Critical Loads of Acidity for Surface Waters in South-Central Ontario, Canada: Regional Application of the First-Order Acidity Balance (FAB) Model

Major sulphur emission control programs have been implemented in North America, resulting in current emissions being ～30% less than those in 1980. However, the level of acidic deposition remaining is still unlikely to promote widespread recovery of aquatic ecosystems. The First-order Acidity Balance (FAB) model has been applied to south-central Ontario (285 lakes in the Muskoka River Catchment) to evaluate the need for further reductions in emissions. As a result of the past decline in deposition, the proportion of lakes with critical loads exceedance has dropped substantially; however, further reductions in sulphur and nitrogen emissions are required to eliminate critical loads exceedance. Based on bulk deposition of sulphate and nitrogen (41.1 mmol_c m^-2 yr^-1 and 62.5 mmol_c m^-2 yr^-1, respectively) for the period 1995–1999, 166 lakes (58.3%) exceedcritical loads. Even with full implementation of SO₂ abatementprograms in Canada (achieved in 1994) and the United States (legislated for 2010), critical loads will be exceeded in a large proportion (46.6%) of the study lakes.     

Modelling Acidification and Recovery of Swedish Lakes

The MAGIC model was calibrated to 143 lakes in Sweden, all of which are monitored in Swedish national monitoring programmes conducted by the University of Agricultural Sciences (SLU). Soil characteristics of the lake catchments were obtained from the National Survey of Forest Soils and Vegetation also carried out by SLU. Deposition data were provided by the Swedish Meteorological and Hydrological Institute (SMHI). The model successfully simulated the observed lake and soil chemistry at 133 lakes and their catchments. The fact that 85% of the lakes calibrated successfully without being treated in an individual way suggests that data gathered by the national monitoring programmes are suitable for modelling of soil and surface water recovery from acidification. The lake and soil chemistry data were then projected into the future under the deposition scenario based on emission reductions agreed in the Gothenburg protocol. Deposition of sulphur (sea salt corrected) was estimated to decrease from 1990 to 2010 by 65–73%; deposition of nitrogen was estimated to decrease by 53%. The model simulated relatively rapid improvements in lake water chemistry in response to the decline in deposition from 1990 to 2010, but the improvements levelled off once deposition stabilised at the lower value. There was a major improvement of simulated lake water charge balance acid neutralising capacity (ANC) from 1990 to 2010 in all lakes. The modelled lakes were divided into acidification sensitive and non-sensitive. The modelled sensitive lakes are representative of 20% of the most sensitive lakes in Sweden. By 2010, the ANC in the sensitive lakes was 10 to 50 μeq L^-1 below estimated pre-industrial levels and did not increase much further from 2010 to 2040. Soils at the majority of the modelled catchments continued to lose base cations even after the simulated decline in acid deposition was complete, i.e. after the year 2010. Based on this model prediction, the acidification of the Swedish soils will in general not be reversed by the deposition reduction experienced over the last 10 years and expected to occur by the year 2010.     

The Role of Cloud Processing in the Relationship Between Wet Deposited Sulphur and Sulphur Dioxide Emissions

It is well established that wet deposition of sulphate in the UKhas fallen by a much smaller fraction than have emissions of sulphur dioxide. Dry deposition of sulphur has decreased in proportion to the decline in emissions. A number of suggestionshave been made which offer possible explanations for this non-linearity between emissions and wet deposition. In this paper amodel of the processing of sulphur dioxide by aqueous phase cloudchemistry in a cloudy boundary layer is presented. This work doesnot simulate all the details of the mechanisms by which sulphate is incorporated into precipitation. It does, however, explorethe non-linearity of this oxidation process. It is shown that theoxidation of sulphur dioxide, in these conditions, over the UK isdominated by oxidation by ozone. The rate of sulphate productionis then controlled by the availability of the one basic trace gasin the atmosphere ammonia. Using realistic concentrations of thereacting species this is found to simulate well the observed non-linearity. The model predicts that sulphate and sulphur dioxideconcentrations will be uncorrelated in the cloudy boundary layerbut that ammonium and sulphate will be well correlated. Fieldobservations at a cloudy site in Northern England are consistentwith these predictions.     

Recovery of Acidified Lakes: Lessons From Sudbury, Ontario, Canada

Over 7,000 lakes around Sudbury, Ontario, Canada were acidified by S deposition associated with emissions from the Sudbury metal smelters and more distant S sources. Air pollution controls have led to widespread changes in damaged Sudbury lakes, including increased pH and decreased concentrations of SO₄, metals and base cations. While chemical improvements have often been substantial, many lakes are still acidified, although water quality recovery is continuing. Biological recovery has been observed in some lakes among various groups of organisms including fish, zooplankton, phytoplankton and zoobenthos. Generally, however, biological recovery is still at an early stage. Lakes around Sudbury are also showing that the recovery of acid-damaged lakes is closely linked to the effects of other major environmental stressors such as climate change, base cation depletion and UV-B irradiance. Future studies of the recovery of acid-damaged lakes around Sudbury, and in other regions, will need to consider the interactions of these and other stressors.     

A Biogeochemical Comparison of Two Well-Buffered Catchments with Contrasting Histories of Acid Deposition

Much of the biogeochemical cycling research in catchments in the past 25 years has been driven by acid deposition research funding. This research has focused on vulnerable base-poor systems; catchments on alkaline lithologies have received little attention. In regions of high acid loadings, however, even well-buffered catchments are susceptible to forest decline and episodes of low alkalinity in streamwater. As part of a collaboration between the Czech and U.S. Geological Surveys, we compared biogeochemical patterns in two well-studied, well-buffered catchments: Pluhuv Bor in the western Czech Republic, which has received high loading of atmospheric acidity, and Sleepers River Research Watershed in Vermont, U.S.A., where acid loading has been considerably less. Despite differences in lithology, wetness, forest type, and glacial history, the catchments displayed similar patterns of solute concentrations and flow. At both catchments, base cation and alkalinity diluted with increasing flow, whereas nitrate and dissolved organic carbon increased with increasing flow. Sulfate diluted with increasing flow at Sleepers River, while at Pluhuv Bor the sulfate-flow relation shifted from positive to negative as atmospheric sulfur (S) loadings decreased and soil S pools were depleted during the 1990s. At high flow, alkalinity decreased to near 100 μeq L^-1 at Pluhuv Bor compared to 400 μeq L^-1 at Sleepers River. Despite the large amounts of S flushed from Pluhuv Bor soils, these alkalinity declines were caused solely by dilution, which was greater at Pluhuv Bor relative to Sleepers River due to greater contributions from shallow flow paths at high flow. Although the historical high S loading at Pluhuv Bor has caused soil acidification and possible forest damage, it has had little effect on the acid/base status of streamwater in this well-buffered catchment.     

Use of the Dynamic Model `MAGIC' to Predict Recovery Following Implementation of the Gothenburg Protocol

Reduction of sulphur deposition causesrecovery of acidified surface waters. Processes in thecatchment delay recovery. The acidification model MAGICwas applied to the Vikedal and Tovdal rivers in southernNorway. Response in water chemsitry is delayed by 10–20 yr. The delay is due to release of old sulphate atVikedal and cation exchange at Tovdal. Assuming that theGothenburg protocol is fully implemented by the year2010, much of the predicted increase of ANC will occur inthe next 10 yr with a levelling off by about 2040. Ifnitrogen leaching increases in the future, however,recovery of ANC will not be as rapid, nor as complete.Critical load for acidity calculated by steady-statemodels is confirmed by the MAGIC predictions. Futurerequirement for mitigation measures such as liming willdecrease in the future as acid deposition decreases. Bythe year 2046 the liming requirement will be reduced byabout 45% at Vikedal and 65% at Tovdal. One of the mainpurposes of the Norwegian national monitoring programmeis to provide documentation of changes in environmentalquality due to long-range transported air pollutants.Modelling applications such as this clearly show that thedata fill this purpose.     

Reconstruction of Long-Term Changes in Lake water Chemistry,Zooplankton and Benthos of a Small,Acidified High-Mountain Lake: Magic Modelling and Palaeolimnogical Analysis

Starolesnianske pleso is a small and shallow acid lake in the High Tatra Mountains, situated at 2000 m above sea level, on granitic bedrock, with sparse and thin soil cover. When detailed measurements began in the 1980s Starolesnianske pleso had pH below 5 and only one species of cladoceran zooplankton, the ubiquitous Chydorus sphaericusPalaeolimnological investigations show changes in cladoceran zooplankton and chironomid zoobenthic assemblages since about 1920 and a major change in 1970–1980. The dynamic acidification model MAGIC was used to reconstruct changes in water chemistry over the past 150 years. The results from MAGIC agree well with the sediment record; pH levels gradually decreased from 6.5 in the mid-1800s to about 5.6 in 1920 (first response in biota) to below 5.0 by 1970, and concentrations of inorganic aluminium rose dramatically beginning about 1960. In the 1990s the lake water chemistry showed clear signs of reversal in acidification brought about by a major decline in S deposition.     

Nitrate Leaching from Moorland Soils: Can Soil C:N Ratios Indicate N Saturation?

Links between forest floor carbon:nitrogen (C:N) ratios, atmospheric N deposition and nitrate leaching into surface waters have been reported for forest ecosystems, but similar studies have not been reported previously for the equivalent compartments of moorland ecosystems in Great Britain, despite the importance of nitrate in contributing to the acidification of moorland streams and lakes in British uplands. In this paper, the relationships between the C:N ratio of moorland soil surface organic matter, N deposition, and nitrate leaching are explored for 13 soils in four moorland catchments. Although there is spatial variability in the C:N ratio of soils, major differences are apparent between soils and especially between catchments. The C:N ratio appears to be inversely related to modelled inorganic N deposition and, to a lesser degree, measured nitrate leaching, for three of the four catchments studied (Allt a'Mharcaidh, Afon Gwy, and Scoat Tarn). Nitrification may make an important contribution to nitrate leaching at the two higher deposition sites. At the fourth site, the heavily acidified River Etherow catchment, extremely high rates of nitrate leaching are not accompanied by low C:N ratios or high nitrification potentials in the upper soil horizons. Hence the C:N ratio of surface soil organic matter may have potential as an indicator of nitrogen saturation and leaching in some systems, but it is not universally applicable.     

Acidification at Plastic Lake,Ontario: Has 20 Years Made a Difference?

In response to reduced sulphur emissions, there has been a large decrease in sulphate (; −0.97 μeq l⁻¹ year⁻¹) and hydrogen (−1.18 μeq l⁻¹ year⁻¹) ion concentration in bulk precipitation between 1980 and 2000 at Plastic Lake in central Ontario. The benefit of this large reduction in deposition on stream water chemistry was assessed using the gauged outflow from a conifer-forested catchment (PC1; 23.3 ha), which is influenced by a small wetland located immediately upstream of the outflow. Sulphate concentrations declined, but not significantly due to large inter-annual variation in concentration. Between 1980 and 2000, there were significant increases in dissolved organic carbon, ammonium and potassium concentration likely reflecting increased mineralisation in the wetland. Calcium concentrations in PC1 decreased during the two decade period (−2.24 μeq l⁻¹ year⁻¹), as a consequence there was no improvement in stream pH and the Ca:Al ratio in PC1 continued to decline. A similar response was noted in an upland-draining sub-catchment of PC1-08 that has been monitored since 1987. Despite large reductions in deposition and almost complete retention of nitrogen in soil, there has been no improvement (in terms of pH) in stream water at PC1 due to a combination of soil acidification and climatic (droughts, increased mineralisation) perturbations.     

Incorporation of Seasonal Nitrogen Dynamics within a Long-Term Acidification Model

This paper describes an application of the long termdynamic model, MAGIC, on a monthly timestep, enablingincorporation of the seasonal dynamics associated with abroad understanding of the ecosystem N cycle. The modelhas been applied to the Dargall Lane catchment in theGalloway region of Scotland where marked seasonal Ndynamics are apparent. Mean monthly proportions ofrainfall, runoff, deposition fluxes and net retention ofN are utilised to drive the model on a monthly timestep.Calibration of the model has successfully reproduced thepresent day observed seasonal variation in streamNO₃ and ANC. Prediction of recovery at the siteunder the second sulphur protocol indicates that,although mean annual ANC increases, mean monthly ANC doesnot rise above zero for all months of the year until2010.     

Satellite and Ground Based Monitoring of Aerosol Plumes

Plumes of atmospheric aerosol have been studied using a rangeof satellite and ground-based techniques. The Sea-viewing WideField-of-view Sensor (SeaWiFS) has been used to observe plumesof sulphate aerosol and Saharan dust around the coast of theUnited Kingdom. Aerosol Optical Thickness (AOT) was retrievedfrom SeaWiFS for two events; a plume of Saharan dusttransported over the United Kingdom from Western Africa and aperiod of elevated sulphate experienced over the Easternregion of the UK. Patterns of AOT are discussed and related tothe synoptic and mesoscale weather conditions. Furtherobservation of the sulphate aerosol event was undertaken usingthe Advanced Very High Resolution Radiometer instrument(AVHRR). Atmospheric back trajectories and weather conditionswere studied in order to identify the meteorologicalconditions which led to this event. Co-located ground-basedmeasurements of PM₁₀ and PM_2.5 were obtained for 4sites within the UK and PM_2.5/10 ratios were calculatedin order to identify any unusually high or low ratios(indicating the dominant size fraction within the plume)during either of these events. Calculated percentiles ofPM_2.5/10 ratios during the 2 events examined show thatthese events were notable within the record, but were in noway unique or unusual in the context of a 3 yr monitoringrecord. Visibility measurements for both episodes have beenexamined and show that visibility degradation occurred duringboth the sulphate aerosol and Saharan dust episodes.     

Assessing the use of poplar tree systems as a landfill evapotranspiration barrier with the SHAW model.

The use of poplar tree systems (PTS) as evapotranspiration barriers on decommissioned landfills is gaining attention as an option for leachate management. This study involved field-testing the Simultaneous Heat and Water (SHAW) model for its ability to reliably estimate poplar transpiration, volumetric soil water content, and soil temperature at a landfill located in southern Ontario, Canada. The model was then used to estimate deep drainage and to ascertain the influence of a young PTS on the soil water balance of the landfill cover. The SHAW model tended to underestimate poplar transpiration [mean difference (MD) ranged from 0.33 to 3.55 mm on a daily total basis] and overestimate volumetric soil water content by up to 0.10 m3 m(-3). The model estimated soil temperature very well, particularly in the upper 1 m of the landfill cover (MD ranged from -0.1 to 1.6 x degrees C in this layer). The SHAW model simulations showed that deep drainage decreased appreciably with the presence of a young PTS largely through increased interception of rainfall, and that PTS have a good potential to act as effective evapotranspiration barriers in northern temperate climate zones.     

Integrated Nitrogen and Flow Modelling (INCA) in a Boreal River Basin Dominated by Forestry: Scenarios of Environmental Change

A new version (v1.7) of the Integrated Nitrogen in CAtchments model(INCA) was applied to the northern boreal Simojoki river basin (3160 km²) in Finland. The INCA model is a semi-distributed, dynamic nitrogen (N) process model which simulates N transport and processes in catchments. The INCA model was applied to model flow and seasonal inorganic N dynamics of the river Simojoki basin over the period 1994–1996, and validated for two more years. Both calibration and validation of the model were successful. The model was able to simulate annual dynamics of inorganic N concentrations in the river. The effects of forest management and atmospheric deposition on inorganic N fluxes to the sea in 2010 were studied. Three scenarios were applied for forestry practices and two for deposition. The effects of forest cutting scenarios and atmospheric deposition scenarios on inorganic N flux to the sea were small. The combination of the maximum technically possible reduction of N deposition and a decrease of 100% in forest cutting and peat mining areas decreased NO₃ ^--N flux by 6.0% and NH₄ ⁺-N flux by 3.1%.     

Conflicting processes in the wetland plant rhizosphere: Metal retention or mobilization?

Increasingly wetlands are used for treatment of metal-contaminated water or as a cover over metal-enriched mine tailings. Natural wetlands may also be contaminated with metals from anthropogenic sources. While wetland conditions tend to be favorable for immobilization of metals, wetland plants could influence metal mobility through redox and pH processes in the rhizosphere. Our current knowledge of these processes is reviewed, focusing on the question of whether the advantages of growing wetland plants in metal-contaminated sediments outweigh the disadvantages. Wetland plants alter the redox conditions, pH and organic matter content of sediments and so affect the chemical speciation and mobility of metals. Metals may be mobilized or immobilized, depending on the actual combination of factors, and it is extremely difficult to predict which effects plants will actually have on metal mobility under a given set of conditions. However, while the effects of plants can extend several tens of centimeters into the sediments, there are no reports suggesting large-scale mobilization of metals by wetland plants.     

The GANE Roof Project: The impact of reduced N & S deposition and experimental warming in an acid grassland

A field-based system used to quantify the response of acid grassland to reduced atmospheric nitrogen and sulphur deposition, and to investigate the effects of elevated soil temperature on acid grassland development is described. The system is based on 12 retractable roofs, covering undisturbed experimental plots of acid grassland and three controls. Nine roofs are used to exclude natural precipitation and three roofs used to retain emitted IR radiation at night. An irrigation system has been developed to simulate natural precipitation, allowing for the application of specific treatment regimes of ambient, reduced nitrogen and reduced nitrogen/sulphur deposition beneath the nine rain exclusion plots. Plant, soil parameters, leachate chemistry and gaseous fluxes are being monitored and initial results on soil water chemistry are described. Warming appeared to enhance nitrate concentrations in soil water but this was not sustained beyond the first year of treatment. In contrast, the deposition reduction treatments decreased soil water nitrate concentrations within a few weeks of reducing deposition. This was not observed for other solutes such as sulphate or ammonium suggesting a more direct link between deposition of nitrate and leaching losses.     

The GANE Roof Project: The impact of reduced N & S deposition and experimental warming in an acid grassland

A field-based system used to quantify the response of acid grassland to reduced atmospheric nitrogen and sulphur deposition, and to investigate the effects of elevated soil temperature on acid grassland development is described. The system is based on 12 retractable roofs, covering undisturbed experimental plots of acid grassland and three controls. Nine roofs are used to exclude natural precipitation and three roofs used to retain emitted IR radiation at night. An irrigation system has been developed to simulate natural precipitation, allowing for the application of specific treatment regimes of ambient, reduced nitrogen and reduced nitrogen/sulphur deposition beneath the nine rain exclusion plots. Plant, soil parameters, leachate chemistry and gaseous fluxes are being monitored and initial results on soil water chemistry are described. Warming appeared to enhance nitrate concentrations in soil water but this was not sustained beyond the first year of treatment. In contrast, the deposition reduction treatments decreased soil water nitrate concentrations within a few weeks of reducing deposition. This was not observed for other solutes such as sulphate or ammonium suggesting a more direct link between deposition of nitrate and leaching losses.     

Neutralisation of Sulphur Dioxide Deposition in a Coniferous Canopy

Previously, it has been observed that the internal circulation (ion leakage) of calcium from a coniferous forest is caused by uptake of sulphur dioxide (SO₂). Here we show that this correlation was not changed when the forest floor is covered with a roof. The reaction takes place in the canopy and is not influenced by deposition and root uptake of calcium and sulphate. The ion leakage of calcium is linked to the loss of acidity in throughfall. The process can, for one of the catchments, schematically be written: SO₂ + H₂O + 0.5 O₂ + 0.58 CaA₂→ SO₄ ^2- + 0.94 H⁺ + 0.58 Ca²⁺ + 1.16 HA, in which A denotes the anion to a weak acid. This reaction also takes place today when the SO₂ concentration is very low, but when the precipitation is still acidic. The ion leakage of manganese also is caused by the uptake of SO₂, but only 0.12 manganese ions are released per SO₂ molecule.     

Chlorinated Solvent Treatment Wetland

A first‐of‐its‐kind wetland restoration project was completed in October 2000 to treat trichloroethene‐(TCE‐)impacted groundwater from a former manufacturing facility prior to discharge into a highly valued recreational surface water body in the upper Midwest. This article summarizes the design, construction, operation, and effectiveness of the restored wetland. The groundwater‐surface water discharge zone at the site was restored as a wetland to improve the natural degradation of TCE and subsequent degradation by‐products. For the past 11 years, the treatment wetland performance was evaluated by monitoring the wetland vegetation, wetland hydraulics, and water chemistry. Water quality data have been used to assess the wetland geochemistry, TCE and TCE‐degradation by‐product concentrations within the wetland, and the surface water quality immediately downgradient of the wetland. The treatment wetland has been performing according to design, with TCE and TCE‐degradation by‐products not exceeding surface water criteria. The monitoring results show that TCE and TCE‐degradation by‐products are entering the treatment wetland via natural hydraulic gradients and that the geochemistry of the wetland supports both reductive dechlorination (anaerobic degradation) and cometabolic degradation (aerobic degradation) of TCE and TCE‐degradation by‐products: cis‐ and trans‐1,2‐dichloroethene and vinyl chloride. © 2013 Wiley Periodicals, Inc.     

Uncertainties in Predictions of Surface Water Acidity using the MAGIC Model

In this study, we have used the MAGIC model together with data from the Birkenes catchment in Norway, at which 27 years of data (1974–2000) are available. We calibrated the MAGIC model to the five year observed average chemistry around 1990, and then used the data from the five year period around 1980 to refine the calibration. From 1990, forecasts were run for the different sets of inputs and parameters, and the sets of inputs and parameters were further refined using observations for the period 1996–2000. Through an automatic calibration routine, the model was calibrated a large number of times with different sets of input data to account for the uncertainties in the observed data using a Monte Carlo set-up. The results show that the uncertainty in the model predictions decreases as more observed data from different points in time are used in the model calibration. The results also show that when usingthe time series data in calibration, the distribution of the forecastchanged. The distribution of the predicted Acid Neutralisation Capacity (ANC) in the future is lower for the more refined model calibration. The 10 and 90 percentiles of predicted ANC in 2010 are –3 to 21 μeq L^-1 when only a five-year average is used for calibration, but are –7 to 9 μeq L^-1 when data from the three different time periods are used.     

Use of Natural 35S to Trace Sulphate Cycling in Small Lakes,Flattops Wilderness Area,Colorado, U.S.A.

Measurements of the cosmogenically-produced ³⁵S, a radioisotope of sulphur (t_1/2 = 87 days), are reported for the Ned Wilson Lake watershed in Colorado. The watershed contains two small lakes and a flowing spring presumed to be representative of local ground water. The watershed is located in the Flattops Wilderness Area and the waters in the system have low alkalinity, making them sensitive to increases in acid and sulphate deposition. Time series of ³⁵S measurements were made during the summers of 1995 and 1996 (July–September) at all three sites. The system is dominated by melting snow and an initial concentration of 16–20 mBq L^-1 was estimated for snowmelt based on a series of snow samples collected in the Rocky Mountains. The two lakes had large initial ³⁵S concentrations in July, indicating that a large fraction of the lake water and sulphate was introduced by meltwater from that year's snowpack. In 1995 and 1996, ³⁵S concentrations decreased more rapidly than could be accounted for by decay, indicating that other processes were affecting ³⁵S concentrations. The most likely explanation is that exchange with sediments or the biota was removing ³⁵S from the lake and replacing it with older sulphate devoid of ³⁵S. In September of 1995 and 1996, ³⁵S concentrations increased, suggesting that atmospheric deposition is important in the sulphate flux of these lakes in late summer. Sulphur-35 concentrations in the spring water were highly variable but never higher than 3.6 mBq L^-1 and averaged 2 mBq L^-1. Using a simple mixing model, it was estimated that 75% of the spring water was derived from precipitation of previous years.