Abstract. Water quality data spanning 13 years and covering an extensive range of major, minor and trace elements in rain and stream waters at Plynlimon in mid Wales, are presented. Rainfall water chemistry is highly variable due to varying proportions of marine and pollutant derived constituents associated with patterns of atmospheric circulation. Stream waters, being composed of different proportions of waters from three chemically distinct sources at any one time (atmospheric deposition, the soil system and deeper groundwaters), are also chemically highly variable. For example, components predominantly derived from deposition such as chloride change only in response to sea-salt deposition episodes. Solutes associated with bedrock weathering such as calcium, magnesium, and alkalinity decrease with increasing flow, those associated with the upper soil layers such as aluminium, many transition metals, dissolved organic carbon and hydrogen ions increase with increasing flow. The nutrients (e.g. nitrate, boron, bromide and iodine) exhibit strong seasonal cycles associated with cycles of vegetation growth and decay. The changes in stream water chemistry resulting from tree harvesting in the Afon Hore catchment are shown to have run their course within a period of eight years. Nutrient increases in the first few years following the commencement of felling have returned to or fallen below pre-felling values. Aluminium changes are shown to be complicated by changes in nitrate and calcium. Aluminium concentrations initially increased and have fallen below their pre-felling value. Data for chloride suggest a reduction in capture of dry and mist deposition; this indicates the importance of understanding reduced deposition as a result of felling. Felling has also affected the soil micro-climate which experiences greater fluctuations in temperature and an increase in the concentration of constituents associated with organic matter. Input-output mass balance estimates show that atmospheric inputs of many constituents are retained strongly by the catchment (e.g. ammonium, phosphate, barium, boron, lead and iodine). In contrast, many of the transition elements as well as divalent base cations, aluminium and alkalinity show a net release from the catchment. Conservative constituents such as chloride and sodium show a net input-output balance.

Abstract. A series of boreholes of up to 50 m depth, drilled into Lower Palaeozoic mudstone, shale and greywacke bedrock in the headwater catchment areas of the River Severn at Plynlimon in Central Wales, shows an extensive chemically- and hydrologically-active shallow groundwater fracture flow system. Groundwater chemistry varies in space and time with lowest water levels and highest alkalinities occurring during the drier summer months. The groundwaters are enriched in base cations, silica, sulphate and alkalinity relative to surface waters indicating significant silicate weathering sources and sulphide oxidation. These sources provide important contributions to both stream water quality and flow. At one site, the introduction of a borehole near to the main river opened bedrock fractures which increased the amount of groundwater entering the river. This had a profound effect on the river water quality by increasing the pH, alkalinity and calcium concentrations. As well as pointing to the possibility of the wider availability of groundwater resources in upland areas, the results highlight (a) the potential value of groundwater as a acid neutralizing resource, (b) the importance of weathering processes and flow routing within the groundwater environment for stream water chemistry, (c) the potential for altering stream water quality by manipulation of groundwater routing and (d) the need to include groundwater characteristics in hydrochemical management models of surface water acidification.

Abstract. The composition of cloudwater samples collected at Plynlimon, Mid Wales by the Institute of Hydrology is described based on one of the most comprehensive chemical records for deposition in the UK. Comparison with bulk rainwater samples for the same area demonstrates a tenfold enrichment of most elements in cloudwater. Large variations in cloudwater composition occur due to variations in marine and terrestrial/anthropogenic sources, general weather patterns, atmospheric circulation and seasonal effects. All trace metal concentrations are associated with anthropogenic contamination. The lanthanides La, Cc and Pr, and Y are highly correlated in ratios associated with lithogenic sources and fossil fuel combustion. Outliers suggest the influence of catalysts used in the petrochemical cracking process. Plantation forestry significantly enhances the annual deposition of solutes from cloudwater; between 15 and 40% of most constituents to upland forested catchments and around 50% for NO3, B and Cd come from cloud deposition. In upland moorland areas, only 10% of the annual deposited load of inorganic constituents comes from cloudwater.

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