Predicting Freshwater Critical Loads from Catchment Characteristics using National Datasets

Maps of freshwater critical loads are used toguide emission strategies for sulphur and nitrogen bothnationally and internationally. Water chemistry data arerequired to calculate critical loads and the production ofnational maps therefore relies on the existence of extensivechemistry datasets. However, the data required to calculatecritical loads are not readily available for all sites. Thisarticle explores how empirical statistical models mightpotentially be used to predict critical loads using nationallyavailable datasets representing a range of catchmentcharacteristics. Initially a global regression model forexplaining freshwater critical load variation across a broadspectrum of catchment types (from lowland agricultural tomountain lakes) throughout mainland Britain is described. Whenattention is focused on more specific catchment types (i.e.upland and non-arable) it is shown that the global model hasless explanatory power. A regionalisation of Great Britain(based on 100 km grid squares) shows that the global modelcannot necessarily be applied successfully within a narrowerregional context. Separate analyses were undertaken on each ofthe regional subsets using backward selection regression. Thevariables emerging as significant predictors variedsubstantially across the regions, as did the explanatory powerof the models. This was also the case when the analysis wasconfined to upland and non-arable catchments. This approachcould be developed so that critical loads assessments can bemade for populations of standing waters rather than simplythose for which water chemistry is available.     

Why Critical Loads of Acidity and N for Soils Should be Based on Pollutant Effective Concentrations Rather Than Deposition Fluxes

Numerous assumptions have been made over the past 17 years when calculating critical loads for soils, both for acidity (based upon base cation steady state mass balances (SMB)) and for N (eutrophication, based upon N mass balances), often without all the assumptions being explicitly stated. The tacit assumptions that the author believes to be implicit in the SMB approach are critically reviewed, with particular reference to upland regions where slope processes are highly significant. It is concluded that many of them cannot be justified, especially those that involve ignoring many key processes known to be important to biogeochemical cycling and soil evolution in upland catchments. The evidence presented suggests that critical loads of acidity and of N for soils should be based upon effective pollutant and, for acidity, also effective base cation deposition concentrations, rather than upon pollutant deposition fluxes. This is because of the dominant role of cation exchange equilibria, rather than weathering rate, in regulation of the pH and base status of the more acidification-sensitive soils, and because of the importance of transport down slope of base cations, alkalinity and N species.     

Critical Loads Exceedances in Germany and their Dependence on the Scale of Input Data

Critical load exceedances have been used as an effects-related parameter for guiding international air emission control negotiations. High-resolution critical load data are combined with low-resolution deposition data.This article shows that doing so systematicallyunderestimates `true' critical load exceedances as obtainedfrom combining critical load and deposition data of identicalhigh spatial resolution. 95th percentile critical loadexceedances in EMEP grids based on high resolution depositiondata are 60 and 150% higher (mean values for nutrientnitrogen and acidity, respectively) than critical loadexceedances based on the low resolution EMEP depositionmodel. The latter are used in international negotiations. Differences in individual EMEP grid squares vary betweeninsignificantly different from zero and 340%, depending onregional deposition and critical load characteristics andcritical load types (nutrient nitrogen versus acidity).Exceedances based on high-resolution deposition values arealso compared to EMEP grid averages of these values forforests only. This comparison excludes the effect ofsystematically higher depositions to forests. Still, thescale difference of (averaged, low-resolution) deposition and(high-resolution) critical loads data yields underestimatesof the 95th percentiles by on average ca. 20%.These systematic errors due to the scale dependence should beborne in mind when interpreting effects of internationalemission control measures.     

Element Removal in Harvested Tree Biomass: Scenarios for Critical Loads in Wallonia,South Belgium

The critical load concept is nowwidely used as a tool for developing emissioncontrol policies in Europe. As a signatorycountry of the Convention of Long-RangeTransboundary Air Pollution, critical loads foracidity, nutrient nitrogen, nitrogen and sulphurhave been calculated for the Flemish and Walloonregions in Belgium. This paper describes themethodology used for estimating critical loadsfor forest soils in the Walloon region accordingto the Steady-State Mass Balance equations. As anexample the methodology was applied to thecatchment `Waroneu', situated in a sensitive areaof the Haute Ardenne. Main input parameters tothe equations were derived from precipitation andrunoff data of the catchment study. Improvedestimates of nitrogen uptake (Nu) and base cationuptake (BCu) were obtained by intensive samplingof Picea abies and Quercus roburtrees. Nutrient contents (Ca, Mg, K, N) andnutrient to nitrogen ratios of Picea abiesreflected the poor soil quality at a site withhigh N deposition. Quercus robur nutrientcontents increased from stem to higher orderbranches with a high proportion of nutrientslocated in the bark. However the simulation ofstem only harvesting had a minor effect oncritical loads. Measured wood densities werelower than reported literature values with a maineffect on Nu and BCu estimates. The use ofrecommended default values and/or data derivedfrom the experimental site resulted in a widerange of critical loads, some of which werelargely overestimated. Results demonstrated theimportance of site specific data for criticalload calculations.     

Deposition Loads of Sulphur and Nitrogen in Germany

High spatial resolution maps of deposition loads in Germanyare produced as an input for abatement strategy research andfor critical loads exceedance calculations on a nationalscale. In this paper methods ofmapping total deposition loads in Germany and preliminarymaps of nitrogen and sulphur deposition loads for the year1993 are presented. A comparison of these mapping resultswith EMEP deposition mapping results has been carried out.The differences in the results of the German national and theEuropean EMEP mapping, due to different databases anddifferent methods, are quantified and discussed. Highresolution maps of deposition loads are compared to Europeanlow resolution maps on the same temporal and spatial scale,assuming that on average both should lead to similar results.However, the average differencescalculated for 23 EMEP 150 × 150 km² grid cells over Germanywere found to be 33% higher for sulphur (S) total depositionby the German method 65% higher for S dry deposition and1% lower for S wet deposition. The German results fornitrogen (N) total deposition are 2% higher than the EMEPresult 22% higher for N dry deposition and 10% lower for Nwet deposition.     

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.     

On the Calculation and Interpretation of Target Load Functions

In this study critical load functions and target load functions of nitrogen and sulphur deposition with respect to acidity and minimum base cation to aluminium ratio were calculated with the SAFE model using three different averaging strategies: (1) averaging based on current forest generation, (2) averaging based on next generation and (3) averaging based on the entire simulation period. From the results it is evident that although target load calculation and indeed critical load calculation is straight forward, there is a problem in translating a predicted recovery according to the target load calculation back to a site-specific condition. We conclude that a policy strategy for emission reductions that ensures recovery, according to calculated target load functions, is likely to be beneficial from an ecosystem point of view. However, such a strategy may not be sufficient to achieve actual non-violation of the chemical criteria throughout the seasonal or rotational variations. To address this issue we propose a method for calculating dynamic critical loads which ensures that the chosen criteria is not violated.     

Freshwater Critical Loads in Wales

The Steady State Water Chemistry (SSWC) modeland the Diatom model have been used to calculate criticalloads for acidity using annual mean chemistry for 102 acidupland streams in Wales sampled as part of the Welsh AcidWaters Survey (WAWS) in 1995. Diatom critical loads werelower than SSWC values reflecting the higher effective[ANC]_limit of the Diatom model compared to the[ANC]_limit of zero used in the SSWC model. The WAWSstream sites were all located within 41 10 × 10 km squares andeach square was assigned the lowest critical load value fromamongst the sites located within it. Comparison with valuesassigned under the UK national critical loads mappingprogramme (UKCLMAP) showed that WAWS critical loads were lowerthan UKCLMAP values in approximately 40% of squares.Differences in critical load class were variable, but exceeded2 keq ha^-1 yr^-1 in up to a maximum of seven squares.It cannot be assumed, therefore, that reducing acid depositionto the currently mapped UKCLMAP critical load will protect allstreams occurring within a given 10 × 10 km grid square inWales. The limited number of sample sites means that even inthose squares where all WAWS sites will be protected, theremay be other, more acid sensitive freshwaters with lowercritical loads. This has important implications for theinterpretation and use of critical loads data for regional andlocal environmental planning.     

Chemical and Microbiological Characteristics of Mineral Spoils and Drainage Waters at Abandoned Coal and Metal Mines

Mining is a long-established human activity. Abandonedmines, tailings, and mine spoils may have considerable impacton neighboring environments long after the sites are abandoned. Of greatest concern are derelict mines and wastes that generateacidic discharge waters that are enriched with iron and othermetals and metalloids. The chemistry and microbiology of thesesites are intricately intertwined. Whilst some indigenousmicroorganisms are responsible for accelerating sulfide mineraloxidation, thereby generating acidity and mobilizing metals,others catalyze reductive processes that essentially reversethese reactions and thereby ameliorate polluted mine waters.This article reviews current knowledge on the chemistry and microbiology of abandoned coal and metal mines, mine spoils and tailings.     

Modeling Acidification Recovery on Threatened Ecosystems: Application to the Evaluation of the Gothenburg Protocol in France

To evaluate the acid deposition reduction negotiated for 2010 within the UNECE LRTAP Gothenburg Protocol, sulphur and nitrogen deposition time-series (1880–2100) were compared to critical loads of acidity on five French ecosystems: Massif Central basalt (site 1) and granite (2); Paris Bassin tertiary sands (3); Vosges mountains sandstone (4) and Landes eolian sands (5). The SAFE model was used to estimate the response of soil solution pH and ratio to the deposition scenario. Among the five sites, critical loads were exceeded in the past at sites 3, 4 and 5. Sites 3 and 4 were still expected to exceed in 2010, the Protocol year. Further reduction of atmospheric deposition, mainly nitrogen, would be needed to achieve recovery on these ecosystems. At sites 3, 4 and 5, the delay between the critical load exceedance and the violation of the critical chemical criterion was estimated to be 10 to 30 years in the top soil and 50 to 90 years in the deeper soil. At site 5, a recovery was expected in the top soil in 2010 with a time lag of 10 years. Unexpectedly, soil pH continued to decrease after 1980 in the deeper soil at sites 2 and 5. This time lag indicated that acidification moved down the soil profile as a consequence of slow base cation depletion by ion exchange. This delayed response of the soil solution was the result of the combination of weathering rates and vegetation uptake but also of the relative ratio between base cation deposition and acid compounds.     

The Importance of Selecting Appropriate Criteria for Calculating Acidity Critical Loads for Terrestrial Ecosystems Using the Simple Mass Balance Equation

The Simple Mass Balance (SMB) equationis commonly used throughout Europe for thecalculation of acidity critical loads for forestsoils. Different criteria can be set in themodel depending on whether the receptor (e.g. treeroots) is more sensitive to the toxic effects ofaluminium or to unfavourable pH conditions. Thispaper examines the effects on critical loadscalculations of using different criteria andcritical limits, and demonstrates the importanceof selecting the most appropriate and justifiablecriteria for the chosen receptor, since they caneffect the critical loads values obtained. Abrief review of the range of different criteriaand limits used throughout Europe is included. In addition, the gibbsite equilibrium constant,used in the SMB equation to represent therelationship between dissolved aluminium andhydrogen ions in soil solution, is discussed. This relationship is not generally described inthe literature as a criterion in the equation,but this work highlights the effects differentgibbsite values have on critical loadcalculations and the importance of applying themost appropriate value for the soil in therooting zone of the receptor.     

Modelling Change in Ground Vegetation Response to Acid and Nitrogen Pollution, Climate Change and Forest Management at in Sweden 1500–2100 a.d.

The ForSAFE model, designed for modelling biogeochemical cycles (water, acidity, base cation, nitrogen and carbon) in terrestrial ecosystems, was modified with a vegetation response module (VEG), incorporating the effects of: nitrogen pollution, acidification, soil moisture, temperature, wind chill exposure, light and shading by trees, grazing by animals, competition between plants, above ground for light and below ground for water and nutrients. The model calculates the response of number ground vegetation plant groups. The integrated model was tested and validated at integrated level II forest monitoring sites across Sweden, four have been shown here, and used to assess the effect of acidification and nitrogen pollution in relation to factors such as climate change, forest management and changing grazing pressure. The response functions have been derived from single-factor experiments and integrated through the model structure for use on whole systems. The tests with the model suggest that the ground vegetation composition is reasonably well predicted, that much research remains before the model is fully tested and operational, and that the model may serve as a tool for assessing impacts of climate change, acid rain and forest management on plant biodiversity in forested areas.     

Natural and Anthropogenic Changes in The Chemistry of Six UK Mountain Lakes, 1988 to 2000

Trends have been analysed for 12 years ofchemical data from six mountain lakes in the UK AcidWaters Monitoring Network (AWMN). With minimal localanthropogenic impacts, these sites offer the bestavailable opportunity for clear identification of surfacewater chemical response to external factors, whethernatural or anthropogenic. Results indicate that naturalclimatic variations have had a major impact on lakechemistry, through fluctuations in (i) intensity ofstorms, which cause dilution of weathering-derived basecations, and/or displacement of hydrogen and aluminiumions on soil exchange sites by deposited marine basecations; and (ii) winter temperature, which is thought tobe inversely related to spring nitrate (NO₃) maxima.Both climatic factors can be linked to the North AtlanticOscillation. For the first decade of AWMN monitoringthese natural `confounding factors' to a significantextent obscured any recovery from acidification due todeclining anthropogenic sulphur deposition. However, theadditional data presented here provide strengtheningevidence for chemical recovery at a number of sites, atwhich decreases in sulphate (SO₄), acidity andlabile aluminium can now be identified. It is believedthat changes at these sensitive mountain lake sites mayherald more widespread recovery in UK surface waters aspollutant emissions decline further. However, largeincreases in dissolved organic carbon, and hence inorganic acidity, may have partially offset reductions inmineral acidity. The cause of these increases remainsuncertain, but may be linked to climatic change.     

The Use of a GIS-based Inventory to Provide a Regional Risk Assessment of Standing Waters in Great Britain Sensitive to Acidification from Atmospheric Deposition

Previous attempts to identify regions of Britain vulnerable to acidification have used sensitivity maps based on the distributionof soils, geology, and land cover across Great Britain. Additionally, a systematic survey of freshwaters undertaken as partof the U.K. critical loads mapping programme provides a regional assessment of both sensitivity (critical loads) and, in tandem withdeposition data, potential impact (critical load exceedance). Both approaches, while useful for identifying regional patterns, do not enable estimates of the number of affected water bodies to be made. Recent EU legislation (e.g., The Water Framework Directive) requires member states to set water quality objectives for all water bodies. We developed a GIS-based inventory of standing water bodies in response to the need for legislation-driven assessments of the status of the U.K. lake population. This paper describes how the inventory can be used to assess the number of standing water bodies in Britain that are vulnerable to acid deposition (at current levels), building on the sensitivity mapping undertaken previously. Using this approach, approximately 31% of all standing waters in Great Britain (excluding the Shetlands and Orkney) larger than 0.02 ha are identified as `at risk' from acidification. Higher proportions are vulnerable in Scotland and Wales. Additionally, large numbers of standing waters in areas designated for environmental protection purposes are also vulnerable.     

Cost-effectiveness Analysis of Reducing the Emission of Nitrogen Oxides in Asia

The purpose of this study is to evaluate cost-effective reduction strategies for nitrogen oxides (NO _x ) in the Asian region. The source-receptor relationships of the Lagrangian “puff” model of long-range transportation, ATMOS-N, were used to calculate the wet/dry deposition of the nitrogen (N) in Asia. Critical loads of N deposition in Asia were calculated from the relationships between the critical load of sulfur (S) and balance of N in and out using the data of S critical load of RAINS-ASIA. The cost functions of N reduction of Asian countries were derived by the regression analysis with the data of cost functions of European countries used in RAINS. In order to assess the environmental impact, the gaps between N deposition and critical load of N were calculated. The emission of NO _x was reduced in some cases of this model, and the changes of gaps between N deposition and critical load were observed as well as the changes of the reduction cost. It is shown that a uniform reduction of NO _x emissions by countries in Asia is not cost-effective strategy.     

Use of slag for dye removal

Adsorption techniques employing activated carbon have been found to be reasonably effective in the removal of some of the ionic impurities in water. However, economic considerations may require the use of inexpensive sorbents which are either naturally available or available as waste products from manufacturing processes. Slag is one such waste product obtained during the manufacture of steel, and the present study investigates dye removal characteristics of slag from colored waters. Aqueous solutions prepared from commercial grade acid, basic, and disperse dyes were used in this study, and batch pH, kinetic, and isotherm studies were undertaken on a laboratory scale. The data were evaluated for applicability to the Langmuir, Freundlich, and BET isotherm models, and the removal capacity of slag was compared with that of granular activated carbon. Results indicated approximately 94% removal of the disperse dye by slag, compared with a removal of approximately 49% achieved by activated carbon. Removal of acid dyes (dyes containing anionic groups) was reasonably good (approximately 47 and 74%), though not as good as obtained using activated carbon (approximately 100%). Column studies were conducted with a disperse dye (nonionic, slightly soluble in water), and analysis of data showed a sorption capacity of 1.3 mg of disperse dye per gram of slag. However, effluent dye concentrations were found to be higher than the permissible levels for discharge to receiving waters.     

Critical Loads of Acidity for Forest Soils: Tentative Modifications

We reviewed the current methods for calculatingcritical loads of acidity for forest soils. The consequencesof four sets of assumptions concerning the soil modelstructure, parameter values and the critical loads criterionwere explored by comparing the values of the averageaccumulated exceedance (AAE) calculated for Finland withdeposition values for the year 1995. The AAE index is given inthe unit of deposition and is a measure of how far a region isfrom being protected in terms of fulfilling a certaincriterion, taking into account the size of the ecosystem areas.Using a critical limit for the molar ratio of theconcentrations of base cations to aluminium in soil solutiongave the lowest average accumulated exceedance. Assumingorgano-aluminium complexes and leaching of organic anions gaveAAE = 4 eq ha^-1 a^-1, which was close to the valueobtained with the standard approach used in Finland, assuminggibbsite equilibrium and no leaching of organic anions,yielding AAE = 5 eq ha^-1 a^-1. With a critical basesaturation limit, instead of the concentrations criterion, theAAE index was 17 eq ha^-1 a^-1. The highest averageaccumulated exceedance (AAE = 25 eq ha^-1 a^-1),corresponding to the lowest critical load, was obtained whenthe effects-based criterion (critical concentration or criticalbase saturation) was substituted with one restricting thedeterioration of the neutralizing capacity of the soil, ANC _le(crit) = 0. These tests illustrate the variabilityof the critical load values for acidity that can be introducedby changing the criterion or by varying the calculation method,without, however, representing the extreme values of criticalloads that could be derived.     

Application of Static Critical Load Models for Acidity to High Mountain Lakes in Europe

Critical load models for acidityprovide a measure of the sensitivity of surfacewaters to acid deposition, and can be used todetermine critical load exceedance and potentiallong-term harmful effects. Three static models,the Steady-State Water Chemistry model, diatommodel and First-order Acidity Balance model, arehere applied to 11 high mountain lakes in Norway,Scotland, the Alps, the Pyrenees and the Tatras.Between five and seven of the lakes show criticalload exceedance, depending on the model used.Nitrogen as well as sulphur deposition isimportant in causing exceedance. Since soil andvegetation cover are generally sparse, geologyand lake retention time appear to be key factorsin the determination of critical load. Retentionof nitrogen is observed, but it is unclearwhether this occurs within the lake or theterrestrial part of the catchment.     

Modelling the aerobic degradation of organic wastes based on slowly and rapidly degradable fractions

Several organic wastes of major production in the world (municipal solid wastes, wastewater sludge, manures and bulking agents) and some already treated organic wastes have been investigated to determine the partition among the several fractions that compose them and their kinetics of biodegradation. Different literature models have been explored for their suitability to predict the behaviour in respiration studies of these wastes. All the models presented limitations related to their simplicity or their excessive complexity, which makes them unsuitable for reliable and fast studies at real scale. A new model based on the rapid, the slowly and the inert organic fractions has been tested for all the wastes, showing excellent correlations with actual respiration activity. Finally, the kinetic parameters for this model in its application to all the wastes studied are presented.     

Modelling of nitrogen release from MBT waste

The "LaNDy" model (landfill nitrogen dynamics model) is a new mathematical tool for the evaluation of the long-term behaviour of nitrogen in mechanical-biologically pretreated (MBP) waste. LaNDy combines a hydraulic model based on RICHARD's equation with one-dimensional heat flow in landfills, kinetics of biological degradation, gas diffusion, nitrification and denitrification. A suitable temperature-dependent N mineralisation sub-model was based on numerous data from the literature and own LSR-experiments. With the "nitrification modus" of the LaNDy model, kinetic data of nitrification, thermodynamic data of denitrification and diffusion characteristics of gaseous components (especially of oxygen and methane) are used as an additional input for the preliminary calculation of the long-time impact of nitrification and denitrification. Examples of predicted temperature distribution and leachate ammonium concentrations, using different landfill size, age of the landfill (10 to approximately 100 a) and hydraulic conductivity of the MBP waste, are presented in this paper.