Predicting Recovery from Acidic Deposition: Applying a Modified TAF (Tracking and Analysis Framework) Model to Maine (USA) High Elevation Lakes

We adapted a reduced-form model, built to predict the aquatic effects of alternative nitrogen and sulfur emissions scenarios on Adirondack lakes, New York, for use on high elevation lakes of Maine (HELM), USA. The Tracking and Analysis Framework (TAF) model was originally designed to evaluate the biotic, economic, and health effects of acid deposition. The TAF model developed in our study was used to assess the biotic effects of different levels of sulfate deposition resulting from alternative emissions scenarios. The aquatic portion of the model is based on a lumped-parameter watershed chemistry model, MAGIC (Model of Acidification of Groundwater in Catchments). The original TAF model was built by calibrating MAGIC to 33 lakes in the Adirondack Mountains. We calibrated MAGIC to 78 HELM lakes, and built reduced-form models from these MAGIC predictions. We evaluated TAF predictions of acid neutralizing capacity (ANC), a fish acid stress index (ASI), and the probability of fish presence in 2030 for four different SO₂ emissions-reduction scenarios. The most dramatic emissions reduction scenario produced only modest increases in mean ANC (16.8 μeq/L ± 7.9 μeq/L) and slight increases in mean predicted probability of presence of acid-sensitive fish (0.07± 0.09) across all lakes. However, a small number of lakes were predicted to have more substantial increases in ANC and improvements in other conditions for acid-sensitive fish. Our results reflect the reality that many of the high elevation lakes of Maine historically had low ANC and that some were even acidic in pre-industrial times. Thus, ’recovery’ for most of the high elevation lakes of Maine will be modest under any scenario of reduced acidic deposition.     

Adirondack headwater lake chemistry relationships with watershed characteristics

The Adirondack Region of New York State has been identified as having surface waters sensitive to acidic deposition and as receiving large annual inputs of acidic deposition. The large amount of data available for this region makes a quantitative study of the region possible. Compiled from a variety of sources, the Adirondack Watershed Data Base (AWDB) contains information on lake chemistry; lake elevation, area, and volume; and associated watershed data, such as size, slope, aspect, elevation, vegetation and wetland types, beaver activity, fire and logging history, and soils data. Bivariate and multivariate procedures were used to examine relationships between watershed attributes and lake chemistry. Because the variables in the data base are being refined and modified, the current relationships should be considered preliminary. Preliminary results indicate that wet deposition, lake elevation, and forest cover are the principal variables that are associated with variance in the data for lake pH and acid neutralizing capacity (ANC) in the Adirondacks. For headwater lakes in the Adirondacks, we estimate approximately 50% have a total ANC ≤ 40 μeq L^?1 and 40% have a pH ≤ 5.5.     

Acidification and Prognosis for Future Recovery of Acid-Sensitive Streams in the Southern Blue Ridge Province

This study applied the Model of Acidification of Groundwater in Catchments (MAGIC) to estimate the sensitivity of 66 watersheds in the Southern Blue Ridge Province of the Southern Appalachian Mountains, United States, to changes in atmospheric sulfur (S) deposition. MAGIC predicted that stream acid neutralizing capacity (ANC) values were above 20???eq/L in all modeled watersheds in 1860. Hindcast simulations suggested that the median historical acidification of the modeled streams was a loss of about 25???eq/L of ANC between 1860 and 2005. Although the model projected substantial changes in soil and stream chemistry since pre-industrial times, simulated future changes in response to emission controls were small. Results suggested that modeled watersheds would not change to a large degree with respect to stream ANC or soil % base saturation over the next century in response to a rather large decrease in atmospheric S deposition. Nevertheless, the magnitude of the relatively small simulated future changes in stream and soil chemistry depended on the extent to which S emissions are reduced. This projection of minimal recovery in response to large future S emissions reductions is important for designing appropriate management strategies for acid-impacted water and soil resources. Exploratory analyses were conducted to put some of the major modeling uncertainties into perspective.     

Spatial Distribution of Acid-sensitive and Acid-impacted Streams in Relation to Watershed Features in the Southern Appalachian Mountains

A geologic classification scheme was combined with elevation to test hypotheses regarding watershed sensitivity to acidic deposition using available regional spatial data and to delimit a high-interest area for streamwater acidification sensitivity within the Southern Appalachian Mountains region. It covered only 28% of the region, and yet included almost all known streams that have low acid neutralizing capacity (ANC ≤20 μeq l^?1) or that are acidic (ANC ≤0). The five-class geologic classification scheme was developed based on recent lithologic maps and streamwater chemistry data for 909 sites. The vast majority of the sampled streams that had ANC ≤20 μeq l^?1 and that were totally underlainby a single geologic sensitivity class occurred in the siliceous class, which is represented by such lithologies as sandstone and quartzite. Streamwater acid-base chemistry throughout the region was also found to be associated with a number of watershed features that were mapped for the entire region, in addition to lithology and elevation, including ecoregion, physiographic province, soils type, forest type and watershed area. Logistic regression was used to model the presence/absence of acid-sensitive streams throughout the region.     

Chemistry differences in two streams entering an acidic lake in the Adirondack Mountains,New York (U.S.A.)

Solution chemistry was measured in two major inlets, lake water column, lake outlet, and soils of the South Lake watershed in the Adirondack Mountains, New York. The east inlet had greater concentrations of H⁺, sulfate-S, and Al and smaller concentrations of base cations and silica than the west inlet (70, 116, 25, 90, 64 and 4, 99, 8, 228, 148 μeq L^?1 of H⁺ and sulfate-S, μmol L^?1 Al, μeq L^?1 total base cations and μmol L^?1 silica in east and west inlets, respectively). Concentrations of base cations in C horizon soil solutions (157 μeq L^?1 total base cations) were smaller and greater than west and east inlets, respectively. This suggests that water flowing into the west inlet contacted deeper mineral layers, whereas water reaching the east inlet did not. Lake and lake outlet concentrations were also intermediate between the two inlets, and the lake was acidic (pH 4.9 to 5.1) with relatively high total monomeric Al concentrations (8 to 9 μmol Al L^?1). The east inlet also had greater DOC concentrations than the west (0.38 and 0.24 μmol C L^?1, respectively), again indicating that soil solutions entering the east inlet passed through the forest floor but had more limited contact with deeper mineral layers in comparison with the west inlet. Differences between the streams are hypothesized to be related to contact of percolating solutions with mineral soil horizons and underlying glacial till, which provides neutralization of acidic solutions and releases base cations. This work indicates that processes controlling surface water acidification can be spatially quite variable over a small watershed.     

Soil geochemistry in relation to water chemistry and sensitivity to acid deposition in Finnish Lapland

Ecosystems in Finnish Lapland are threatened by heavy metal pollution and acid deposition derived from emissions of Cu-Ni smelters in Kola Peninsula and to varying extent to pollution from southern Fennoscandian and Central European sources. Extensive chemical analyses of small lake waters collected in Finnish Lapland have demonstrated that a significant number of lakes are acidified (ANC < 0μcq/l) or their buffering capacity is critical (ANC = 0–50μe/l). The relative abundance of mafic, ultramafic and carbonate rock components in the catchment were the chief factors controlling ANC and the main base cation (Ca²⁺, Mg²⁺) concentrations of lake waters. Both humic and clearwater lakes with low buffering capacity (ANC < 50μeq/l) were mainly located in the catchment areas identified as sensitive to acidification on the basis of low content of base cations (Ca²⁺ +Mg²⁺ +K⁺ < 500 meq/kg) in till. The ratio of the catchment area to the lake area was distinctly smaller for acidic lakes than for the well-buffered lakes, indicating the importance of catchment processes in determining the ANC and main base cations. The high sulphur concentrations (median 60μeq/1) of acidic lakes in northeastern Lapland, near the Finnish-Norwegian border, were strongly correlated with the highest deposition of sulphur derived from smelters of Kola Peninsula. The anomalously high concentrations of sulphur of well-buffered lakes in the western part of Lapland were due to sulphide minerals of soil and bedrock. The acidity of humic lakes in southern Lapland was in large part due to the organic acidity derived from peatlands.     

Acidification of a Small Stream on Kureha Hill Caused by Nitrate Leached from a Forested Watershed

Nitrate leakage to a stream from a small forested watershed on Kureha Hill in Toyama Prefecture, Japan was investigated in order to assess its acid-base chemistry. Kureha Hill, located in Toyama City, receives high nitrogen loading from the atmosphere. In this area, there are several small streams characterized by a high concentration of nitrate and low ANC. Hyakumakidani, one of the most acidic streams on that hill, the average pH and ANC were 5.2 and ?8 µeq/l, respectively. The weighted average nitrate concentration, which was 125 µeq/l, increased up to 370 µeq/l during high-discharge periods caused by heavy rainfall, while ANC decreased to ?24 µeq/l at the same time. Our preliminary study using a two-stage tank model simulating the flow paths in the soil indicated that during high-discharge periods, the increased subsurface flow containing a high concentration of nitrate contributed to the increased nitrate concentration. In this watershed, the annual nitrogen budget from Aug. 1998 to Aug. 1999 showed that the loss of nitrogen exceeded the bulk nitrogen deposition, indicating that this watershed is under condition of nitrogen saturation. However, no visible attenuation has been observed.     

Seasonal,annual and long-term variability in the water chemistry of a remote high mountain lake: Acid rain versus natural changes

Seasonal fluctuations as well as long-term trends in water chemistry were studied in Schwarzsee ob Sölden (Tyrol, Austria), an oligotrophic softwater lake situated at 2796 m a.s.l. The catchement is composed of granite, plagioclase and micaschists containing considerable amounts of sulphur, with little soil cover. The lake is ice covered for about nine months, during this time the deepest layers (>16m) become anoxic. During summer overturn, alkalinity (ALK) is lowest (?8 μeq l^?1) in the whole water column, whereas pH reaches its minimum (4.88) at the surface during snowmelt. A decrease of pH from 5.8 to 5.4 during winter is caused by CO₂ oversaturation, but deep water ALK increases to up to 130 μeq l^?1 due to in-lake ALK generation by reductive processes and base cation (BC) release. The seasonal pattern of ALK in SOS is driven by in-lake processes in winter, the snowmelting in spring and watershed processes and precipitation during summer. Since 1989 summer sulfate concentrations in SOS, originating mainly from the catchment, show a tendency to increase presumably caused by enhanced weathering. In contrast, SO₄ ^2? concentrations in other high mountain lakes which are dominated by atmospheric depositions show a decreasing trend. SOS is a good example for the complexity of interactions between catchment and in-lake processes which act at different time scales and depend on climate changes and atmospheric inputs.     

Lake and watershed neutralization strategies

The Experimental Watershed Liming Study (EWLS) evaluated the application of CaCO₃, to a forested watershed to mitigate the acidification of surface water. During October 1989, 6.9 Mg CaCC₃/ha was applied by helicopter to two subcatchments of about 50% (102.5 ha) of the Woods Lake watershed area. The EWLS team investigated the response to treatment of soils (chemistry and microbial processes), vegetation, wetland, stream and lake waters, and phytoplankton and fish, and applied the Integrated Lake Watershed Acidification (ILWAS) model in predicting a watershed treatment duration of up to 50 years. Observations showed a gradual change in pH, acid neutralizing capacity (ANC) and Ca²⁺ in the water column; direct lake additions of CaCO₃ (three different times) were characterized by abrupt changes following base addition and subsequent rapid reacidification. Moreover, the watershed treatment eliminated the snowmelt acidification of the near-shore region of the lake observed during direct lake treatments. Positive ANC water in the tributary and near-shore area improved conditions for fish reproduction and for a viable fish population. Budgets for 12-month periods before and after the watershed treatment showed that the lake shifted from a source of ANC to a sink due to retention of elevated inputs of Ca²⁺ from the watershed CaCO₃ application.     

The consequences of liming a highly acidified catchment in central Scotland

Research during the mid 1980s identified acidified, forested catchments in central Scotland whose hydrochemistry was not capable of supporting native fish populations. Calcium concentrations were around 20 μeq l^?1, less than the suggested critical value of 50 μeq l^?1, with hydrogen concentrations around 70 μeq l^?1, greater than the critical value of about 30 μeq l^?1. Limestone was applied by aerial application to the source areas of selected streams in 1990 with around 5% (15 ha) of the total catchment area of 270 ha treated at 10 tonnes ha^?1. Stream monitoring, carried out over the period 1989–1995, showed an immediate response to liming followed by a progressive decline. Calcium values were elevated to >150 μeq l^?1 and hydrogen concentrations reduced to 20 μeq l^?1, reverting in time towards pre-liming values. Although salmonid survival was improved during low flow conditions in summer, only a few fry survived to the autumn as acid episodes increased, and these were subsequently lost from the system during the winter period. Budget calculations indicated losses of around 30% of the applied calcium during the first four years. Studies on the vegetation and soils revealed a greater than expected penetration of calcium to depth (10–20 cm) in the soil profile. Results suggest that source area liming at this rate has had minimal effects on the vegetation and by increasing the proportion of the catchment limed to 15% could have a much greater success in reducing the frequency of biologically damaging episodes.     

Assessment of critical loads in liuzhou,China using static and dynamic models

The project Comprehensive Control and Demonstration for Acid Deposition in Liuzbou area is a national key project in the 8th Five-year-plan, and the study on critical loads will provide scientific and quantitative accordance for formulating control strategy. In this paper, critical loads of acid deposition to soil in Lirzhou area, China, were calculated using the Steady State Mass Balance method (SMB and PROFILE) and dynamic modeling methods(MAGIC), based on data obtained from field investigations and physiochemical properties measured through experiments such as the organic content, cation exchange capacity, base saturation, sulfate adsorption capacity, gibbsite coefficient, biomass base cation uptake and selectivity coefficient for cations. Weathering rates necessary to calculate soil chemistry in applying SMB and MAGIC model were determined by computation with PROFILE using independent geophysical properties such as soil texture and mineralogy as the input data, or by the total soil base cation content correlation. The results have shown that the critical loads of acidity in this area are in the range of 0.7–6.0 keq ha^–1 yr^–1, indicating sulfur deposition should be cut down by 50–90 percent of the present level. The upper soil layer is the most sensitive. The maximum allowable deposition loading of this area is also presented in the paper.     

Trends in the Chemistry of Acidified Bohemian Lakes from 1984 to 1995: I. Major Solutes

Temporal changes in major solute concentrations in six Czech Republic lakes were monitored during the period 1984–1995. Four chronically-acidic lakes had decreasing concentrations of strong-acid anions (C_SA = SO₄ ^2- + NO^{3 -} + Cl^-), at rates of 3.0 to 9.0 μeq L^-1 yr^-1. Decreases in SO₄ ^2-, NO₃ ^-, and Cl^- (at rates up to 5.1 μeq L^-1 yr^-1, 3.2 μeq L^-1 yr^-1, and 0.6 μeq L^-1 yr^-1, respectively) occurred. The response to the decrease in deposition of S was rapid and annual decline of SO₄ ^2- in lake water was directly proportional to SO₄ ^2- concentrations in the acidified lakes. Changes in NO₃ ^- concentrations were modified by biological consumption within the lakes. The decline in C^SA was accompanied in the four most acidic lakes by decreases in Al_T, increases in pH at rates of 0.011 to 0.016 pH yr^{- 1}, and decreases of Ca²⁺ and Mg²⁺ (but not Na⁺) in three lakes. The acid neutralizing capacity (ANC) increased significantly in all six lakes. Increases in base cation concentrations (CB = Ca²⁺ + Na⁺ + Mg²⁺ + K⁺) were the principal contributing factor to ANC increases in the two lakes with positive ANC, whereas decrease in C_SA was the major factor in ANC increases in the four chronically-acidic lakes. The continued chemical recovery of these lakes depends on the uncertain trends in N deposition, the cycling of N in the lakes and their catchments, and the magnitude of the future decrease in S deposition.     

Acid-base chemistry of high-elevation streams in the great smoky mountains

Longitudinal and temporal variations in water chemistry were measured in several low-order, high-elevation streams in the Great Smoky Mountains to evaluate the processes responsible for the acid-base chemistry. The streams ranged in average base flow ANC from ?30 to 28 μeq L^?1 and in pH from 4.54 to 6.40. Low-ANC streams had lower base cation concentrations and higher acid anion concentrations than did the high-ANC streams. NO₃ ^? and SO₄ ^2? were the dominant acid anions. NO₃ ^? was derived from a combination of high leaching of nitrogen from old-growth forests and from high rates of atmospheric deposition. Streamwater SO₄ ^2? was attributed to atmospheric deposition and an internal bedrock source of sulfur (pyrite). Although dissolved Al concentrations increased with decreasing pH in the study streams, the concentrations of inorganic monomeric Al did not follow the pattern expected from equilibrium with aluminum trihydroxide or aluminum silicate phases. During storm events, pH and ANC declined by as much as 0.5 units and 15 μeq L^?1, respectively, at the downstream sites. The causes of the episodic acidification were increases in SO₄ ^2? and DOC.     

Effects of experimental acidification and alkalinization on soil and growth and health of Acer saccharum Marsh.

Experimental application of eight acidifying, neutral, or alkalizer compounds (range: –16 to 16 kmol ha^–1 of acid‐neutralizing capacity [ANC]) was realized in two northern hardwood stands having significantly different soil base saturation (BS) (a “poor” and a “rich” site) to assess responses of soil physico‐chemical properties, and nutrition, growth, and health of sugar maple (Acer saccharum Marsh.) trees in the short (3 y) and longer term (10 y). The treatments influenced the main indicators of acidity in the forest floor (soil exchangeable‐Ca saturation [S_Ca], BS, exchangeable‐acidity saturation [S_H+Al], and the S_Ca/S_H+Al ratio) at both sites, their values increasing (decreasing for S_H+Al) along the ANC treatment gradient in both the short and longer term, except for pH. Base saturation of the upper 15 cm of the mineral B horizons of soils was influenced at the two sites 10 y after treatment application. Although ANC treatments affected nutrient concentrations of tree foliage in the short term, their effect was no longer detectable after 10 y at the two sites. Growth, however, was strongly related to ANC treatments after 10 y, but only at the poor site. From 1990 to 2000, the basal‐area growth rate of trees at the poor site was (mean ± SE) –0.62 ± 0.28 cm² y^–2 tree^–1 for the most negative ANC treatment to +0.90 ± 0.20 cm² y^–2 tree^–1 for the most positive ANC treatment. A climatic‐stress episode occurring in 1995/96 appeared to accentuate the growth decline of trees subjected to the most negative ANC treatment at the poor site. The experimental results support the hypothesis that atmospheric acid deposition load can cause forest soil base‐cation depletion, acidification, and predispose sugar maple to health and growth decline in the longer term in base‐cation‐poor soils, and that the phenomenon may be reversible by adding alkalizers.     

Acidity status of surface waters in Massachusetts

The Massachusetts Acid Rain Monitoring project surveyed 80.5% of the state's 5294 named water bodies between 1983 and 1985. PH and acid neutralizing capacity (ANC) were measured monthly the first 14 mo and semi-annually afterwards. Sample collection and analysis were performed by volunteers. The majority of surface waters in Massachusetts were found to be sensitive to possible long term acidification, with 63% exhibiting ANC less than 200 μeq L^?1 and 22% with ANC less than 40 μeq L^?1. Seasonal patterns in ANC were observed, the median ANC being 384 μeq L^?1 in summer/fall and 134 μeq L^?1 in winter/spring. Geographical differences were also found across the state: the streams and lakes with lowest pH and ANC were located in the southeastern and north-central parts of the state, while the most alkaline surface waters were found in the western-most part of the state, which is the only area of the state with significant limestone deposits.     

Magic Modeling of Long-Term Lake Water and Soil Chemistry at Abborrträsket, Northern Sweden

The geochemical model MAGIC has been applied to the Abborrträsket lake catchment in northern Sweden for the period 1843-2000. The two objectives were to 1.) simulate historical biogeochemical fluxes and pools and 2.) test whether the MAGIC model of biogeochemical cycling contradicts the published diatom record of a relatively stable pH (around 6) during the last two centuries in this weakly buffered, acid sensitive lake. Abborrträsket has received elevated sulfur and nitrogen deposition in the second half of the 20th Century and had a large part of its catchment clearcut in 1975. The MAGIC simulation of very small pH decline from 6.1 to 5.9 between 1843 and 1987 was comparable to the published diatom reconstructions of almost stable lake water pH up until the lake was limed in 1988. MAGIC also simulated the modern soil and water chemistry, including lake liming. Thus the diatom indication of stable pH cannot be dismissed as necessarily incorrect.     

Effects of acid sulphate on DOC release in mineral soils: the influence of SO42− retention and Al release

Dissolved organic carbon (DOC) in acid‐sensitive upland waters is dominated by allochthonous inputs from organic‐rich soils, yet inter‐site variability in soil DOC release to changes in acidity has received scant attention in spite of the reported differences between locations in surface water DOC trends over the last few decades. In a previous paper, we demonstrated that pH‐related retention of DOC in O horizon soils was influenced by acid‐base status, particularly the exchangeable Al content. In the present paper, we investigate the effect of sulphate additions (0–437 µeq l^?1) on DOC release in the mineral B horizon soils from the same locations. Dissolved organic carbon release decreased with declining pH in all soils, although the shape of the pH‐DOC relationships differed between locations, reflecting the multiple factors controlling DOC mobility. The release of DOC decreased by 32–91% in the treatment with the largest acid input (437 µeq l^?1), with the greatest decreases occurring in soils with very small % base saturation (BS, < 3%) and/or large capacity for sulphate (SO₄^2?) retention (up to 35% of added SO₄^2?). The greatest DOC release occurred in the soil with the largest initial base status (12% BS). These results support our earlier conclusions that differences in acid‐base status between soils alter the sensitivity of DOC release to similar sulphur deposition declines. However, superimposed on this is the capacity of mineral soils to sorb DOC and SO₄^2?, and more work is needed to determine the fate of sorbed DOC under conditions of increasing pH and decreasing SO₄^2?.     

Calculating Critical Loads of Sulfur Deposition for 100 Surface Waters in China Using the Magic Model

Although decades of acid deposition have apparently not resulted in surface water acidification in China, some surface waters may have the potential trend of being acidified, especially those in southern China. In this paper, a dynamic acidification model–MAGIC was applied to 100 surface waters in southern and northeastern China to evaluate the impact of acid deposition to surface waters and to determine their critical loads of S deposition, both regions having distinguishing soil, geological and acid deposition characteristics. Results indicate that most surface waters included in this paper are not sensitive to acid deposition, with critical loads of S for these waters comparatively high. On the other hand, surface waters in southern China, especially those in Fujian, Jiangxi and Guangdong provinces, are more susceptible to acidification than those in northeastern China, which coincides with their different patterns of soil, geological and acid deposition conditions. Among all the waters, a few small ponds, such as those on top of the Jinyun mountain and Emei mountain, are the most sensitive to acid deposition with critical loads of 1.84 and 3.70 keq·ha^?1·yr^?1, respectively. For the considerable ANC remaining in most 100 surface waters, it is not likely that acidification will occur in the near future for these waters.     

Acidic precipitation: Considerations for an air quality standard

Acidic precipitation, wet or frozen precipitation with a H⁺ concentration greater than 2.5 μeq l^?1, is a significant air pollution problem in the United States. The chief anions accounting for the H⁺ in rainfall are nitrate and sulfate. Agricultural systems may derive greater net nutritional benefits from increasing inputs of acidic rain than do forest systems when soils alone are considered. Agricultural soils may benefit because of the high N and S requirements of agricultural plants. Detrimental effects to forest soils may result if atmospheric H⁺ inputs significantly add to or exceed H⁺ production by soils. Acidification of fresh waters of southern Scandinavia, southwestern Scotland, southeastern Canada, and northeastern United States is caused by acid deposition. Areas of these regions in which this acidification occurs have in common, highly acidic precipitation with volume weighted mean annual H⁺ concentrations of 25 μeq l^?1 or higher and slow weathering of granitic or precambrian bedrock with thin soils deficient in minerals which would provide buffer capacity. Biological effects of acidification of fresh waters are detectable below pH 6.0. As lake and stream pH levels decrease below pH 6.0, many species of plants, invertebrates, and vertebrates are progressively eliminated. Generally, fisheries are severely impacted below pH 5.0 and are completely destroyed below pH 4.8. At the present time studies documenting effects of acidic precipitation on terrestrial vegetation are insufficient to establish an air quality standard. It must be demonstrated that current levels of precipitation acidity alone significantly injure terrestrial vegetation. For aquatic ecosystems, current research indicates that establishing a maximum permissible value for the volume weighted annual H⁺ concentration of precipitation at 25 μeq l^?1 may protect the most sensitive areas from permanent lake acidification. Such a standard would probably protect other systems as well.