Deposition of atmospheric ammonia to moorlands

Micrometeorological methods were applied to measure fluxes of atmospheric ammonia (NH3) to moorlands. Measurements were made in a wide variety of surface conditions and included both Calluna vulgaris (L.) Hull and Eriophorum vaginatum L. dominated sites. NH3 was found to deposit rapidly to all the sites investigated, providing large deposition velocities (Vd, typically 10-40 mm s(-1)) and usually minimal surface resistances (rc). A small number of measurements were made in frozen conditions and suggest a possible exception to this pattern with mean rc of 50-200 s m(-1). The effect of vegetation drying was also investigated and a possible increase in rc observed, though this was small (< 10 s m(-1)). The results are interpreted in terms of the processes controlling exchange; it is shown that NH3 deposition is predominantly to the leaf surfaces and that the net NH3 compensation point approaches zero. Annual estimates show that dry deposition of NH3 is a major source of atmospheric nitrogen to moorland ecosystems. For two typical UK sites subject to background air concentrations, NH3 dry deposition is of similar magnitude to equivalent NH4+ inputs in wet deposition. In the vicinity of emission sources, NH3 dry deposition is expected to dominate inputs of atmospheric nitrogen.     

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.     

An introduction to critical loads

The critical loads approach to emission controls of gaseous pollutants is a concept with a short but eventful history. Despite difficulties with definitions and agreed values, its acceptance within the UN-ECE Convention on Long Range Transboundary Air Pollution has provided the impetus for developing methods to put critical loads to a practical use-the revision of the UNECE emission protocols for sulphur and nitrogen. Methodologies first focus upon quantifying a pollutant threshold at which harmful effects occur on particular sensitive receptors (usually biological species). This threshold is known as the critical load for deposited pollutants, and as the critical level for gaseous pollutants acting on receptors. To calculate a critical load, biological effects are usually 'translated' to critical chemical values, e.g. harmful effects on fish 'translate' to alkalinity or aluminium concentrations in water; thus, critical load calculations may be based upon the chemistry of a system. Such calculations may be performed using simple, steady-state models, whilst the use of more complex, dynamic models provides an insight into the past and future trends. Maps of critical loads can be drawn using calculated values, and maps of pollutant deposition data will then show geographical areas where critical loads are exceeded. Spatial emission-deposition models can identify sources contributing to areas of excess loads and quantify necessary emission reductions. Optimization procedures applied to such models can derive abatement strategies related to economic costs and critical load effects. The critical load calculations may also be used to underpin the setting of target loads; these are pollutant loads, determined by political agreement, which take account of social, economic and political considerations.     

Deposition of ozone to a mature spruce forest: measurements and comparison to models

Removal of ozone at terrestrial surfaces provides a major sink for tropospheric ozone and, therefore, a constraint on the peak concentrations achieved during photochemical episodes. This study reports results from 5 years of almost continuous measurements of vertical profiles of ozone and related meteorological variables over a mature spruce forest in Bavaria. Deposition velocities calculated from flux/gradient and eddy correlation flux measurements have been compared with estimates based on a resistance model and yield satisfactory agreement during fine weather conditions. The results also suggest that biogenic emissions of reactive hydrocarbons from the forest influence the vertical profile of ozone.     

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.     

Statistical analyses of regional surface water quality in southeastern Ontario

Historical records from Ontario's Provincial Water Quality Monitoring Network (PWQMN) for rivers and streams were analyzed to assess the feasibility of mapping regional water quality patterns in southeastern Ontario which spans two major geologic zones, the Precambrian Shield and the St. Lawrence Lowlands, thus serving as a paradigm for much of Ontario. Despite biases toward the populated Lowlands and associated pollution problems, general spatial trends are evident via the analysis of intervariable relations, individual parameter maps and multivariate analysis. Using a robust algorithm designed to identify outliers and abstract underlying bivariate relations, a linear regional hardness-alkalinity relation was derived, where most anomalies proved to be mine drainage impacted sites. Regionally, multivariate ordination reveals that central tendencies of common indicators of ionic strength and nutrient richness correlate positively and that site clusters broadly reflect the transition from oligotrophic Shield waters to eutrophic conditions of heavily agricultural Lowland streams. Results suggest that on the Shield more precisely delineated aquatic regions may be realized by applying GIS to integrate river and synoptic lake survey data. Further synthesis with bedrock and surficial geology, physiography, pedology and other temporally invariant spatial attributes should yield regional patterns of background quality from which locally attainable water objectives might be defined. Additional synoptic surveys of sedimentary Lowland streams may be required as most available sites relflect anthropogenic pollution.