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'.     

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.     

Detecting the signal of atmospheric N deposition in recent national-scale vegetation change across Britain

Model estimates of NO_y and NH_x deposition across Britain for 1996 (5 km square resolution) were applied as explanatory variables to account for national-scale, fine-grained changes in plant species composition between 1990 and 1998. Plant species data were recorded from up to 27 fixed plots located within a stratified random sample of 596 1 km². The response variable was a cover-weighted Ellenberg fertility score for each plot. Analyses were carried out separately for woodlands, semi-natural grasslands and heaths/bogs. Most of the variation in the botanical response variable occurred between plots within squares and so could not be explained by the model deposition data. NH_x deposition estimates accounted for significant, but small components of between 1 km² variation in the change in Ellenberg score in grasslands (5.6%) and heath/bogs (9.8%) but not woodlands. NO_y deposition estimates were not significantly associated with vegetation change. Linear models provided the best fit and the slope of the relationship was lower for heath/bogs than grasslands. Further signal attribution at sub-kilometre square scales requires the development of fine-grained models of N deposition that can be generalised across regional sampling domains.     

Detecting the signal of atmospheric N deposition in recent national-scale vegetation change across Britain

Model estimates of NO_y and NH_x deposition across Britain for 1996 (5 km square resolution) were applied as explanatory variables to account for national-scale, fine-grained changes in plant species composition between 1990 and 1998. Plant species data were recorded from up to 27 fixed plots located within a stratified random sample of 596 1 km². The response variable was a cover-weighted Ellenberg fertility score for each plot. Analyses were carried out separately for woodlands, semi-natural grasslands and heaths/bogs. Most of the variation in the botanical response variable occurred between plots within squares and so could not be explained by the model deposition data. NH_x deposition estimates accounted for significant, but small components of between 1 km² variation in the change in Ellenberg score in grasslands (5.6%) and heath/bogs (9.8%) but not woodlands. NO_y deposition estimates were not significantly associated with vegetation change. Linear models provided the best fit and the slope of the relationship was lower for heath/bogs than grasslands. Further signal attribution at sub-kilometre square scales requires the development of fine-grained models of N deposition that can be generalised across regional sampling domains.     

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.     

Development and Application of Critical,Target and Monitoring Loads for the Management of Acid Deposition in Alberta,Canada

The Alberta, Canada acid deposition management framework, based upon the application of critical, target and monitoring loads, is described. This framework is the culmination of four years work by stakeholders brought together within Alberta's Clean Air Strategic Alliance (CASA). The elements of the framework include scientific aspects of measurement, model estimation, and monitoring of acid deposition, assessment of receptor sensitivity, and management processes to reduce emissions and deposition (should reductions become necessary). All loads are applied to grid cells measuring 1°latitude × 1° longitude, with each cell being categorized as sensitive, moderately sensitive or of low sensitivity on the basis of the sensitivities of the soil and water systems within the cell. Critical loads have been set at 0.25, 0.50 and 1.00 keq H⁺ ha^-1 yr^-1 for grid cells that are categorized as sensitive, moderately sensitive, and of low sensitivity, respectively. Target loads, the environmental management objectives, have been set at 0.22, 0.45, and 0.90 keq H⁺ ha^-1 yr^-1, and monitoring loads, a new concept in acid deposition management, have been set at 0.17, 0.35 and 0.70 keq H⁺ ha^-1 yr^-1 for the three sensitivity classes. When model prediction indicates that deposition may be exceeding the monitoring load, deposition monitoring and receptor sensitivity studies are to be initiated to confirm the deposition model prediction, and to ensure that the sensitivity of the recipient systems is understood. In this manner, management actions that occur in the event of a target load exceedance will be based upon receptor sensitivity and deposition data rather than upon model prediction alone. A process for stakeholder involvement in the evaluation of the framework and its application in long-term, long-range management of emissions and deposition is also included within the framework.     

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.     

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.     

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.     

Identification of PM10 Sources in a Mediterranean Island

Due to the dry Mediterranean climate in Cyprus, particulate matter is resuspended from soils and other surfaces. From November 2002 to August 2003, gravimetric PM₁₀ measurements were carried out at three characteristic sites (traffic, residential and rural). A significant seasonal trend with high winter concentrations was observed at the traffic site. Special events, e.g. long-range transport of Sahara dust storms, were recorded over traffic, residential and rural areas in the order of six to eight events per year, with a major frequency in summer and spring periods. This contributes to the increase of 24-h EU limit value exceedances for PM₁₀ at the three investigated sites. The origin of the PM₁₀ load was determined by enrichment factors based on analyses of the local soil deposition at the investigated sites. Furthermore, positive matrix factorisation modelling was applied to find the sources of PM₁₀. Results indicate that the major emission sources affecting the PM₁₀ load were mineral soil, sea salt, road dust, oil combustion, secondary pollutants and gasoline vehicles. The natural contribution (local mineral soil and sea salt) at the three sites was in the range of 7–9 μg m^?3 in PM₁₀. Besides the Sahara dust storms and natural background concentrations, the vehicular pollution was found as the largest contributor (12–14 μg m^?3) to PM₁₀ load at the traffic site.     

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.     

Uncertainties in Large Scale Assessments of Critical Load Exceedances

In the 1999 Gothenburg protocol to the UN/ECE LRTAP Convention andin the negotiations for an EU acidification strategy the area withexceedances of critical loads has been the preferred measure forenvironmental impacts. The aim of this study has been to assessthe influence of the uncertainty and spatial variation of both thecritical loads and deposition values on the calculated area withexceedances of critical loads. This has been done on a nationalscale for Denmark and on the European scale based on the dataincluded in the RAINS model. It is demonstrated that includinguncertainty and spatial variation in exceedance calculations, ingeneral gives larger exceeded area for the critical load ofacidity, CL(A). The picture for the critical load of nutrientnitrogen, CL_nut(N), is more mixed because of the higherproportion of exceeded areas. A further point of interest is thepossibility of validating relationships between critical loadexceedances and observable damage based on large scale monitoringand model data. It is demonstrated that it will probably not bepossible to use exceedance calculations on European scale as basisfor validation exercises, linking exceedances to observable damage.     

The Applicability of National Critical Loads Data in Assessing Designated Sites

Critical loads have been successfully used within Europe in the development of effects-based policies for pollution abatement, including the Second Sulphur Protocol and the Protocol to abate acidification, eutrophication and ground-level ozone (CLRTAP, 1979). This success has encouraged the UK Environment Agency and Conservation Agencies to use the national critical load maps as a screening tool in assessing the threats from acidification and eutrophication to designated (Natura 2000) sites. The UK maps of critical loads are based on national-scale data sets appropriate for national-scale assessments, and were never intended for use at the site-specific level. Site-based assessments are often targeted at Special Areas of Conservation, a sub-set of the UK Natura 2000 sites. The spatial data available includes the boundaries of the sites but not the location of the designated features. Ancillary data is variable from one site to another; habitat types may be described in detail with cross-reference to classes of the National Vegetation Classification (NVC: Rodwell, 1991 et seq), but information available on soils and geology is generalised and has not been related to the habitats or species being protected. Hence it can be difficult to relate the individual sites to the national maps, even where appropriate to do so. This paper examines the underlying uncertainties in the national critical load maps showing how the maps could give misleading results if used for site-specific assessments. It also includes advice on how to determine when the national data may be appropriate as a policy-tool at the site-level.     

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.     

Validating a New Model for N Sequestration in Forest Soil Organic Matter

A conceptual model for N sequestration into the terrestrial nitrogen(N) sink is presented. The model uses foliar litter-fall data, limit values for litter decomposition, and calculated N concentration at the limit value (N_limit), giving the N concentration in the hypothesized stable remains. The N_limit values were determined extrapolating a linear relationship between accumulated litter mass loss and the increasing litter N concentration to the limit value. Thesequestration rates for N in boreal forest humus were calculated and validated for a Scots pine (Pinus sylvestris L.) monocultural stand and mixed stands with Scots pine, Norway spruce (Picea abies L.), and silver birch (Betula pendula L.). The calculated stable N fraction was compared to actually measured amounts of N in humus layers that started to accumulate 2984, 2081, 1106, and 120 yr BP. Sequestration rates of N were measured to be 0.255, 0.221, 0.147, and 0.168 g m^-2 yr^-1 and modeled to be 0.204, 0.207, 0.190, and 0.190 g m^-2 yr^-1, respectively, with missing fractions being 11.0, 1.5, 30.8, and 13.3%, respectively. The more N-rich the litter, the larger was the N fraction sequestered. This was found for experimental Scots pine needle litter (n = 6) and for 53 decomposition studies, encompassing seven litter species. The amounts of N sequestered annually ranged from ca. 1–2 kg ha^-1 yr^-1 under nutrient-poor boreal conditions to about 30 kgha^-1 yr^-1 in temperate, more nutrient-rich forests.     

Particle Surface Hydrophobicity and the Dechlorination of Chloro-Compounds by Iron Sulfides

Halogenated aliphatic compounds (HACs) can be reduced by iron sulfides in aqueous systems. Generally, the thermodynamics and kinetics of dehalogenation reactions are controlled by the mineralogical and particle surface characteristics of the iron sulfide, the composition of the HAC and reaction conditions such as component concentrations, pH and Eh. In this theoretical and experimental investigation of CCl₄ and C₂Cl₆ reduction by FeS and FeS₂, the roles of hydrophobic and hydrophilic sites on the iron sulfides were analyzed. Experimental data obtained through zeta potential measurements, were used along with the Gouy-Chapman model and the simple two-layer surface complexation model to relate iron sulfide surface hydroxyl densities to the degree of HAC dehalogenation. The surface hydroxyl site densities of FeS and FeS₂ were found to be 0.11 sites/nm² and 0.21 sites/nm², respectively. During the dehalogenation reaction process, CCl₄ was found to decrease to its first intermediate product CHCl₃ within the first 20 hours followed by a slower process of conversion to CH₂Cl₂. The results also show that FeS is less hydrated (more hydrophobic) than FeS₂. For CCl₄ and C₂Cl₆, FeS is a better dehalogenator than FeS₂. These results imply that particle surface hydrophobicity is a critical factor in surface-mediated dehalogenation of chlorinated compounds.     

Nutrients Seasonal Variation and Budget in Jiaozhou Bay,China: A 3-Dimensional Physical–Biological Coupled Model Study

A 3-D biological model was developed and coupled to a hydrodynamic model, i.e., Princeton Ocean Model, to simulate the seasonal variation and budget of dissolved inorganic nitrogen, phosphate, and silicate in Jiaozhou Bay. The modeled nutrients distribution pattern is consistent with observation. Silicate, the most important limiting element for phytoplankton growth, is characterized by consumption in spring, increase in summer and autumn, and accumulation in winter, whereas dissolved inorganic nitrogen and phosphorous have increasing trend with low rates in spring, due to excessive river loads. Phytoplankton plays an important role in nutrient renewal by photosynthesis and respiration processes. During an annual cycle, 7.83 × 10³ t N, 0.28 × 10³ t P, and 3.93 × 10³ t Si are transported to the bay’s outer sea, i.e., the Yellow Sea, suggesting that Jiaozhou Bay is a significant source of nutrients for the Yellow Sea. The spatial distribution of nutrients is characterized by vertically homogeneous profiles, with high concentration inside the bay and low concentration toward the bay channel. These features are mainly governed by strong turbulent mixing, fluvial influx, water exchange rate, and Yellow Sea water intrusion. Numerical experiments suggest that the government should pay enough attention to proper layout of sewage drainage.     

Soil Respiration in Relation to Small-Scale Patterns of Lead and Mercury in Mor Layers of Southern Swedish Forest Sites

Pollution-related lead (Pb) andmercury (Hg) in mor layers of Southern Swedenmight have effects on soil biology, although inthe literature effect concentrations have beenidentified at much higher levels. Considerablesmall-scale spatial variability in heavy metalcontents and microbial respiration in mor layersof forest sites was used to calculatecorrelations that could reveal toxic effects.Negative correlations were always strongest atsites with high loads of Pb or Hg, which was considered to indicate metal toxicity. The highload sites were found in Southwestern Sweden,locally at a motorway and at a chlorine-alkalifactory. Other factors of possible influence,such as other pollutants, age of organic materialor climatic differences, would affect high andlow load sites alike. Negative correlations withrespiration were found for Pb at sites with 74 g g^-1 of mean Pb content in O_f-layer and for Hg at 0.25 g g^-1.