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.     

Responses of microbial populations in the rhizosphere to deposition of simulated acidic rain onto foliage and/or soil

Air pollutants or some chemicals applied to plant foliage can alter the ecology of the rhizosphere. Experiments were conducted to distinguish among possible foliage-mediated versus soil- or root-mediated effects of acid deposition on microorganism in the rhizosphere. Seedlings of a sorghum x sudangrass hybrid in pots of non-sterile soil-sand mix in a greenhouse were exposed to simulated rain solution adjusted with H2SO4 + HNO3 to pH 4.9, 4.2, 3.5 or 2.8. Solutions were applied as simulated rain to foliage and soil, foliage only (soil covered by plastic, and deionized water applied directly to the soil), or soil only (solution applied directly to the soil). Solutions were applied on 16 days during a 6-week period (1.5 cm deposition in 1 h per application). Plant shoot and root dry weights and population densities of selected types of bacteria, filamentous actinomycetes and fungi in the rhizosphere were quantified after exposures were completed. Deposition of simulated acidic rain onto foliage alone had no effect on plant biomass or microbial population densities in the rhizosphere (colony-forming units per gram of rhizosphere soil). However, plant growth was stimulated and all microbial populations in the rhizosphere increased 3- to 8-fold with increased solution acidity (relative to pH 4.9 solution) when solution penetrated the soil. Statistical analyses indicated that the acid dose-population response relationships for soil-only and foliage-and-soil applications were not different. Thus, no foliage-mediated effect of simulated acidic rain on rhizosphere ecology was detected.     

Response of the Plastic Lake catchment, Ontario, to reduced sulphur deposition

As a consequence of decreases in the emission rate of sulphur in eastern North America in the late 1970s and early 1980s, sulphate deposition in central Ontario declined by about 40%, but has remained constant for about six years. Plastic Lake, a small, dilute lake on the Precambrian shield that the authors have studied since 1979, acidified between the start of the study and about 1986, but since then has not changed. The authors also monitored the chemistry of streamwater draining the Plastic Lake catchment. Water quality of runoff from an upland site improved rapidly (pH and alkalinity increased, SO4(2-) and Al decreased), but two factors offset these improvements. A small wetland area downstream reversed most of these changes, resulting in a constant output of strong acid from the catchment. In addition, in extremely dry years (1983, 1987, 1989) there were very high concentrations of SO4(2-) in the streamwater, suggesting substantial re-oxidation of reduced S in the catchment.     

Comparative impacts of forest harvest and acid precipitation on soil and streamwater acidity

Annual H+ budgets were calculated for a catchment with a 65-year-old spruce-fir forest, and for an adjacent catchment at three years after a whole-tree harvest. In the harvested catchment sinks for H+ due to weathering and mineralization reactions were 85% greater, and sources of H+ due to biomass uptake were 60% greater than in the undisturbed catchment. There was an overall net consumption of 550 eq H+ ha(-1) year(-1) at year 3 after harvest compared to a net generation of 520 eq H+ ha(-1) year(-1) for the 65-year-old forest. Soil pH increased by 0.2-0.4 units soon after harvest, but there was little change in pH of streamwater from the harvested watershed. The whole-tree harvest resulted in a total production of about 30,000 eq H+ ha(-1) due to biomass removal. In contrast, wet and dry deposition at rates measured in this study could add more than 50,000 eq H+ ha(-1) in the 65-year period before the next harvest. Reducing the intensity of harvest may lessen long-term impacts of these sources of H+ on acidification of soils and streams.     

Food aid and food crisis in Sub-Saharan Africa: Statistical trends and implications*

This paper documents the rapid expansion and changes in food aid flows to Sub-Saharan Africa up to mid-1985. Trends for Sub-Saharan Africa as a whole and for the more seriously affected countries are examined, as are the comparative experiences of food aid of individual countries in the region. Table 11 lists the Sub-Saharan African countries and indicates the most seriously affected food-short countries, as defined by the WFP/FAO task force. It should be borne in mind that some practical problems exist in compiling data on food aid. These include lack of availability of reliable data, especially of most recent data; lack of common terminology and definitions; and different accounting systems. These data problems are sometimes a source of confusion. However, the basic facts are clear: food aid gradually emerged during the early 1980s as a resource too often of considerable significance to many countries of Sub-Saharan Africa. These trends were only accelerated with the crisis of 1984-1985. These facts provide a point of reference for further analysis of the sources of the crisis, its actual dimensions and consequences.