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.     

Recovery from acidification in Swedish forest streams

Sulphur deposition in Sweden has decreased to less than half of the levels recorded in 1970 and now signs of recovery from acidification of surface waters are beginning to appear. We investigated time trends of water chemistry between 1985 and 1998 in 13 streams draining small forested catchments with generally shallow acid sensitive soils. At nine of the catchments, bulk deposition was monitored as well. Sulphate concentrations decreased in both stream water and deposition, although with somewhat smaller trends in stream water compared with deposition. The magnitude of the trends in sulphate increased from north to south, following a gradient of increasing industrial influence. Five sites in the southern half of the country showed weak signs of recovery from acidification in terms of increasing concentrations of acid neutralising capacity and decreasing concentrations of hydrogen ions, corresponding to annual increases of 0.01 pH units. Changes in stream discharge and concentrations of marine salts and organic acids could not explain the observed decrease in acidity and the results were interpreted as recovery from anthropogenic acidification. For the northern half of Sweden, any changes in water chemistry could be attributed to natural variation in climate and marine influence, and the effect of anthropogenic acidification was negligible.     

Modelling assessment of regional groundwater contamination due to historic smelter emissions of heavy metals

Historic emissions from ore smelters typically cause regional soil contamination. We developed a modelling approach to assess the impact of such contamination on groundwater and surface water load, coupling unsaturated zone leaching modelling with 3D groundwater transport modelling. Both historic and predictive modelling were performed, using a mass balance approach for three different catchments in the vicinity of three smelters. The catchments differ in their hydrology and geochemistry. The historic modelling results indicate that leaching to groundwater is spatially very heterogeneous due to variation in soil characteristics, in particular soil pH. In the saturated zone, cadmium is becoming strongly retarded due to strong sorption at neutral pH, even though the reactivity of the sandy sediments is low. A comparison between two datasets (from 1990 to 2002) on shallow groundwater and modelled concentrations provided a useful verification on the level of statistics of "homogeneous areas" (areas with comparable land use, soil type and geohydrological situation) instead of comparison at individual locations. While at individual locations observations and the model varies up to two orders of magnitude, for homogeneous areas, medians and ranges of measured concentrations and the model results are similar. A sensitivity analysis on metal input loads, groundwater composition and sediment geochemistry reveals that the best available information scenario based on the median value of input parameters for the model predicts the range in observed concentrations very well. However, the model results are sensitive to the sediment contents of the reactive components (organic matter, clay minerals and iron oxides). Uncertainty in metal input loads and groundwater chemistry are of lesser importance. Predictive modelling reveals a remarkable difference in geochemical and hydrological controls on subsurface metal transport at catchment-scale. Whether the surface water load will peak within a few decades or continue to increase until after 2050 depends on the dominant land use functions in the areas, their hydrology and geochemical build-up.     

Distribution of Al-, Fe- and Mn-pools and their correlation in soils from two acid deposition small catchments in Hunan, China

Distribution of Al-, Fe- and Mn-pools was investigated in five forest soil profiles (consisting of four horizons) in each of two Hunan catchments (BLT and LKS) where acid deposition has been considered critical. Al- and Fe-pools were higher in BLT than those in LKS, but Mn-pools much lower in BLT. Mn-pools vary from topsoils to bottom soils, but there are different trends for different Mn speciation. Al- and Fe-pools, except amorphous Fe_ox, were positively correlated to contents of soil organic matter (OM) showed by the loss on ignition in the two catchments. Accumulation of Al- and Fe-pools may occur in the area where soil organic matter was enriched (e.g. in top soil and rhizosphere soil). However, no direct correlation is observed between Mn and OM. Acidic atmospheric deposition may affect transforming among speciations of Al-, Fe- and Mn-pools and leaching of soil Al, Fe and Mn through formation of soluble organo-metal dissolved Al which was potentially toxic, increased. There were significant correlations between Al-pools complexes or change of oxidation–reduction conditions. Mn_ex (exchangeable Mn) and Mn_ox (amorphous and organic Mn) were highly linearly correlation with soil pH values at LKS but at BLT. Under acid deposition, the availability of the nutrient Fe increased with the amount of dissolved Al, which was potentially toxic, in the two catchments. There are no significant correlations between Al_ex (exchangeable Al) and Mn_ex, Fe_ex (exchangeable Fe) and Mn_ex in this work, indicating potentially toxic Mn increase seldom accompanying with Al increase in the two catchments.     

Influence of soil hydrological pathways on stream aluminium chemistry at Llyn Brianne, mid-wales

Storm runoff in afforested catchments at Llyn Brianne is acidic and Al-bearing. At baseflows, stream water is well-buffered with low Al levels. This paper presents the results of a study into how hydrological pathways account for these variations in stream-water chemistry. The investigation was carried out in the LI1 catchment; a 0.4-ha subcatchment covered by stagnohumic gley soils was monitored between October 1988 and September 1989. An instrumented hill-slope was established to identify the hydrological pathways that control the hydrochemistry of storm runoff draining from the subcatchment. Perched watertables developed in the surface horizons of the soil during storm episodes and produced lateral flow above the impeding subsoil. This near-surface flow path was responsible for generating acid, Al-rich storm runoff. Some water drained vertically through the soil profile into the underlying slope drift; seepage from groundwater in the drift sustained baseflows. Buffering reactions in the groundwater zone reduced the acidity and Al levels of baseflows. These hydrochemical characteristics are likely to be representative of other areas of stagnohumic gley soils, which cover 19% of the LI1 catchment: these soils may therefore provide a substantial source of acid, Al-bearing storm runoff in LI1 and similar afforested catchments.     

Effects of acidic deposition on forest and aquatic ecosystems in New York State

Acidic deposition is comprised of sulfuric and nitric acids and ammonium derived from atmospheric emissions of sulfur dioxide, nitrogen oxides, and ammonia, respectively. Acidic deposition has altered soil through depletion of labile pools of nutrient cations (i.e. calcium, magnesium), accumulation of sulfur and nitrogen, and the mobilization of elevated concentrations of inorganic monomeric aluminum to soil solutions in acid-sensitive areas. Acidic deposition leaches essential calcium from needles of red spruce, making this species more susceptible to freezing injury. Mortality among sugar maples appears to result from deficiencies of nutrient cations, coupled with other stresses such as insect defoliation or drought. Acidic deposition has impaired surface water quality in the Adirondack and Catskill regions of New York by lowering pH levels, decreasing acid-neutralizing capacity, and increasing aluminum concentrations. Acidification has reduced the diversity and abundance of aquatic species in lakes and streams. There are also linkages between acidic deposition and fish mercury contamination and eutrophication of estuaries.     

Afforestation, seasalt episodes and acidification--a paired catchment study in western Norway

As acid deposition has declined during the past 15-20 years in western Norway, afforestation and episodic seasalt deposition have become factors of increasing importance in explaining the mobilization of toxic aluminum (Aln+) to rivers and lakes. We conducted a paired catchment at four sites in western Norway across a gradient in acid deposition to evaluate the importance of afforestation and seasalt episodes. Streamwater was sampled intensively before, during and after seasalt episodes over a three-year period. A seasalt episode in January 2003 caused considerable impact on the streamwater chemistry. pH dropped and concentrations of Aln+ increased due to cation exchange of Na+ ions for H+ and Aln+ in the soil. The response was larger in streams draining the catchments which receive high acid deposition and in those afforested with spruce as compared with adjacent catchments in native birch. The results indicate that acid pulses induced by episodic inputs of seasalts are exacerbated by land use change from native birch to planted spruce.     

The influence of organic acids in relation to acid deposition in controlling the acidity of soil and stream waters on a seasonal basis

Much uncertainty still exists regarding the relative importance of organic acids in relation to acid deposition in controlling the acidity of soil and surface waters. This paper contributes to this debate by presenting analysis of seasonal variations in atmospheric deposition, soil solution and stream water chemistry for two UK headwater catchments with contrasting soils. Acid neutralising capacity (ANC), dissolved organic carbon (DOC) concentrations and the Na:Cl ratio of soil and stream waters displayed strong seasonal patterns with little seasonal variation observed in soil water pH. These patterns, plus the strong relationships between ANC, Cl and DOC, suggest that cation exchange and seasonal changes in the production of DOC and seasalt deposition are driving a shift in the proportion of acidity attributable to strong acid anions, from atmospheric deposition, during winter to predominantly organic acids in summer.     

Surface water acidification in the South Pennines I. Current status and spatial variability

The South Pennines, an area of acid-sensitive geology at the centre of a major industrial region, have undergone perhaps the most severe historic exposure to sulphur and nitrogen deposition in the UK. This study addresses a lack of existing research on the region by presenting the findings of a survey of 62 surface waters sampled during a 1-week period in April 1998. Results indicate that acidification in the region is acute; 27 of the sampled surface waters had a negative acid neutralising capacity (ANC) and 28 had a pH below 5.0. Minimum recorded pH values were below 4.0. Non-marine sulphate levels were extremely high (median 222 microeq/1), and widespread high nitrate concentrations (median 41 microeq/1) suggest that soils in the region as a whole may be at an advanced stage of nitrogen saturation. A consistent relationship was identified between site acidity and the balance between the major weathering-derived cations, calcium and magnesium, and sulphate. This could in turn be linked to catchment soil type and land use, with the most acidic conditions occurring in peat-dominated catchments, where weathering is minimal and the influence of atmospheric deposition most pronounced. Percentage of peat in each catchment was the single best predictor of surface water acidity. Nitrate concentrations, although not a dominant control on acidity, varied significantly according to land use. Elevated concentrations were observed in catchments containing forestry, due to enhanced deposition inputs, and in catchments containing improved land, linked to fertiliser use. Ammonium concentrations, although low at most catchments, were a significant component of the inorganic nitrogen total in a number of surface waters draining waterlogged peat catchments.     

Trace metals in interstitial waters from sandstones: acidic inputs to shallow groundwaters

There is some evidence from southern Britain that shallow groundwaters in non-carbonate lithologies may be affected by acidic deposition. To investigate this, interstitial water profiles down to 12 m have been obtained from unsaturated sands or semi-consolidated sandstones from the Folkestone Beds (Lower Greensand) of Surrey and the Sherwood Sandstone of the West Midlands. The pH of the interstitial waters generally increased with depth and reflected an increase in the base saturation of the exchange complex. Beneath the highly acidic surface soil horizons (pH 3.0-3.5), interstitial waters with a pH of 4.0-4.5 were found down to depths of several metres. The pH progressively increased to around pH 5.5 because of base cation desorption and the weathering of silicate minerals. High concentrations of aluminium (10-20 mg litre(-1)) and other metals (Fe, Mn, Cu, Ni, Co, Zn, Be) were found in the interstitial water in the upper unsaturated zone. Most metal concentrations were strongly pH-dependent but also reflected the geochemical characteristics of the parent sands or sandstones. H+ and trace element concentrations were slightly higher beneath areas of afforestation than beneath heathland. The downward fluxes of solutes have been estimated using rainfall-derived chloride as a non-reactive solute. The profiles retain a record of 10-20 years input allowing the past inputs from SO4 and other species to be estimated using solute/chloride ratios. Cation exchange sites are probably depleted over a period of decades and there can be a significant decrease in the unsaturated zone pH as a result of increased or sustained acidic deposition. The shallow groundwater environment (0-15 m) in non-carbonate terrains is therefore a sensitive environment where high metal concentrations may be generated and may ultimately lead to water quality problems in shallow water supplies.     

Riparian Zone Influence on Stream Water Dissolved Organic Carbon Concentrations at the Swedish Integrated Monitoring Sites

Short-term variability in stream water dissolved organic carbon (DOC) concentrations is controlled by hydrology, climate and atmospheric deposition. Using the Riparian flow-concentration Integration Model (RIM), we evaluated factors controlling stream water DOC in the Swedish Integrated Monitoring (IM) catchments by separating out hydrological effects on stream DOC dynamics. Model residuals were correlated with climate and deposition-related drivers. DOC was most strongly correlated to water flow in the northern catchment (Gammtratten). The southern Aneboda and Kindla catchments had pronounced seasonal DOC signals, which correlated weakly to flow. DOC concentrations at Gårdsjön increased, potentially in response to declining acid deposition. Soil temperature correlated strongly with model residuals at all sites. Incorporating soil temperature in RIM improved model performance substantially (20–62% lower median absolute error). According to the simulations, the RIM conceptualization of riparian processes explains between 36% (Kindla) and 61% (Aneboda) of the DOC dynamics at the IM sites.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

Chemical fluxes in time through forest ecosystems in the UK - Soil response to pollution recovery

Long term trend analysis of bulk precipitation, throughfall and soil solution elemental fluxes from 12 years monitoring at 10 ICP Level II forest sites in the UK reveal coherent national chemical trends indicating recovery from sulphur deposition and acidification. Soil solution pH increased and sulphate and aluminium decreased at most sites. Trends in nitrogen were variable and dependant on its form. Dissolved organic nitrogen increased in bulk precipitation, throughfall and soil solution at most sites. Nitrate in soil solution declined at sites receiving high nitrogen deposition. Increase in soil dissolved organic carbon was detected - a response to pollution recovery, changes in soil temperature and/or increased microbial activity. An increase of sodium and chloride was evident - a possible result of more frequent storm events at exposed sites. The intensive and integrated nature of monitoring enables the relationships between climate/pollutant exposure and chemical/biological response in forestry to be explored.     

The application of a simplified method to map the aerobic acetate mineralization rates at the groundwater table of the Netherlands

A simplified method is used to assess the microbial activity of subsoils and soils across a broad geographic scale. Acetate was selected because it is a major intermediate in catabolic biochemical pathways. In order to get minimal disturbance, only a small amount of tritium labelled acetate and water is added to the subsoil material. After an incubation time, the subsoil material is separated from the water by centrifugation and the formed tritium labelled water is separated from the remaining acetate by evaporation. The data of 128 locations in the Netherlands were plotted in a soil map and were also compared with the depth, dry weight, electric conductivity, pH and nitrate concentration. The peat areas consisted of limed meadows with a high groundwater level whereas the sand areas often showed deeper groundwater levels and a lower pH. The subsoils at the groundwater table of the peat areas, which are in contact with soil air, showed a higher mineralization rate compared with the surface soils in our study. In contrast, the mineralization rate of the subsoil at the groundwater table of sandy soils showed on average a factor 30 lower rate. Nevertheless, the self purification capacity of the subsoil can be vital under weather conditions where the surface soil becomes less active.     

The groundwater contribution to surface water contamination in a region with intensive agricultural land use (Noord-Brabant, The Netherlands)

Traditionally, monitoring of soil, groundwater and surface water quality is coordinated by different authorities in the Netherlands. Nowadays, the European Water Framework Directive (EU, 2,000) stimulates an integrated approach of the complete soil-groundwater-surface water system. Based on water quality data from several test catchments, we propose a conceptual model stating that stream water quality at different discharges is the result of different mixing ratios of groundwater from different depths. This concept is used for a regional study of the groundwater contribution to surface water contamination in the Dutch province of Noord-Brabant, using the large amount of available data from the regional monitoring networks. The results show that groundwater is a dominant source of surface water contamination. The poor chemical condition of upper and shallow groundwater leads to exceedance of the quality standards in receiving surface waters, especially during quick flow periods.     

Critical loads and steady-state chemistry for streams in the state of Maryland

The critical loads to streams, steady-state stream chemistry and catchment chemical weathering rate in 73 catchments has been determined in the state of Maryland, USA. It was calculated with the PROFILE model from chemical limits for biological indicators, soil mineralogy, soil texture, annual average temperature, average soil moisture, net long-term uptake of base cations and nitrogen to the vegetation, annual precipitation and runoff and deposition of sulphur and nitrogen precursors of acid deposition. The results show a full range of critical loads from very low values in the sensitive catchments of western Maryland and the Coastal Plain on the Chesapeake Bay, to insensitive catchments in the Fredrick Valley and Ridge and the Piedmont plain. The critical loads will be used as an input to an integrated regional assessment of the quantitative sensitivity of streams to acid rain, and the assessment of regional stream alkalinity response to different abatement strategies. The mapping of steady-state stream chemistry indicates that streams in Maryland are still acidfying under the present deposition load. Land-use seems to play an important role in maintaining neutral pH in many of the streams of Maryland.     

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.     

Impacts of afforestation on water quality trends in two catchments in mid-Wales

The impact of afforestation on stream-water chemistry for two catchments in central Wales is investigated. Trends in water chemistry are evaluated with forest age progressing at 8-15 years and 20-27 years. To assess the possible exacerbating effect of afforestation on surface-water acidification two moorland catchments are used as controls. Absolute differences in inter-catchment streamwater chemistry are evident. Differences in acidity between the moorland and the young forest site reflect site preparation and modifications to water pathways. Differences in the observed present day chemistry between the young and old forest result from past interactions between deposition changes during forest development. An estimate of the future impact of forest growth was attained from model predictions. The model was calibrated to present day stream-water chemistry and incorporates, cation uptake, evapotranspiration/ concentration effect and increased scavenging of occult and dry deposition. Predictions suggest the pH will decline to 5.3 when the young forest progresses to 20 years of age, which is still much higher than the pH recorded at the older forest site at the age of 20 years.     

Mercury fluxes and pools in three subtropical forested catchments, southwest China

Forested catchments are an important part of the mercury (Hg) cycle and a link between the atmospheric and the aquatic environments. In this study, Hg input and output fluxes and its retention were investigated at subtropical forested catchments in southwest China. Significantly enhanced atmospheric Hg inputs were observed, and the contribution of litterfall Hg plays a more important role at these subtropical forested catchments. The ratios of Hg output fluxes from stream water to total input were 2.5% and 1.2% for LGS and TSP, which were markedly lower than those reported from Europe and North America. The current annual input Hg only accounted for 0.8 and 1.8 per mille to the Hg stored in the upper 90 cm of soil in LGS and TSP. These suggest that subtropical forested catchments are important for retention of atmospheric mercury deposition in southwest China.     

Monitoring leachate composition at a municipal landfill site in New Delhi, India

Most of the landfills in developing countries do not have any liner at the base, or a drainage layer or a proper top cover, which results in the potential problem of groundwater/surface water contamination due to the leachate. Hence, to decide whether the leachate is to be collected and treated, or may be allowed to discharge into the adjoining soil or public sewer or surface waterbody, it is essential to have an estimate of the amount of leachate and, more importantly, the composition and strength of the leachate and variation of leachate contaminants with time as the landfill site develops. In this paper, the experimental work carried out at one of the landfills in New Delhi, India, to ascertain the composition of leachate, and its effect on the groundwater in the existing situation is presented. The variation in the leachate composition with the age of deposition of solid waste has been studied. The study indicates that the leachate composition varies considerably with the age of deposition of the waste. It may be worthwhile to use different methods for the treatment of leachate from different parts of the landfill, if collected separately. It has also been concluded that since leachate contains high concentrations of organic and inorganic constituents, including heavy metals, liners must be used at the landfills. The presence of bore wells at landfill sites to draw groundwater threatens to contaminate the groundwater, and immediate remediation steps should be taken at all landfill sites that have groundwater bore wells.