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.     

Investigating the Uncertainties in the Simple Mass Balance Equation for Acidity Critical Loads for Terrestrial Ecosystems in the United Kingdom

The Simple Mass Balance (SMB)equation has been developed and used as one ofthe principal methods for calculating criticalloads of acidity for forest ecosystems. Criticalloads have formed the basis for informing policyrelated to the control and abatement of emissionsof acidifying pollutants. The SMB equationrelies on a variety of assumptions and dataderived from a variety of sources. Each of thesecomponent constituents has a potential source oferror depending on the method(s) used for theirderivation and the value(s) assigned. The resultis the possibility of generating a range ofcritical load values for a single ecosystem. This paper summarises the SMB equation, examinesthe uncertainties in deriving input values andreviews other works on the key assumptions.     

The Link Between the Exceedance of Acidity Critical Loads for Freshwaters,Current Chemical Status and Biological Damage: A Re-Interpretation

Critical loads have for several years been employed bypolicymakers to aid in the development of strategies for aciddeposition abatement. They provide an effects-based approachwhereby an acid deposition flux greater than the critical load(known as critical load exceedance) implies that long-termharmful effects on a selected target organism will occur.Implicit in this approach are two assumptions: first, theexceedance of a critical load will harm the target organism,and second, the severity of biological impact is related to themagnitude of exceedance. However, static models give noindication of when the predicted damage might occur. One suchmodel, the Steady-State Water Chemistry (SSWC) model, employs aseries of empirical relationships to derive the pre-industrial,baseline leaching rate of base cations from measured waterchemistry using the so-called `F-factor'. The SSWC model setsthe critical load relative to pre-industrial base cationleaching (a permanent buffer of acid deposition) and a selectedacid neutralizing capacity (ANC) value which corresponds with aknown likelihood of damage to a biological target organism.Here we interpret the meaning of critical load exceedance as aprediction of steady-state ANC, and explore the relationshipbetween exceedance of the critical load and current chemistry. We demonstrate that a critical loadexceedance with the SSWC model does not necessarily indicatethat the critical chemical threshold (zero ANC) has alreadybeen crossed, and there may be no correlation betweenexceedance and biological status. A reformulation of the SSWCmodel is proposed which provides a direct link between currentdeposition and current chemical conditions, and is thereforemore likely to indicate current biological damage. Thereformulation illustrates the discrepancy between currentchemical status and that predicted by the SSWC model atsteady-state, which is a function of the `F-factor'.     

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.     

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.     

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.     

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.     

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.     

Using Multiple Chemical Criteria for Critical Loads of Acidity in Maritime Regions

Critical loads have become a well-establishedpart of the work programme of the UnitedNations Economic Commission for Europe (UNECE) Conventionon Long-Range Transboundary Air Pollution (CLRTAP). Thelinking of ecosystem response to deposition level is thecentral principal of the critical loads approach. Foreach ecosystem, a biological indicator is chosen, asuitable chemical criterion selected and a criticalchemical limit assigned. The Bc:Al ratio is the mostwidely used chemical criterion for setting criticalloads. However, critical loads based on this criterionare very sensitive to marine deposition. In regions whichreceive high depositions of marine-derived base cations,such as the Republic of Ireland (ROI) and the UnitedKingdom (UK), critical loads based on the Bc:Al criterionwill inevitably be high. Therefore, it is proposed thatcritical loads are estimated using multiple chemicalcriteria with appropriate critical limits to protect thechosen biological indicators. The range of publishedchemical criteria have been applied to the ROI and theUK. The chemical criterion corresponding to the mostsensitive critical load have been mapped and thecontribution of each to the final maps investigated. Thesimulations indicate that the most sensitive criteria forsetting critical loads are based on specifying critical Hor Al concentrations. However, the choice of critical limits andmodel parameters will ultimately effect the criticalloads. Therefore, it is important that appropriate criticallimits are chosen to protect the biological indicator andreceptor ecosystem from long-term damage.     

A Novel Method for Mapping Critical Loads Across a River Network: Application to the River Dart,Southwest England

To date, estimates of freshwater critical loads have beenbased on a single sample site within a given area, in theUK the `most sensitive' surface water in each 10 km gridsquare. The critical loads obtained are thus highlydependent on the sites chosen, and at a relatively coarsespatial resolution. To produce a higher resolutioncritical load assessment, the PEARLS (Prediction ofAcidification and Recovery on a Landscape Scale)procedure has been used to estimate critical loads acrossa large (248 km²), partially acid-sensitivecatchment in Southwest England. PEARLS utilises availablesoils and land-use databases, and sampled streamchemistry data, to derive characteristic runoffcompositions for a set of landscape types. Mixingequations are then used to calculate runoff chemistry,and subsequently critical loads, throughout the streamnetwork. Results show major spatial variability, withcritical loads lowest in streams draining peat-moorlandheadwaters, and generally increasing downstream asagricultural land contributes an increasing proportion ofrunoff. The 5th percentile freshwater critical loadfor the catchment is estimated at 0.29 keq H⁺ ha^-1yr^-1,and critical loads are exceeded for around 40% of totalstream length. The PEARLS methodology provides a novelopportunity to assess the spatial variability infreshwater critical loads, and to provide estimates ofexceedance at whole catchment scale. It has potentialapplication in the assessment of surface watersensitivity to acidification across wider areas in the UKand elsewhere.     

The Role of Mineral Weathering Rate Determinations in Generating Uncertainties in the Calculation of Critical Loads of Acidity and their Exceedance

Current legislation within Europe aimed at limitingecosystem damage resulting from inputs of atmosphericpollution is based on the critical load concept. Mineralweathering rates are central to the calculation ofcritical loads (acceptable levels) of acid deposition.The authors have undertaken a number of studies whichillustrate the complications and limitations inherent inpredicting mineral weathering rates and the implicationswhich these have for critical loads calculations andmapping. Calculated weathering rates and critical loadsfor two acid-sensitive parent materials (greywackes andgranites) are presented and are used to illustrate theimpact that uncertainty can have on critical loadexceedances. The results have obvious implications forportraying the uncertainties of critical loads to policy makers.     

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 and Exceedances of Acid Deposition and Associated Forest Growth in the Northern Hardwood and BorealConiferous Forests in Québec,Canada

We used the Québec forest monitoring network (`Réseaud'Étude et de Surveillance des Écosystèmes Forestiers' or RESEF)along with its atmospheric monitoring stations to assess criticalS and N loads and their combined soil acidification exceedancesfor natural ecosystems of the northern hardwood and borealconiferous forests in Québec, Canada. Critical loads (CL) forforest soil acidification were calculated using the simple mass-balance (SMB) approach and with the steady-state PROFILE model.Atmospheric deposition rates for water, S, N, Ca, Mg, Na, and K,for the years 1989–1993, and detailed, plot-specific forest andsoil characteristics were used as input. The SMB model alsorequired information regarding nutrient uptake and storage in theaboveground woody biomass. The CL calculations indicated that,from the 31 RESEF plots, 18 received atmospheric acidic inputs inexcess of their CL (55 and 61% of the hardwood and coniferousplots, respectively). The range of CL exceedance varied from 60to 470 eq ha^-1 yr^-1 for the hardwood stands, and from 10to 590 eq ha^-1 yr^-1 for the coniferous stands. The standswith CL exceedance were mainly located in the western and centralpart of the province. Stand growth associated with exceedanceclass of acidity was determined using the RESEF plots along withselected permanent forest survey plots having similar sitecharacteristics, but for which longer growth records wereavailable. We found a significant negative correlation betweenforest growth rates and critical soil acidification exceedancefor both the northern hardwood and the boreal conifer sites.Specifically, plots with critical load exceedances were found tohave a growth reduction of about 30% during the 1974–1982 andthe 1972–1990 measurement (plots with no soil acidificationexceedance served as a control). While this correlation is notnecessarily causal, it is nevertheless consistent with theexpectation that increased losses of soil base cations on accountof increased soil acidification should and could lead todeteriorating forest health conditions.     

Chemical and biological extraction of metals present in E waste: A hybrid technology

Management of metal pollution associated with E-waste is widespread across the globe. Currently used techniques for the extraction of metals from E-waste by using either chemical or biological leaching have their own limitations. Chemical leaching is much rapid and efficient but has its own environmental consequences, even the future prospects of associated nanoremediation are also uncertain. Biological leaching on the other hand is comparatively a cost effective technique but at the same moment it is time consuming and the complete recovery of the metal, alone by biological leaching is not possible in most of the cases. The current review addresses the individual issues related to chemical and biological extraction techniques and proposes a hybrid-methodology which incorporates both, along with safer chemicals and compatible microbes for better and efficient extraction of metals from the E-waste.     

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.     

Uncertainty in Estimation of Wet Deposition of Sulphur

A model is described for predicting wet deposition ofsulphur in Britain from rainfall and site measurementsof ion concentration in precipitation. This modelincludes orographic enhancement of both rainfall andion concentration. The model output is comparedagainst available measurement data. Sensitivity anduncertainty analyses are used to predict the outputuncertainty. If the stated assumptions can be shown tobe correct, the wet deposition for Britain at the 5 kmscale is accurate to ±35% across the country. Theanalyses show a larger uncertainty in central Englandand a possible bias towards underestimation of wetdeposition, the latter being of importance incalculating critical load exceedances in remote areas.     

无患子皂苷与柠檬酸协同洗脱污染土壤中镉铅

以某废弃铅锌矿区重金属污染土壤为研究对象,采用无患子皂苷与柠檬酸(CA)协同洗脱污染土壤中的Cd和Pb.以无患子果皮投加量为20 g/L所得水浸提液和浓度为0.3 mol/L的CA配制复配淋洗剂.在浸提液中添加CA后,能有效提高对土壤中Pb的去除率.在浸提液和CA的体积比为1:3、淋洗剂pH为5、淋洗时间为12.0 h...     

Comparison of batch leaching tests and influence of pH on the release of metals from construction and demolition wastes

Construction and demolition wastes are suitable for use in road construction. However, leaching characterization of recycled materials is required to determine their pollutant potential and the consequence of their application in different scenarios. The motivation of this paper is derived from the increasing use of different leaching test methods. In Europe, the confusion resulting from the wide variety of tests used to evaluate environmental properties of construction materials implies that an evaluation of the current practices and the attempt to consolidate the approaches are required.Two equilibrium-based leaching tests (the Dutch test and the European standard) were conducted to assess the environmental impact of four recycled aggregates. Three natural limestone aggregates were used as controls. Both tests measure the potential release of hazardous elements under extreme conditions using different leaching parameters (L/S ratio, pH value and contact time). The results proved that pH is the most relevant factor on the assessment of the differences between leaching methods due to its strong control on the pollutant release.To classify the materials according to their environmental effects, the concentration limit values of the metals imposed by Council Decision 2003/33/EC were used as a reference. The comparison allowed the classification of the recycled aggregates as inert wastes, with the exception of the MR-2 aggregate, which was classified as non-hazardous material.     

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.     

Long-term leaching test of incinerator bottom ash: evaluation of Cu partition

Two types of leaching tests were performed on the bottom ash from municipal solid waste incinerators. A short-term batch test specified by the America Nuclear Society (ANS) and long-term column tests with acetic acid (pH 5.2) as leaching solution were used to evaluate copper leachability. The Cu leaching after the 5-d ANS test is about 1% of the original Cu content of 5300 mg/kg. Upon addition of a stabilizing agent, the Cu leaching quantity is reduced; the extent of reduction depends on the type of chemical used (phosphate, carbonate and sulfide). The 1.6% Na(2)S addition showed negligible Cu leaching, and Na(2)S was, therefore, used in subsequent column tests. The 30-d column test indicates a steady increase of Cu leaching amount with time and reaches about 1.5% of the original Cu content after 30 d. A 180-d column test further increased the Cu leaching to about 5.1% of the original Cu content, whereas no appreciable Cu leaching was found with the addition of 1.6% Na(2)S. A sequential extraction was conducted on the raw ash, ash with the addition of Na(2)S and the residue ash after 30 d of operation to characterize Cu affinity for different solid fractions. The data were used to evaluate the fate of Cu through these interactions.