Stream Acid Neutralizing Capacity Research Articles

Assessing impacts of sulfur deposition on aquatic ecosystems: A decision support system for the Southern Appalachians

AbstractWith climate change and ongoing impacts from human development and resource extraction, US federal land management agencies are acutely concerned with managing for healthy aquatic ecosystems in the Southern Appalachian Mountain (SAM) Region. Here, we describe development of a spatial decision support application to assess the biological and ecological impacts of atmospheric S and N deposition on aquatic ecosystems of the region. We first summarize foundational published work to predict continuous maps of surface water acid neutralizing capacity (ANC) and soil base cation weathering (BCw). We use the predicted ANC and BCw maps to estimate steady‐state critical loads (CLs) of atmospheric S and N deposition. We included estimated CLs of atmospheric N to get a complete picture of CLs and potential exceedances. We then present a logic‐based decision support model for assessing effects of S and N deposition based on statistically modeled stream ANC and CL exceedance. The model is easily modified for continuous monitoring of CL exceedance patterns as new S and N deposition and ANC data become available. We present mapped model results for the SAM study area and an important subset of the region, the Great Smoky Mountains National Park. ANC modeling results revealed that predicted acid sensitivity was spatially variable, with areas of relatively low stream ANC (<50 μeq · L−1) and soil BCw (<50 meq · m−2 · year−1) predominantly found in certain critical areas. Within the Great Smoky Mountains National Park, evidence for S CL exceedance based on an ANC criterion of 50 μeq · L−1 was strong at locations where ambient S deposition was at least two times the CL. We also predicted likely impacts of CL exceedances on aquatic insect species richness and native fish abundance. Responses for insect species richness and fish impact showed variability similar to CL exceedance, with increasing impact positively correlated with elevation. Finally, we discuss ways that the decision support system can be used to prioritize management across the region.

Regional target loads of atmospheric nitrogen and sulfur deposition for the protection of stream and watershed soil resources of the Adirondack Mountains, USA

Acidic deposition contributes to a range of environmental impacts across forested landscapes, including acidification of soil and drainage water, toxic aluminum mobilization, depletion of available soil nutrient cations, and impacts to forest and aquatic species health and biodiversity. In response to decreasing levels of acidic deposition, soils and drainage waters in some regions of North America have become gradually less acidic. Thresholds of atmospheric deposition at which adverse ecological effects are manifested are called critical loads (CLs) and/or target loads (TLs). Target loads are developed based on approaches that account for spatial and temporal aspects of acidification and recovery. Exceedance represents the extent to which current or projected future levels of acidic deposition exceed the level expected to cause ecological harm. We report TLs of sulfur (S) and nitrogen (N) deposition and the potential for ecosystem recovery of watershed soils and streams in the Adirondack region of New York State, resources that have been less thoroughly investigated than lakes. Regional TLs were calculated by statistical extrapolation of hindcast and forecast simulations of 25 watersheds using the process-based model PnET-BGC coupled with empirical observations of stream hydrology and established sensitivity of sugar maple (Acer saccharum) to soil base saturation and brook trout (Salvelinus fontinalis) to stream acid neutralizing capacity (ANC). Historical impacts and the expected recovery timeline of regional soil and stream chemistry and fish community condition within the Adirondack Park were evaluated. Analysis suggests that many low-order Adirondack streams and associated watershed soils have low TLs (<40 meq/m2/yr of N + S deposition) to achieve specified benchmarks for recovery of soil base saturation or stream ANC. Acid-sensitive headwater and low-order streams and watershed soils in the region are expected to experience continued adverse effects from N and S deposition well into the future even under aggressive emissions reductions. Watershed soils and streams in the western Adirondack Park are particularly vulnerable to acidic deposition and currently in exceedance of TLs. The methods used for linking statistical and process-based models to consider chemical and biological response under varying flow conditions at the regional scale in this study can be applied to other areas of concern.

The response of stream ecosystems in the Adirondack region of New York to historical and future changes in atmospheric deposition of sulfur and nitrogen

The present-day acid-base chemistry of surface waters can be directly linked to contemporary observations of acid deposition; however, pre-industrial conditions are key to predicting the potential future recovery of stream ecosystems under decreasing loads of atmospheric sulfur (S) and nitrogen (N) deposition. The integrated biogeochemical model PnET-BGC was applied to 25 forest watersheds that represent a range of acid sensitivity in the Adirondack region of New York, USA to simulate the response of streams to past and future changes in atmospheric S and N deposition, and calculate the target loads of acidity for protecting and restoring stream water quality and ecosystem health. Using measured data, the model was calibrated and applied to simulate soil and stream chemistry at all study sites. Model hindcasts indicate that historically stream water chemistry in the Adirondacks was variable, but inherently sensitive to acid deposition. The median model-simulated acid neutralizing capacity (ANC) of the streams was projected to be 55 μeq L-1 before the advent of anthropogenic acid deposition (~1850), decreasing to minimum values of 10 μeq L-1 around the year 2000. The median simulated ANC increased to 13 μeq L-1 by 2015 in response to decreases in acid deposition that have occurred over recent decades. Model projections suggest that simultaneous decreases in sulfate, nitrate and ammonium deposition are more effective in restoring stream ANC than individual decreases in sulfur or nitrogen deposition. However, the increases in stream ANC per unit equivalent decrease in S deposition is greater compared to decreases in N deposition. Using empirical algorithms, fish community density and biomass are projected to increase under several deposition-control scenarios that coincide with increases in stream ANC. Model projections suggest that even under the most aggressive deposition-reduction scenarios, stream chemistry and fisheries will not fully recover from historical acidification by 2200.

Relationships between indicators of acid-base chemistry and fish assemblages in streams of the Great Smoky Mountains National Park

The acidity of many streams in the Great Smoky Mountains National Park (GRSM) has increased significantly since pre-industrial (∼1850) times due to the effects of highly acidic atmospheric deposition in poorly buffered watersheds. Extensive stream-monitoring programs since 1993 have shown that fish and macroinvertebrate assemblages have been adversely affected in many streams across the GRSM. Matching chemistry and fishery information collected from 389 surveys performed at 52 stream sites over a 22-year period were assessed using logistic regression analysis to help inform the U.S. Environmental Protection Agency’s assessment of the environmental impacts of emissions of oxides of nitrogen (NOx) and sulfur (SOx). Numerous logistic equations and associated curves were derived that defined the relations between acid neutralizing capacity (ANC) or pH and different levels of community richness, density, and biomass; and density and biomass of brook trout, rainbow trout, and small prey (minnow) populations in streams of the GRSM. The equations and curves describe the status of fish assemblages in the GRSM under contemporary emission levels and deposition loads of nitrogen (N) and sulfur (S) and provide a means to estimate how newly proposed (and various alternative) target deposition loads, which strongly influence stream ANC, might affect key ecological indicators. Several examples using ANC, community richness, and brook trout density are presented to illustrate the steps needed to predict how future changes in stream chemistry (resulting from different target deposition loads of N and S) will affect the probabilities of observing specific levels of selected biological indicators in GRSM streams. The implications of this study to the regulation of NOx and SOx emissions, water quality, and fisheries management in streams of the GRSM are discussed, but also qualified by the fact that specific examples provided need to be further explored before recommendations concerning their use as ecological indicators could be proposed.

The response of soil and stream chemistry to decreases in acid deposition in the Catskill Mountains, New York, USA

The Catskill Mountains have been adversely impacted by decades of acid deposition, however, since the early 1990s, levels have decreased sharply as a result of decreases in emissions of sulfur dioxide and nitrogen oxides. This study examines trends in acid deposition, stream-water chemistry, and soil chemistry in the southeastern Catskill Mountains. We measured significant reductions in acid deposition and improvement in stream-water quality in 5 streams included in this study from 1992 to 2014. The largest, most significant trends were for sulfate (SO42−) concentrations (mean trend of −2.5 μeq L−1 yr−1); hydrogen ion (H+) and inorganic monomeric aluminum (Alim) also decreased significantly (mean trends of −0.3 μeq L−1 yr−1 for H+ and −0.1 μeq L−1 yr−1 for Alim for the 3 most acidic sites). Acid neutralizing capacity (ANC) increased by a mean of 0.65 μeq L−1 yr−1 for all 5 sites, which was 4 fold less than the decrease in SO42− concentrations. These upward trends in ANC were limited by coincident decreases in base cations (−1.3 μeq L−1 yr−1 for calcium + magnesium). No significant trends were detected in stream-water nitrate (NO3−) concentrations despite significant decreasing trends in NO3− wet deposition. We measured no recovery in soil chemistry which we attributed to an initially low soil buffering capacity that has been further depleted by decades of acid deposition. Tightly coupled decreasing trends in stream-water silicon (Si) (−0.2 μeq L−1 yr−1) and base cations suggest a decrease in the soil mineral weathering rate. We hypothesize that a decrease in the ionic strength of soil water and shallow groundwater may be the principal driver of this apparent decrease in the weathering rate. A decreasing weathering rate would help to explain the slow recovery of stream pH and ANC as well as that of soil base cations.

Critical loads and exceedances for nitrogen and sulfur atmospheric deposition in Great Smoky Mountains National Park, United States

AbstractAcid deposition has impacted sensitive streams, reducing the amount of habitat available for fish survival in the Great Smoky Mountains National Park (GRSM) and portions of the surrounding Southern Appalachian Mountains by decreasing pH and acid neutralizing capacity (ANC) and mobilizing aluminum dissolved from soil. Land managers need to understand whether streams can recover from the elevated acid deposition and sustain the healthy aquatic biota, and if so, how long it would take to achieve this condition. We used a dynamic biogeochemical model, PnET‐BGC, to evaluate past, current, and potential future changes in soil and water chemistry of watersheds of the GRSM in response to the projected changes in acid deposition. The model was parameterized with soil, vegetation, and stream observations for 30 stream watersheds in the GRSM. Using model results, the level of atmospheric deposition (known as a “critical load”) above which harmful ecosystem effects (defined here as modeled stream ANC below a defined target) occur was determined for the 30 study watersheds. In spite of the recent marked decreases in atmospheric sulfur and nitrate deposition, our results suggest that stream recovery has been limited and delayed due to the high sulfate adsorption capacity of soils in the park resulting in a long lag time for recovery of soil chemistry to occur. Model simulations suggest that over the long term, increases in modeled stream ANC per unit decrease in NH4+ deposition are greater than unit decreases in SO42− or NO3− deposition, due to high SO42− adsorption capacity and the limited N retention of the watersheds. Watershed simulations were used to extrapolate the critical load results to 387 monitored stream sites throughout the park and depict the spatial pattern of atmospheric deposition exceedances. These types of model simulations inform park managers on the amount of air quality improvement needed to meet the stream restoration goals.

High elevation watersheds in the southern Appalachians: Indicators of sensitivity to acidic deposition and the potential for restoration through liming

Southern Appalachian high elevation watersheds have deep rocky soils with high organic matter content, different vegetation communities, and receive greater inputs of acidic deposition compared to low elevation sites within the region. Since the implementation of the Clean Air Act Amendment in the 1990s, concentrations of acidic anions in rainfall have declined. However, some high elevation streams continue to show signs of chronic to episodic acidity, where acid neutralizing capacity (ANC) ranges from 0 to 20μeqL−1. We studied three 3rd order watersheds (North River in Cherokee National Forest, Santeetlah Creek in Nantahala National Forest, and North Fork of the French Broad in Pisgah National Forest) and selected four to six 1st order catchments within each watershed to represent a gradient in elevation (849–1526m) and a range in acidic stream ANC values (11–50μeqL−1). Our objectives were to (1) identify biotic, physical and chemical catchment parameters that could be used as indices of stream ANC, pH and Ca:Al molar ratios and (2) estimate the lime required to restore catchments from the effects of excess acidity and increase base cation availability. We quantified each catchment’s biotic, physical, and chemical characteristics and collected stream, O-horizon, and mineral soil samples for chemical analysis seasonally for one year. Using repeated measures analysis, we examined variability in stream chemistry and catchment characteristics; we used a nested split-plot design to identify catchment characteristics that were correlated with stream chemistry. Watersheds differed significantly and the catchments sampled provided a wide range of stream chemical, biotic, physical and chemical characteristics. Variability in stream ANC, pH, and Ca:Al molar ratio were significantly correlated with catchment vegetation characteristics (basal area, tree height, and tree diameter) as well as O-horizon nitrogen and aluminum concentrations. Total soil carbon and calcium (an indicator of parent material), were significant covariates for stream ANC, pH and Ca:Al molar ratios. Lime requirement estimates did not differ among watersheds but this data will help select catchments for future restoration and lime application studies. Not surprisingly, this work found many vegetation and chemical characteristics that were useful indicators of stream acidity. However, some expected relationships such as concentrations of mineral soil extractable Ca and SO4 were not significant. This suggests that an extensive test of these indicators across the southern Appalachians will be required to identify high elevation forested catchments that would benefit from restoration activities.

Sensitivity analyses of MAGIC modelled predictions of future impacts of whole-tree harvest on soil calcium supply and stream acid neutralizing capacity

Forest biofuel is a main provider of energy in Sweden and the market is expected to grow even further in the future. Removal of logging residues via harvest can lead to short-term acidification but the long-term effects are largely unknown. The objectives of this study were to 1) model the long-term effect of whole-tree harvest (WTH) on soil and stream water acidity and 2) perform sensitivity analyses by varying the amounts of logging residues, calcium (Ca2+) concentrations in tree biomass and site productivity in nine alternate scenarios. Data from three Swedish forested catchments and the Model of Acidification of Groundwater in Catchments (MAGIC) were used to simulate changes in forest soil exchangeable Ca2+ pools and stream water acid neutralizing capacity (ANC) at Gammtratten, Kindla and Aneboda. Large depletions in soil Ca2+ supply and a reversal of the positive trend in stream ANC were predicted for all three sites after WTH. However, the magnitude of impact on stream ANC varied depending on site and the concentration of mobile strong acid anions. Contrary to common beliefs, the largest decrease in modelled ANC was observed at the well-buffered site Gammtratten. The effects at Kindla and Aneboda were much more limited and not large enough to offset the general recovery from acidification. Varying the tree biomass Ca2+ concentrations exerted the largest impact on modelled outcome. Site productivity was the second most important variable whereas changing biomass amounts left on site only marginally affected the results. The outcome from the sensitivity analyses pointed in the same direction of change as in the base scenario, except for Kindla where soil Ca2+ pools were predicted to be replenished under a given set of input data. The reliability of modelled outcome would increase by using site-specific Ca2+ concentrations in tree biomass and field determined identification of site productivity.

Acid-base characteristics of the Grass Pond watershed in the Adirondack Mountains of New York State, USA: interactions among soil, vegetation and surface waters

Abstract. Grass Pond watershed is located within the southwestern Adirondack Mountain region of New York State, USA. This region receives some of the highest rates of acidic deposition in North America and is particularly sensitive to acidic inputs due to many of its soils having shallow depths and being generally base poor. Differences in soil chemistry and tree species between seven subwatersheds were examined in relation to acid-base characteristics of the seven major streams that drain into Grass Pond. Mineral soil pH, stream water BCS (base-cation surplus) and pH exhibited a positive correlation with sugar maple basal area (p = 0.055; 0.48 and 0.39, respectively). Black cherry basal area was inversely correlated with stream water BCS, ANC (acid neutralizing capacity)c and NO3- (p = 0.23; 0.24 and 0.20, respectively). Sugar maple basal areas were positively associated with watershed characteristics associated with the neutralization of atmospheric acidic inputs while in contrast, black cherry basal areas showed opposite relationships to these same watershed characteristics. Canonical correspondence analysis indicated that black cherry had a distinctive relationship with forest floor chemistry apart from the other tree species, specifically a strong positive association with forest floor NH4, while sugar maple had a distinctive relationship with stream chemistry variables, specifically a strong positive association with stream water ANCc, BCS and pH. Our results provide evidence that sugar maple is acid-intolerant or calciphilic tree species and also demonstrate that black cherry is likely an acid-tolerant tree species.

Influence of basin characteristics on baseflow and stormflow chemistry in the Great Smoky Mountains National Park, USA

Relationships between stream chemistry and elevation, area, Anakeesta geology, soil properties, and dominant vegetation were evaluated to identify the influence of basin characteristics on baseflow and stormflow chemistry in eight streams of the Great Smoky Mountains National Park. Statistical analyses were employed to determine differences between baseflow and stormflow chemistry, and relate basin-scale factors governing local chemical processes to stream chemistry. Following precipitation events, stream pH was reduced and aluminium concentrations increased, while the response of acid neutralizing capacity (ANC), nitrate, sulfate, and base cations varied. Several basin characteristics were highly correlated with each other, demonstrating the interrelatedness of topographical, geological, soil, and vegetative parameters. These interrelated basin factors uniquely influenced acidification response in these streams. Streams in higher-elevation basins (>975 m) had significantly lower pH, ANC, sodium, and silicon and higher nitrate concentrations (p 10%) had significantly lower pH and sodium concentrations, and higher aluminium concentrations. Chemical and physical soil characteristics and dominant overstory vegetation in basins were more strongly correlated with baseflow and stormflow chemical constituents than topographical and geological basin factors. Saturated hydraulic conductivity, of all the soil parameters, was most related to concentrations of stormflow constituents. Basins with higher average hydraulic conductivities were associated with lower stream pH, ANC, and base cation concentrations, and higher nitrate and sulfate concentrations. These results emphasize the importance of soil and geological properties influencing stream chemistry and promote the prioritization of management strategies for aquatic resources. Copyright © 2012 John Wiley & Sons, Ltd.

Target loads of atmospheric sulfur deposition for the protection and recovery of acid-sensitive streams in the Southern Blue Ridge Province

An important tool in the evaluation of acidification damage to aquatic and terrestrial ecosystems is the critical load (CL), which represents the steady-state level of acidic deposition below which ecological damage would not be expected to occur, according to current scientific understanding. A deposition load intended to be protective of a specified resource condition at a particular point in time is generally called a target load (TL). The CL or TL for protection of aquatic biota is generally based on maintaining surface water acid neutralizing capacity (ANC) at an acceptable level. This study included calibration and application of the watershed model MAGIC (Model of Acidification of Groundwater in Catchments) to estimate the target sulfur (S) deposition load for the protection of aquatic resources at several future points in time in 66 generally acid-sensitive watersheds in the southern Blue Ridge province of North Carolina and two adjoining states. Potential future change in nitrogen leaching is not considered. Estimated TLs for S deposition ranged from zero (ecological objective not attainable by the specified point in time) to values many times greater than current S deposition depending on the selected site, ANC endpoint, and evaluation year. For some sites, one or more of the selected target ANC critical levels (0, 20, 50, 100μeq/L) could not be achieved by the year 2100 even if S deposition was reduced to zero and maintained at that level throughout the simulation. Many of these highly sensitive streams were simulated by the model to have had preindustrial ANC below some of these target values. For other sites, the watershed soils contained sufficiently large buffering capacity that even very high sustained levels of atmospheric S deposition would not reduce stream ANC below common damage thresholds.

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 μeq/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 μeq/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.

Predicting Acidification Recovery at the Hubbard Brook Experimental Forest, New Hampshire: Evaluation of Four Models

The performance and prediction uncertainty (owing to parameter and structural uncertainties) of four dynamic watershed acidification models (MAGIC, PnET-BGC, SAFE, and VSD) were assessed by systematically applying them to data from the Hubbard Brook Experimental Forest (HBEF), New Hampshire, where long-term records of precipitation and stream chemistry were available. In order to facilitate systematic evaluation, Monte Carlo simulation was used to randomly generate common model input data sets (n = 10,000) from parameter distributions; input data were subsequently translated among models to retain consistency. The model simulations were objectively calibrated against observed data (streamwater: 1963-2004, soil: 1983). The ensemble of calibrated models was used to assess future response of soil and stream chemistry to reduced sulfur deposition at the HBEF. Although both hindcast (1850-1962) and forecast (2005-2100) predictions were qualitatively similar across the four models, the temporal pattern of key indicators of acidification recovery (stream acid neutralizing capacity and soil base saturation) differed substantially. The range in predictions resulted from differences in model structure and their associated posterior parameter distributions. These differences can be accommodated by employing multiple models (ensemble analysis) but have implications for individual model applications.

Long-Term Effects of Acidic Deposition on Water Quality in a High-Elevation Great Smoky Mountains National Park Watershed: Use of an Ion Input–Output Budget

Impacts from acidic deposition on stream water quality in the Great Smoky Mountains National Park (GRSM) have long been reported; however, a better understanding of the biogeochemical processes that regulate stream acidification is needed for resource management. Water quality monitoring of Noland Divide Watershed (NDW), a high-elevation watershed in the GRSM, was used to generate an ion input–output budget in order to evaluate what processes have influenced stream pH and acid neutralizing capacity (ANC) over the long term. NDW was equipped with wet deposition, throughfall, soil lysimeters, and stream collection stations, and monitoring began in 1991 and continues to the present. Using data from 1991 to 2006, this study found annual deposition fluxes of SO42− and NO3− averaged 1,735 and 863 eq ha−1 year−1, respectively. Data indicated that 61% of the net SO42− entering the watershed was retained, suggesting soil adsorption dominates as a biogeochemical process. Although net SO42− retention was observed, SO42− appeared to move rapidly through NDW during large precipitation events causing stream acidification, as evidenced by significant inverse correlations between biweekly throughfall SO42− flux and stream event pH and ANC. Nitrogen uptake by forest vegetation and nitrification play key roles in regulating NO3− export to the stream as observed by 32% retention of net inorganic nitrogen, and 96% of NH4+ input was converted to NO3− in the uppermost soil horizon. Net export of base cations (Ca2+, Mg2+, Na+) is observed and apparently moderates stream acidification. In contrast, 71% of net K+ input was retained, which is likely due to forest vegetation uptake. Net export of Ca2+ was 867 eq ha−1 year−1 compared to net throughfall of 790 eq ha−1 year−1. Long-term cation depletion from the NDW soils could limit recovery potential in stream water quality. Findings from this NDW study suggest that future stream acidification conditions in high-elevation GRSM watersheds are dependent on interrelated biogeochemical processes and precipitation patterns, illustrating the need to better understanding potential impacts of climate variability on stream water quality.

PH and Acid Anion Time Trends in Different Elevation Ranges in the Great Smoky Mountains National Park

Quarterly base flow water quality data collected from October, 1993 to November, 2002 at 90 stream sites in the Great Smoky Mountains National Park were used in step-wise multiple linear regression models to analyze pH, acid neutralizing capacity (ANC), and sulfate and nitrate long-term time trends. The potential predictor variables included cumulative Julian day, seasonality, elevation, basin slope, stream order, precipitation, surrogate streamflows, geology, and acid depositional fluxes. Modeling revealed statistically significant decreasing trends in pH and sulfate with time at lower elevations, but generally no long-term time trends in stream nitrate or ANC. The best forecasting models were chosen based on maximizing the r2 of a holdout data set. If conditions remain the same and past trends continue, the forecasting models suggest that 30.0% of the sampling sites will reach pH values less than 6.0 in less than 10 years , 63.3% in less than 25 years , and 96.7% in less than 50 years . The pH forecasti...

Factors controlling long-term changes in soil pools of exchangeable basic cations and stream acid neutralizing capacity in a northern hardwood forest ecosystem

Understanding the factors regulating the concentrations of basic cations in soils and surface waters is critical if rates of recovery are to be predicted in response to decreases in acidic deposition. Using a dynamic simulation model (PnET-BGC), we evaluated the extent to which atmospheric deposition of strong acids and associated leaching by strong anions, atmospheric deposition of basic cations through changes in emissions of particulate matter, and historical forest cutting have influenced soil pools of exchangeable basic cations and the acid-base status of stream water at the Hubbard Brook Experimental Forest (HBEF) in New Hampshire. Historical deposition of basic cations was reconstructed from regression relationships with particulate matter emissions. Simulation results indicate that the combination of these factors has resulted in changes in the percent soil base saturation, and stream pH and acid neutralizing capacity (ANC) from pre-industrial estimates of ∼20%, ∼6.3 and ∼45 μeq L−1, respectively, to current values of ∼10%, ∼5.0 and ∼−5 μeq L−1, respectively. These current values fall within the critical thresholds at which forest vegetation and aquatic biotic are at risk from soil and surface water acidification due to acidic deposition. While the deposition of strong acid anions had the largest impact on the acid-base status of soil and stream water, the reduction in deposition of basic cations associated with reductions in particulate emissions was estimated to have contributed about 27% of the depletion in soil Ca2+ exchange pool and 15% of the decreases in stream water concentrations of basic cations. Decline in stream water concentrations of basic cation occurred under both increasing and decreasing exchangeable pools, depending on the process controlling the acid base status of the ecosystem. Model calculations suggest that historical forest cutting has resulted in only slight decreases in soil pools of exchangeable basic cations, and has had a limited effect on stream ANC over the long-term.

Evaluation of an integrated biogeochemical model (PnET‐BGC) at a northern hardwood forest ecosystem

An integrated biogeochemical model (PnET‐BGC) was formulated to simulate chemical transformations of vegetation, soil, and drainage water in northern forest ecosystems. The model operates on a monthly time step and depicts the major biogeochemical processes, such as forest canopy element transformations, hydrology, soil organic matter dynamics, nitrogen cycling, geochemical weathering, and chemical equilibrium reactions involving solid and solution phases. The model was evaluated against soil and stream data at the Hubbard Brook Experimental Forest, New Hampshire. Model predictions of concentrations and fluxes of major elements generally agreed reasonably well with measured values, as estimated by normalized mean error and normalized mean absolute error. Model output of soil base saturation and stream acid neutralizing capacity were sensitive to parameter values of soil partial pressure of carbon dioxide, soil mass, soil cation exchange capacity, and soil selectivity coefficients of calcium and aluminum. PnET‐BGC can be used as a tool to evaluate the response of soil and water chemistry of forest ecosystems to disturbances such as clear‐cutting, climatic events, and atmospheric deposition.

Acidic deposition, ecosystem processes, and nitrogen saturation in a high elevation Southern Appalachian watershed

High-elevation red spruce-Fraser fir forests in the Southern Appalachian mountains: 1) receive among the highest rates of atmospheric deposition measured in North America, 2) contain old-growth forests, 3) have shown declines in forest health, 4) have sustained high insect-caused fir mortality, and 5) contain poorly buffered soils and stream systems. High rates of nitrogen and sulphur deposition (∼1900 and ∼2200 Eq·ha−1·yr−1, respectively) are dominated by dry and cloud deposition processes. Large leaching fluxes of nitrate-nitrogen (100–1400 Eq·ha−1·yr−1) occur within the soil profile. We have expanded the study to the watershed scale with monitoring of: precipitation, throughfall, stream hydrology, and stream chemistry. Two streamlets drain the 17.4 ha Noland Divide Watershed (1676–1920m) located in the Great Smoky Mountains National Park. A network of 50 20x20 m plots is being used to assess stand structure, biomass, and soil nutrient pools. Nitrate is the predominant anion in the streamlets (weighted concentrations: 47 and 54 μeq·L−1 NO3 −; 31 and 43 μeq·L−1 SO4 2−). Watershed nitrate export is extremely high (∼1000 Eq·ha−1 yr−1), facilitating significant base cation exports. Stream acid neutralizing capacity values are extremely low (−10 to 20 μeq·L−1) and episodic acidifications (pH declines of a full unit in days or weeks time) occur. Annual streamwater sulfate export is on the order of 770 Eq·ha−1yr−1 or about one-third of total annual inputs, indicating there is net watershed sulfate retention. The system is highly nitrogen saturated (Stage 2, Stoddard, 1994) and this condition promotes both chronic and episodic stream acidification.

Beaver pond biogeochemistry: Acid neutralizing capacity generation in a headwater wetland

A beaver pond and its associated inlet and outlet waters in the Adirondack Mountains of New York were monitored for major chemical solutes for 26 months in an effort to quantify underlying chemical controls on the production and consumption of acid neutralizing capacity (ANC). The pond was a net annual sink for inlet Al, SO4 2−, NO3 −; and H4SiO4. The pond was a net annual source of dissolved organic carbon (DOC), NH4 +, and Fe2−. Losses of ANC resulting from Al and basic cation retention, as well as organic anion release (RCOO−) associated with DOC, were more than offset by SO4 2−, and NO3 − retention and Fe2− and NH4 + release, resulting in a net production of ANC. Rates of ANC generation were 120 meq m−2 yr−1 and 310 meq m−2 yr−1, respectively (based on pond surface area), for the non-summer (October-June) and summer (July–September) periods. Seasonal variations in ANC in the outlet stream were largely associated with Fe2+ and DOC release, while ANC in the upland inlet stream was associated with Al, NO3 −, and basic cations, with much less seasonal variation. Controls on stream chemistry were temporally and longitudinally different, for the inlet and outlet streams. The shift to seasonal control of outlet stream ANC by processes associated with organic matter decomposition reactions and anaerobic zone nutrient transformations may be characteristic of headwater wetlands, in temperate zones with seasonal temperature extremes. Beaver impoundments and wetlands may also be important in the upstream mobilization or retention of geologically bound solutes like Al, Fe, and H4SiO4. Headwater wetlands, as sinks for solutes associated with acidic deposition and watershed acidification (i.e., SO4 2−, NO3 −, and Al), may play a role in the amelioration of the effects of these solutes on downstream receiving waters and associated biota. Depending on their location in relation to drainage patterns, these ponded systems may influence the nutrient dynamics of receiving waters through nitrogen transformations and organic carbon cycling.

The effects of acidic deposition on streams in the Appalachian Mountain and Piedmont Region of the Mid‐Atlantic United States

Streams in the Appalachian Mountain area of the mid‐Atlantic receive some of the largest acidic deposition loadings of any region of the United States. A synthesis of the survey data from the mid‐Appalachians yields a consistent picture of the acid base status of streams. Acidic streams, and streams with very low acid neutralizing capacity (ANC), are almost all located in small (&lt;20 km2), upland, forested catchments in areas of base‐poor bedrock. In the subpopulation of upland forested systems, which comprises about half the total stream population in the mid‐Appalachian area, data from various local surveys show that 6–27% of the streams are acidic, and about 25–50% have ANC less than 50 μeq L−1. After excluding streams with acid mine drainage, National Stream Survey estimates for the whole region show that there are 2330 km of acidic streams and 7500 km of streams with ANC less than 50 μeq L−1. Many of the streams with base flow ANC less than 50 μeq L−1 become acidic during storm or snowmelt episodes. Sulfate from atmospheric deposition is the dominant source of strong acid anions in acidic mid‐Appalachian streams. Their low pH (median, 4.9) and high levels of inorganic monomeric aluminum (median, 129 μg L−1) leached through soils by acidic deposition are causing damage to aquatic biota. Quantification of the extent of biological effects, however, is not possible with available data. Localized studies have shown that stream water ANC is closely related to bedrock mineralogy. Attempts to quantify this relationship across the mid‐Appalachians, however, were frustrated by the lack of adequate scale geologic mapping throughout the region. Sulfate mass balance analyses indicate that soils and surface waters of the region have not yet realized the full effects of elevated sulfur deposition due to watershed sulfate retention. Sulfur retention is likely to decrease in the future, resulting in further losses of stream ANC.