Modelling episodic acidification of surface waters: the state of science

Field studies of chemical changes in surface waters associated with rainfall and snowmelt events have provided evidence of episodic acidification of lakes and streams in Europe and North America. Modelling these chemical changes is particularly challenging because of the variability associated with hydrological transport and chemical transformation processes in catchments. This paper provides a review of mathematical models that have been applied to the problem of episodic acidification. Several empirical approaches, including regression models, mixing models and time series models, support a strong hydrological interpretation of episodic acidification. Regional application of several models has suggested that acidic episodes (in which the acid neutralizing capacity becomes negative) are relatively common in surface waters in several regions of the US that receive acid deposition. Results from physically based models have suggested a lack of understanding of hydrological flowpaths, hydraulic residence times and biogeochemical reactions, particularly those involving aluminum. The ability to better predict episodic chemical responses of surface waters is thus dependent upon elucidation of these and other physical and chemical processes.     

Comparison of episodic acidification in Canada, Europe and the United States

Episodic acidification is practically a ubiquitous process in streams and drainage lakes in Canada, Europe and the United States. Depressions of pH are often smaller in systems with low pre-episode pH levels. Studies on European surface waters have reported episodes most frequently with minimum pH levels below 4.5. In Canada and the United States, studies have also reported a number of systems that have had minimum pH levels below 4.5. In all areas, change in water flowpath during hydrological events is a major determinant of episode characteristics. Episodic acidification is also controlled by a combination of other natural and anthropogenic factors. Base cation decreases are an important contributor to episodes in circumneutral streams and lakes. Sulphate pulses are generally important contributors to episodic acidification in Europe and Canada. Nitrate pulses are generally more important to episodic acidification in the Northeast United States. Increases in organic acids contribute to episodes in some streams in all areas. The sea-salt effect is important in near-coastal streams and lakes. In Canada, Europe and the United States, acidic deposition has increased the severity (minimum pH reached) of episodes in some streams and lakes.     

Effects of clearfelling on stream and soil water aluminium chemistry in three UK forests

Data are presented demonstrating how clearfelling has changed soil and stream water aluminium chemistry. For soil waters, a strong empirical relationship was observed between inorganic aluminium (Al(inorg)) and total inorganic anion (TIA) concentrations. Before felling, chloride and sulphate accounted for the largest proportion of the TIA concentration. After felling, in soils where nitrification was active, nitrate became increasingly important. Where this led to an increase in TIA, Al(inorg) concentrations increased. Over five years, nitrate concentrations have fallen, along with TIA, resulting in a sympathetic decline in Al(inorg). Streams draining clearfelled areas initially became more acid, although chloride and sulphate concentrations decreased. Stream water nitrate concentrations increased soon after felling and remained higher than controls for up to four years. While nitrate concentrations were high, Al(inorg) remained unchanged. Subsequently, as nitrate and TIA decreased, Al(inorg) also declined to concentrations below those in the control stream. Clearfelling upland forests will not necessarily result in immediate improvements in water quality, although long-term benefits may be seen before canopy-closure of the next crop.     

Seasonal trend of fog water chemical composition in the Po Valley

Fog frequency in the Po Valley, Northern Italy, can be as high as 30% of the time in the fall-winter season. High pollutant concentrations have been measured in fog water samples collected in this area over the past few years. The combined effects of high fog occurrence and high pollutant loading of the fog droplets can determine, in this area, appreciable chemical deposition rates. An automated station for fog water collection was developed, and deployed at the field station of S. Pietro Capofiume, in the eastern part of the Po Valley for an extended period: from the beginning of November 1989 to the end of April 1990. Time-resolved sampling of fog droplets was carried out during all fog events occurring in this period, and chemical analyses were performed on the collected samples. Statistical information on fog occurrence and fog water chemical composition is reported in this paper, and a tentative seasonal deposition budget is calculated for H+, NH4+, NO3- and SO4(2-) ions. The problems connected with fog droplet sampling in sub-freezing conditions are also addressed in the paper.     

Observations of H2O2 and PAN in a rural atmosphere

Measurements of gaseous H2O2 and peroxyacetyl nitrate (PAN) concentrations in air are given for a site in rural southern England over an approximately 4-year period. In both cases the data show both diurnal and seasonal patterns. Temperature and wind direction had clear influences on the recorded concentrations of both species. There was an indication of increasing H2O2 concentrations with time. The use of a two-dimensional global model confirmed that this would be expected to occur alongside growth in ozone formation. It is suggested that, during photochemical episodes, the sequential build-up of ozone, PAN and H2O2 could be important in influencing the ability of vegetation to resist the effects of aggressive pollutants.     

Cadmium availability to the cyanobacterium Synechocystis aquatilis in solutions containing chloride

Availability of cadmium to Synechocystis aquatilis (estimated by 109Cd sorption and cadmium toxicity-14C method) in solutions containing cadmium and complexing (KCl) or non-complexing (KNO3) salts, in the range of 0-0.5 m was investigated. Both cadmium surface adsorption and transport into the cells were lower in solutions containing cadmium chloride complexes (CdCl+, CdCl2, CdCl3-) than in those containing cadmium in the form of Cd2+. Also, cadmium toxicity in solutions of higher KCl concentrations, in which CdCl+ and CdCl2 forms predominated, was significantly limited.     

Impacts of afforestation on water quality trends in two catchments in mid-Wales

The impact of afforestation on stream-water chemistry for two catchments in central Wales is investigated. Trends in water chemistry are evaluated with forest age progressing at 8-15 years and 20-27 years. To assess the possible exacerbating effect of afforestation on surface-water acidification two moorland catchments are used as controls. Absolute differences in inter-catchment streamwater chemistry are evident. Differences in acidity between the moorland and the young forest site reflect site preparation and modifications to water pathways. Differences in the observed present day chemistry between the young and old forest result from past interactions between deposition changes during forest development. An estimate of the future impact of forest growth was attained from model predictions. The model was calibrated to present day stream-water chemistry and incorporates, cation uptake, evapotranspiration/ concentration effect and increased scavenging of occult and dry deposition. Predictions suggest the pH will decline to 5.3 when the young forest progresses to 20 years of age, which is still much higher than the pH recorded at the older forest site at the age of 20 years.     

The effect of temperature and salinity on copper body-burden and copper toxicity to Hediste (Nereis) diversicolor

Temperature from 12 to 22°C and salinity from 30.5 to 7.6 increased accumulation of copper in Hediste diversicolor. Copper accumulated ranged from 85.83 to 217.14 g g^-1. Sediments reduced accumulation of copper under temperature-salinity combinations. Accumulated copper ranged from 90.19 to 153.26 g g^-1.However, mortality of the worms was not solely dependent upon copper body-burden. It ranged from 34 to 45% and from 38 to 80% in the presence of sediment. A combination of osmoregulatory and thermal stresses increased the toxic effect of copper to the worms.     

The effects of salinity,temperature and sediment on the toxicity of copper to juvenile Hediste (Nereis) diversicolor (O. F. Muller)

Without sediment, increasing salinity (7.3 to 29.2) and increasing temperature (12 to 22 °C) reduced the toxicity of copper to juvenile Hediste diversicolor. The LC₅₀ values ranged from 357 gL^-1 in 7.3 to 513 g L^-1 in 29.2 at 12°C and from 247 to 500 g L^-1 at 22°C. In deionized water all the juvenile were dead in all solutions to which copper was added (100 to 600 g L^-1). Dead worms were swollen and everted their pharynxs. In higher doses of copper (500 to 600 g L^-1) the worms were abnormal in behaviour in all salinities (0 to 29.2). The ability to swim or crawl was disturbed.With sediments increasing temperature and increasing salinity increased the toxicity of copper to the worms. The LC₅₀ values ranged from 3200 to 4100 g L^-1 at 22°C. The response of the juvenile to copper was antagonistic to increasing temperature and salinity and synergistic to increasing salinity and increasing temperature without and with the sediment respectively.     

Trace metals in interstitial waters from sandstones: acidic inputs to shallow groundwaters

There is some evidence from southern Britain that shallow groundwaters in non-carbonate lithologies may be affected by acidic deposition. To investigate this, interstitial water profiles down to 12 m have been obtained from unsaturated sands or semi-consolidated sandstones from the Folkestone Beds (Lower Greensand) of Surrey and the Sherwood Sandstone of the West Midlands. The pH of the interstitial waters generally increased with depth and reflected an increase in the base saturation of the exchange complex. Beneath the highly acidic surface soil horizons (pH 3.0-3.5), interstitial waters with a pH of 4.0-4.5 were found down to depths of several metres. The pH progressively increased to around pH 5.5 because of base cation desorption and the weathering of silicate minerals. High concentrations of aluminium (10-20 mg litre(-1)) and other metals (Fe, Mn, Cu, Ni, Co, Zn, Be) were found in the interstitial water in the upper unsaturated zone. Most metal concentrations were strongly pH-dependent but also reflected the geochemical characteristics of the parent sands or sandstones. H+ and trace element concentrations were slightly higher beneath areas of afforestation than beneath heathland. The downward fluxes of solutes have been estimated using rainfall-derived chloride as a non-reactive solute. The profiles retain a record of 10-20 years input allowing the past inputs from SO4 and other species to be estimated using solute/chloride ratios. Cation exchange sites are probably depleted over a period of decades and there can be a significant decrease in the unsaturated zone pH as a result of increased or sustained acidic deposition. The shallow groundwater environment (0-15 m) in non-carbonate terrains is therefore a sensitive environment where high metal concentrations may be generated and may ultimately lead to water quality problems in shallow water supplies.