of leaching of inorganic ions and hydrocarbons from the deposit. Active breakdown of the weathered oil occurred within the oiled beach sand, but hydrocarbons from the original material, or arising as a result of degradation, did not follow the same leaching pattern as inorganic ions; they remained within the original deposit. The results suggest that weathered oil coming ashore from spills at sea can be mixed with sand and buried to degrade in coastal soils, without risk of groundwater contamination by hydrocarbons.