Modelling future soil chemistry at a highly polluted forest site at Istebna in Southern Poland using the "SAFE" model

The multi-layer dynamic model SAFE was applied to the forested catchment Istebna (Southern Poland), to study recovery from acidification. Environmental pollution in the area has been historically high. The model uses data from an intensive monitoring plot established in 1999 in a spruce stand, which was planted in 1880. Observations showed that the soil was depleted of base cations. The measured base saturation in 1999 was between 5 and 8% in the different soil layers. Model predictions assuming full implementation of the UNECE 1999 Gothenburg Protocol and present day base cation deposition show that the base saturation will slowly increase to 20% by 2100. Despite large emission reductions, Istebna still suffers from the very high loads of acidifying input during the past decades. Soil recovery depends on future emissions especially on base cation deposition. The recovery will be even slower if the base cation deposition decreases further.     

Acid-sensitive waters of the English Lake District: a steady-state model of streamwater chemistry in the upper Duddon catchment

Data on deposition and streamwater chemistry, obtained for the upper catchment of the River Duddon in the 1970s and 1980s, are reviewed. These data, together with soil chemical data, are used to deduce key processes in the deposition-catchment interaction, the analysis being based on current concepts of acidification. The processes are incorporated into a steady-state model that allows streamwater compositions to be calculated. The large baseflow pH range (5-7) of Duddon streams is accounted for in the model by a range of base cation weathering rates. Other processes invoked are evapotranspiration, the uptake of nitrogen by plants, dissolution of Al(OH)(3) in the mineral soil, precipitation of Al(OH)(3) in the baserock zone and in streamwater, Al(3+) hydrolysis, and reactions of the carbonate system. Both cation exchange and sulphate adsorption are ignored, because they are assumed to influence rates-of-change between steady states, but not steady-state water compositions per se. The model can be used to estimate variations in streamwater composition with flow. Model calculations suggest that a 50% decrease in depositional acidifying components (sulphur oxides and NH(4)(+)) would result in increases of up to 1 pH unit in streamwaters with present-day baseflow pH values of 5 or less. It appears that water quality in the upper Duddon is currently more sensitive to inputs of NH(4)(+) than of H(2)SO(4). To improve the reliability of model predictions, more information is required on (a) the pH dependence of base cation weathering, (b) transformations involving nitrogen, (c) aluminium chemistry and (d) partial pressures of CO(2) in soil and baserock.     

Effects of heavy metal contamination on macronutrient availability and acidification parameters in forest soil in the vicinity of the Harjavalta Cu-Ni smelter, SW Finland

Four experiments were established (1992) in Scots pine stands at distances of 0.5, 2, 4 and 8 km along a line running to the SE of the Cu-Ni smelter at Harjavalta, SW Finland, in order to investigate the effects of Cu and Ni emissions on macronutrient availability and estimates of cation exchange capacity (CEC) and base saturation (BS). The accumulation of Cu and Ni (total, exchangeable) in forest soil close to the smelter has resulted in a deficit of base cations (exchangeable Ca, Mg, K and BS) in the organic layer caused by inhibition of mineralisation and the displacement of base cations from cation exchange sites by Cu and Ni cations. No signs of soil acidification were found in the topmost layers of the soil measured as a change in pH, exchangeable acidity and Al. The determination of CEC by the summation method in heavy-metal polluted forest soils is not recommended unless heavy metal cations are also included in the calculations.     

Acid rain and acidification in China: the importance of base cation deposition

Acid deposition has been recognized as a serious environmental problem in China. Most acid deposition studies have focused on sulfur deposition and the pH of precipitation. However, as high concentration of alkaline dust is an important feature of the atmosphere in large parts of China, base cation deposition must be taken into account when discussing possible effects on soils and vegetation from acid deposition. We estimate the deposition of sulfur as well as calcium, i.e. the dominating anion and cation, on a regional scale in China using data both from measurements and modeling. The ratio of sulfur/calcium in deposition is then used as an indicator for identifying areas where deposition acidity exceeds alkalinity, and where soils may be at risk to acidification. The dynamic soil acidification model MAGIC is applied with data from two sites receiving high deposition loads in southwest China. The model predictions indicate that considerable soil acidification has been going on for the last decades due to acid deposition inputs. Effects on the spatial distribution of acidic deposition in China, using different future deposition scenarios, are illustrated. As the size of the anthropogenic fraction of the base cation deposition is unknown, different possible future trends in calcium deposition were used. Soil response, according to the model, using different combinations of sulfur and calcium deposition scenarios is shown. Applying the most strict measures to reduce sulfur emission will almost eliminate the acid deposition problem; however, such a scenario is not economically feasible in the short term. A strict, but possibly realistic, future scenario for sulfur may be enough to keep the situation at the present level, assuming only moderate reductions in calcium deposition. With large decreases in base cation deposition, increased soil acidification can be expected even with considerable sulfur emission reductions.     

Assessment of Uncertainty in Long-Term Mass Balances for Acidification Assessments: A MAGIC Model Exercise

Long-term (1860–2010) catchment mass balance calculations rely on models and assumptions which are sources of uncertainty in acidification assessments. In this article, we report on an application of MAGIC to model acidification at the four Swedish IM forested catchments that have been subject to differing degrees of acidification stress. Uncertainties in the modeled mass balances were mainly associated with the deposition scenario and assumptions about sulfate adsorption and soil mass. Estimated base cation (BC) release rates (weathering) varied in a relatively narrow range of 47–62 or 42–47 meq m⁻² year⁻¹, depending on assumptions made about soil cation exchange capacity and base saturation. By varying aluminum solubility or introducing a dynamic weathering feedback that allowed BC release to increase at more acidic pHs, a systematic effect on predicted changes in acid neutralizing capacity (ΔANC ca. 10–41 μeq l⁻¹) and pH (ca. ΔpH = 0.1–0.6) at all sites was observed. More robust projections of future changes in pH and ANC are dependent on reducing uncertainties in BC release rates, the timing, and extent of natural acidification through BC uptake by plants, temporal changes in soil element pools, and fluxes of Al between compartments.     

Systematic comparison of ILWAS, MAGIC, and ETD watershed acidification models: 3. Mass balance budgets for acid neutralizing capacity

Three watershed acidification models-ILWAS, MAGIC, and ETD-were quantitatively compared to determine model structural differences by using a combination of input mapping and ANC mass balance budgets. Input mapping is a set of rules and algorithms to ensure that consistent input values were simultaneously derived for all three models. ANC budget analysis under current SO4(2-) deposition and a 70% reduction in SO4(2-) deposition allows examination of the relative importance of biogeochemical processes in affecting predictions of ANC or predicted changes in ANC. Model inputs were based on two dissimilar watersheds having characteristics typical of watersheds in the northeastern US. After mapping inputs, the three models predicted values of outflow ANC fluxes that were similar among the models for each watershed and deposition scenario. Within each watershed, the changes in outflow ANC fluxes between the scenarios were similar for the three models. Terrestrial weathering was the major source of ANC for all three models for both watersheds and deposition scenarios. The contributions of other processes to the ANC of the two watersheds were, under certain conditions, model-specific. Cation exchange was responsible for changes in ANC when deposition decreased for the three models. Other processes responsible for changes in ANC between scenarios were SO4(2-) sorption (for MAGIC) and in-lake weathering (for ETD). The processes responsible for the change in ANC from a change in deposition (cation exchange, SO4(2-) sorption, and in-lake weathering) were different from the processes contributing to the absolute ANC for a given deposition scenario (terrestrial weathering). The budget analysis complements an earlier Monte Carlo analysis that showed that the three models are structurally different and that predictions viewed on a relative scale are more similar than absolute scale predictions.     

Comparison among model estimates of critical loads of acidic deposition using different sources and scales of input data

The critical load (CL) of acidic atmospheric deposition represents the load of acidity deposited from the atmosphere to the earth’s surface at which harmful acidification effects on sensitive biological receptors are thought to occur. In this study, the CL for forest soils was estimated for 27 watersheds throughout the United States using a steady-state mass balance approach based on both national and site-specific data and using different approaches for estimating base cation weathering. Results suggested that the scale and source of input data can have large effects on the calculated CL and that the most important parameter in the steady-state model used to estimate CL is base cation weathering. These results suggest that the data and approach used to estimate weathering must be robust if the calculated CL is to be useful for its intended purpose.     

Impacts of simulated acid rain on recalcitrance of two different soils

Laboratory experiments were conducted to estimate the impacts of simulated acid rain (SAR) on recalcitrance in a Plinthudult and a Paleudalfs soil in south China, which were a variable and a permanent charge soil, respectively. Simulated acid rains were prepared at pH 2.0, 3.5, 5.0, and 6.0, by additions of different volumes of H₂SO₄ plus HNO₃ at a ratio of 6 to 1. The leaching period was designed to represent 5 years of local annual rainfall (1,200 mm) with a 33 % surface runoff loss. Both soils underwent both acidification stages of (1) cation exchange and (2) mineral weathering at SAR pH?2.0, whereas only cation exchange occurred above SAR pH?3.5, i.e., weathering did not commence. The cation exchange stage was more easily changed into that of mineral weathering in the Plinthudult than in the Paleudalfs soil, and there were some K⁺ and Mg²⁺ ions released on the stages of mineral weathering in the Paleudalfs soil. During the leaching, the release of exchangeable base cations followed the order Ca²⁺?>?K⁺?>?Mg²⁺?>?Na⁺ for the Plinthudult and Ca²⁺?>?Mg²⁺?>?Na⁺?>?K⁺ for the Paleudalfs soil. The SARs above pH?3.5 did not decrease soil pH or pH buffering capacity, while the SAR at pH?2.0 decreased soil pH and the buffering capacity significantly. We conclude that acid rain, which always has a pH from 3.5 to 5.6, only makes a small contribution to the acidification of agricultural soils of south China in the short term of 5 years. Also, Paleudalfs soils are more resistant to acid rain than Plinthudult soils. The different abilities to prevent leaching by acid rain depend upon the parent materials, types of clay minerals, and soil development degrees.     

Quantifying the role of forest soil and bedrock in the acid neutralization of surface water in steep hillslopes

The role of soil and bedrock in acid neutralizing processes has been difficult to quantify because of hydrological and biogeochemical uncertainties. To quantify those roles, hydrochemical observations were conducted at two hydrologically well-defined, steep granitic hillslopes in the Tanakami Mountains of Japan. These paired hillslopes are similar except for their soils; Fudoji is leached of base cations (base saturation <6%), while Rachidani is covered with fresh soil (base saturation >30%), because the erosion rate is 100-1000 times greater. The results showed that (1) soil solution pH at the soil-bedrock interface at Fudoji (4.3) was significantly lower than that of Rachidani (5.5), (2) the hillslope discharge pH in both hillslopes was similar (6.7-6.8), and (3) at Fudoji, 60% of the base cations leaching from the hillslope were derived from bedrock, whereas only 20% were derived from bedrock in Rachidani. Further, previously published results showed that the stream pH could not be predicted from the acid deposition rate and soil base saturation status. These results demonstrate that bedrock plays an especially important role when the overlying soil has been leached of base cations. These results indicate that while the status of soil acidification is a first-order control on vulnerability to surface water acidification, in some cases such as at Fudoji, subsurface interaction with the bedrock determines the sensitivity of surface water to acidic deposition.     

Recovery from acidification in central Europe--observed and predicted changes of soil and streamwater chemistry in the Lysina catchment,Czech Republic

The geochemical model MAGIC was applied to estimate streamwater and soil chemistry between 1851 and 2030 at the Lysina catchment, an acid-sensitive granitic catchment covered by planted Norway spruce monoculture in the western Czech Republic. The total deposition of sulfur to the catchment was 164 meq m(-2) in 1991, but had declined to 52 meq m(-2) by 2000. Although SO2 emissions in the region declined by 90% compared to the 1980s, acidification recovery was small within the period 1990-2000. Stream pH increased only slightly (from 3.92 to 4.07), although SO4 concentration declined sharply from 568 microeq l(-1) (1990) to 232 microeq l(-1) (2000). Organic acids played an important role in streamwater buffering. According to the MAGIC prediction using deposition measured in 1999-2000, streamwater pH will increase to 4.3 and soil base saturation will increase to 6.2% by 2030 (from 5.7% in 2002). Pre-industrial pH was estimated to be 5.5 and soil base saturation 24.7%. The loss of base cations (Ca, Mg, Na, K) was caused predominantly by atmospheric acidity, but intensive forestry was responsible for approximately one third of the net base cation loss via accumulation in harvested biomass. Severely damaged sites, under continued pressure from forestry, will not return to a good environmental status in the near future (if ever) when the acid deposition input is only partially reduced.     

Base-cation deposition in Europe—part II. Acid neutralization capacity and contribution to forest nutrition

An assessment was made of the capacity of base cations to neutralize acid deposition and of the contribution of base cation deposition to forest nutrition in Europe. In large parts of southern Europe more than 50% of the potential acid deposition was found counteracted by deposition of non-sea salt Mg²⁺ + Ca²⁺ + K⁺. In central and northwestern Europe, base cation deposition usually amounted to less than 25% of the acid input. Smallest base cation deposition relative to potential acid deposition was found in southern Scandinavia, Denmark, northern Germany and The Netherlands. A similar spatial pattern was found for the neutralization of acid anions in precipitation. Whereas in Scandinavia weathering is the dominant supplier of base cation to forest soils, in eastern and southern Europe, forests mainly rely on atmospheric deposition for the supply of base cations. Using error propagation, the random and systematic error in acid neutralization capacity for an average grid cell of 10 × 20 km was estimated to equal 45–55% and 50–55%, respectively.     

Acidification in developing countries: ecosystem sensitivity and the critical load approach on a global scale

Acidification represents a growing threat to certain developing country ecosystems in tropical and subtropical climates. A methodology investigating the extent of acidification risks from sulfur emissions on a global scale is presented. Atmospheric transfer models have been used to calculate transfer and deposition of sulfur (using emissions for 1990 and a projection for 2050) and alkaline soil dust. A method to derive the relative sensitivity of terrestrial ecosystems is explained and preliminary critical load values are assigned. A range of values for critical loads and base cation deposition have been used to investigate uncertainty in maps depicting the excess of deposition above critical loads. These show an increasing risk of acidification in 2050 in extended regions of southern and eastern Asia, as well as parts of southern Africa, in comparison to 1990. Certain areas, especially in Asia, are shown at risk even when high values of critical load and base cation deposition are used.     

Simulating the long-term chemistry of an upland UK catchment: major solutes and acidification

CHUM-AM was used to investigate changes in soil and water chemical variables in four moorland sub-catchments in Cumbria UK, to which non-marine S deposition has declined by 65% since the 1970s. The principal processes represented in the model comprise N and S uptake and release, water movements, the binding of cations by soil organic matter, chemical interactions in solution, and chemical weathering. CHUM-AM reproduced reasonably well the current soil pH and pools of N and S, and changes in streamwater chemistry over the period 1970-2000, notably decreases in the concentrations of alkaline earth cations and sulphate, and increases in pH. The model also predicts streamwater pH-Al relationships in agreement with observations. Predictive calculations suggest that constant atmospheric deposition of N at present rates will lead to N saturation and re-acidification, whereas a 50% reduction in N would stabilise soil and streamwater pH at about the present levels.     

Modelling changes in forest soil chemistry at 16 Swedish coniferous forest sites following deposition reduction

The dynamic forest ecosystem model ForSAFE was applied at 16 coniferous forest sites in Sweden to investigate past and future changes in soil chemistry following changes in atmospheric deposition. The simulation shows a considerable historical soil acidification. Acidification in the southwest, where deposition has been greatest, was more expressed in the deepest soil layers, while it was more evenly distributed through the soil profile in central Sweden, and was greater in the upper soil layers in the north. The simulation also shows that a slight recovery took place after the reduction in emissions, but was counteracted by the effect of harvesting. The simulation predicts an increase in the number of acidified sites in the future. The results also suggest that future acidification will be mainly due to the enhanced tree growth resulting from the chronic high deposition of nitrogen and the removal of soil base cations through harvesting.     

Soil solution nitrogen and cations influenced by (NH4)2SO4 deposition in a coniferous forest

The effects of chronically enhanced (NH(4))(2)SO(4) deposition on ion concentrations in soil solution and ionic fluxes were investigated in a Picea abies plot at Grizedale forest, NW England. Soil cores closed at the base and containing a ceramic suction cup sampler were 'roofed' and watered every 2 weeks with bulk throughfall collected in the field. Treatments consisted of the inclusion of living roots from mature trees in the lysimeters and increasing (NH(4))(2)SO(4) deposition (NS treatment) to ambient + 75 kg N ha(-1) a(-1). Rainfall, throughfall and soil solutions were collected every 2 weeks during 18 months, and analysed for major cations and anions. NO(3)(-) fluxes significantly increased following NS treatment, and were balanced by increased Al(3+) losses. Increased SO(4)(2-) concentrations played a minor role in controlling soil solution cation concentrations. The soil exchange complex was dominated by Al and, during the experimental period, cores of all treatments 'switched' from Ca(2+) to Al(3+) leaching, leading to mean [Formula: see text] molar ratios in soil solution of NS treated cores of 0.24. The experiment confirmed that the most sensitive soils to acidification (through deposition or changing environmental conditions) are those with low base saturation, and with a pH in the lower Ca, or Al buffer ranges.     

Dry deposition of particles and canopy exchange: Comparison of wet,bulk and throughfall deposition at five forest sites in Italy

The contribution of dry deposition to the total atmospheric input of acidifying compounds and base cations is of overwhelming importance. Throughfall measurements provide an estimate of the total deposition to forest soils, including dry deposition, but some uncertainties, related to the canopy interaction processes, affect this approach. We compared the concentrations and the fluxes of the main ions determined in wet-only, bulk and throughfall samples collected at five forest sites in Italy. The contribution of coarse particles deposited onto the bulk samplers was of prime importance for base cations, representing on average from 16% to 46% of the bulk deposition. The extent of this dry deposition depended on some geographical features of the sites, such as the distance from the sea and the annual rainfall. The possibility of applying specific bulk/wet ratios to estimate the wet deposition proved to be limited by the temporal variability of these ratios, which must be considered together with the spatial variability. A direct comparison of the dry contribution deriving from the bulk–wet and the throughfall–wet demonstrated that an extensive natural surface (forest canopy) performs better than a small synthetic surface (funnel of the bulk sampler) in collecting dry deposition of SO₄²⁻, NO₃⁻ and Na⁺. The canopy exchange model was applied to both bulk and wet data to estimate the contribution of dry deposition to the total input of base cations, and the uncertainty associated to the model discussed. The exclusive use of bulk data led to a considerable underestimation of base cation dry deposition, which varies among the study sites.     

Soil sensitivity to acidification in Asia: status and prospects

Exceedance of steady-state critical loads for soil acidification is consistently found in southern China and parts of SE Asia, but there is no evidence of impacts outside of China. This study describes a methodology for calculating the time to effects for soils sensitive to acidic deposition in Asia under potential future sulfur (S), nitrogen (N), and calcium (Ca) emission scenarios. The calculations are matched to data availability in Asia to produce regional-scale maps that provide estimates of the time (y) it will take for soil base saturation to reach a critical limit of 20% in response to acidic inputs. The results show that sensitive soil types in areas of South, Southeast, and East Asia, including parts of southern China, Burma, Hainan, Laos, Thailand, Vietnam, and the Western Ghats of India, may acidify to a significant degree on a 0-50 y timescale, depending on individual site management and abiotic and biotic characteristics. To make a clearer assessment of risk, site-specific data are required for soil chemistry and deposition (especially base cation deposition); S and N retention in soils and ecosystems; and biomass harvesting and weathering rates from sites across Asia representative of different soil and vegetation types and management regimes. National and regional assessments of soils using the simple methods described in this paper can provide an appreciation of the time dimension of soil acidification-related impacts and should be useful in planning further studies and, possibly, implementing measures to reduce risks of acidification.     

Soil acidification and foliar nutrient status of Ontario's deciduous forest in 1986 and 2005

To assess the impacts of the decline in sulphur (S) deposition over the past 20 years in Ontario, soil chemistry and sugar maple (Acer saccharum Marsh) foliar chemistry were measured at 17 sites in south and central Ontario in 2005 and compared with archived samples collected in 1986. Foliar S concentrations were lower in 2005, reflecting the decline in S deposition whereas foliar N remained unchanged, reflecting the lack of change in N deposition in Ontario. Mineral soil pH, exchangeable base cations were lower in 2005 whereas total S, N and cation exchange capacity (CEC) were unchanged. Foliar concentrations of Ca were positively related to soil Ca levels in the A-horizon and were lower in 2005. Despite evidence of increasing soil acidity and losses of calcium, foliar base cation concentrations at most sites were adequate for sugar maple and forest health in terms of canopy appearance (Decline Index) improved.     

Terrestrial ecosystem recovery--modelling the effects of reduced acidic inputs and increased inputs of sea-salts induced by global change

The reduced emissions of acidifying sulfur and nitrogen in Europe since the late 1970s will be further reduced when the Gothenburg protocol is fully implemented by 2010. Here we address the consequences for the recovery of acidified terrestrial ecosystems using the acidification model MAGIC applied to 3 large-scale "clean rain" experiments, the so-called roof experiments at Risdalsheia, Norway; G?rdsj?n, Sweden, and Klosterhede, Denmark. Implementation of the Gothenburg protocol will initiate recovery of the soils at all 3 sites by rebuilding base saturation. The rate of recovery is small and base saturation increases less than 5% over the next 30 years. A climate-induced increase in storm severity will increase the sea-salt input to the ecosystems. This will provide additional base cations to the soils and more than double the rate of the recovery, but also lead to strong acid pulses following high sea-salt inputs as the deposited base cations exchange with the acidity stored in the soil. Future recovery of soils and runoff at acidified catchments will thus depend on the amount and rate of reduction of acid deposition, and in the case of systems near the coast, the frequency and intensity of sea-salt episodes as well.     

Modeling Past and Future Acidification of Swedish Lakes

Decades of acid deposition have caused acidification of lakes in Sweden. Here we use data for 3000 lakes to run the acidification model MAGIC and estimate historical and future acidification. The results indicate that beginning in about 1920 a progressively larger number of lakes in Sweden fell into the category of “not naturally acidified” (∆pH > 0.4). The peak in acidification was reached about 1985; since then many lakes have recovered in response to lower levels of acid deposition. Further recovery from acidification will occur by the year 2030 given implementation of agreed legislation for emissions of sulphur (S) and nitrogen (N) in Europe. But the number of catchments with soils being depleted in base cations will increase slightly. MAGIC-reconstructed history of acidification of lakes in Sweden agrees well with information on fish populations. Future acidification of Swedish lakes can be influenced by climate change as well as changes in forest harvest practices.