Soil Type and Forest Vegetation Influences on Forest Floor Nitrogen Dynamics at the Bear Brook Watershed in Maine (BBWM)

The paired watershed experiment at the Bear Brook Watershed in Maine (BBWM) provided an opportunity to study changes in forest soil O horizon properties as a result of experimental, chronic N additions. The West Bear brook watershed received elevated N and S inputs since November 1989 as bimonthly applications of (NH4)2SO4. Forest floor samples (O horizon) were collected in July of 1992 from three dominant stand and five soil types at BBWM. The (NH4)2SO4 amendments in the treated watershed (West Bear) stimulated potential net nitrification, but significant increases were found only in hardwood O horizons after three years of treatment. Hardwood stand forest floor soil materials had the lowest C:N ratios (mean=23), compared with mixedwood (mean=27) and softwood stands (mean=33). NH4-N accounted for over 95% of the inorganic N in the forest floor. The lack of a strong relationship between soil type and potential net N mineralization at BBWM, coupled with conflicting results in the literature, suggested that stand characteristics were more important than conventional soil nomenclature based on pedogenetic features, or 2.5 years of treatments, in defining differences in soil N dynamics and responses to increased N inputs.     

Nitrogen mineralization in O horizon soils during 27 years of nitrogen enrichment at the Bear Brook Watershed in Maine,USA

Chronic elevated nitrogen (N) deposition has altered the N status of temperate forests, with significant implications for ecosystem function. The Bear Brook Watershed in Maine (BBWM) is a whole paired watershed manipulation experiment established to study the effects of N and sulfur (S) deposition on ecosystem function. N was added bimonthly as (NH₄)₂SO₄ to one watershed from 1989 to 2016, and research at the site has studied the evolution of ecosystem response to the treatment through time. Here, we synthesize results from 27 years of research at the site and describe the temporal trend of N availability and N mineralization at BBWM in response to chronic N deposition. Our findings suggest that there was a delayed response in soil N dynamics, since labile soil N concentrations did not show increases in the treated watershed (West Bear, WB) compared to the reference watershed (East Bear, EB) until after the first 4 years of treatment. Labile N became increasingly available in WB through time, and after 25 years of manipulations, treated soils had 10× more extractable ammonium than EB soils. The WB soils had 200× more extractable nitrate than EB soils, driven by both, high nitrate concentrations in WB and low nitrate concentrations in EB. Nitrification rates increased in WB soils and accounted for ~?50% of net N mineralization, compared to ~?5% in EB soils. The study provides evidence of the decadal evolution in soil function at BBWM and illustrates the importance of long-term data to capture ecosystem response to chronic disturbance.     

Chemistry of Dissolved Organic Carbon at Bear Brook Watershed, Maine: Stream Water Response to (NH4)2SO4 Additions

This study was conducted to determine the response of stream water DOC and organic acidity to increased inputs of ammonium sulfate to a whole catchment. Precipitation, throughfall, soil solutions (from Spodosols) and stream waters were characterized for DOC concentrations and fractions (hydrophobic acids and neutrals, hydrophilic acids, bases, and neutrals) in both the control (East Bear) and the treatment (West Bear) catchments of Bear Brook Watershed, Maine (BBWM), a northern hardwood forest. In all solutions except precipitation, DOC was composed primarily of organic acids, with hydrophobic acids dominating (> 60% of DOC) in forest floor leachates (5000 mol C L-1), and a balance of hydrophobic and hydrophilic acids in deep B horizons and stream waters ( 150 mol C L-1). Stream waters had higher concentrations of DOC during storm or snowmelt events (high discharge), often reaching 300 to 400 mol C L-1. Forest floor leachate C was rapidly attenuated by the mineral soils under all flow conditions, indicating how important mineral soil sorption of DOC was in reducing the loss of C via surface water from BBWM. No differences occurred between control and treatment streams for concentration or composition of DOC due to treatment from 1989 through 1994. In 1995, West Bear Brook had much lower concentrations of DOC than East Bear for the first time. However, this occurred during a year of record low runoff, suggesting that hydrology may have affected export of C. Average annual export of DOC from the catchments was similar (1000 to 2000 mol C ha-1 yr-1). Organic anions in streamwaters increased slightly during high flow events (e.g., East Bear had means of 15 and 19 eq L-1 organic anions during base flow and high discharge in 1995). Treatment of West Bear caused a decrease in organic anions, both in concentration and contribution to overall anion composition (organic anions during high discharge as a percentage of total anions decreased from about 8 to 4% for 1987-89 and 1993-95 samples, respectively). This was probably due to decreased solution pH (greater protonation of organics) and higher concentrations of inorganic anions. Overall, there were no clear, detectable changes in stream water DOC, with only minor changes in organic anions, as a result of treatment with ammonium sulfate.     

Soilaluminum, Iron, and Phosphorus Dynamics in Response to Long-Term Experimental Nitrogen and Sulfur Additions at the Bear Brook Watershed in Maine, USA

Atmospheric deposition of nitrogen (N) and sulfur (S) containing compounds affects soil chemistry in forested ecosystems through (1) acidification and the depletion of base cations, (2) metal mobilization, particularly aluminum (Al), and iron (Fe), (3) phosphorus (P) mobilization, and (4) N accumulation. The Bear Brook Watershed in Maine (BBWM) is a long-term paired whole-watershed experimental acidification study demonstrating evidence of each of these acidification characteristics in a northeastern U.S. forested ecosystem. In 2003, BBWM soils were studied using the Hedley fractionation procedure to better understand mechanisms of response in soil Al, Fe, and P chemistry. Soil P fractionation showed that recalcitrant P was the dominant fraction in these watersheds (49%), followed by Al and Fe associated P (24%), indicating that a majority of the soil P was biologically unavailable. Acidification induced mobilization of Al and Fe in these soils holds the potential for significant P mobilization. Forest type appears to exert important influences on metal and P dynamics. Soils supporting softwoods showed evidence of lower Al and Fe in the treated watershed, accompanied by lower soil P. Hardwood soils had higher P concentrations in surface soils as a result of increased biocycling in response to N additions in treatments. Accelerated P uptake and return in litterfall overshadowed acidification induced P mobilization and depletion mechanisms in hardwoods.     

Comparing decadal responses of whole-watershed manipulations at the Bear Brook and Fernow experiments

The Bear Brook Watershed in Maine (BBWM), USA, and the Fernow Experimental Forest in West Virginia, USA, represent unique, long-term, paired, whole watershed, experimental manipulations focusing on the effects of nitrogen (N) and sulfur (S) deposition on temperate forests. Both watersheds began whole-ecosystem additions of N and S as (NH₄)₂SO₄ in the fall of 1989, and both are entering their third decade of chronic enrichment of the treated watersheds, while the reference watersheds offer unique opportunities to evaluate forest watershed responses to recovery. Differences between BBWM and Fernow in the history of atmospheric deposition, soil properties, and forest composition all contribute to different response trajectories in stream chemical exports over time. The four watersheds represent a spectrum of N enrichment and retention, ranging from ≈98% N retention in the reference watershed in Maine, to ≈20% N retention in the treated watershed in West Virginia. Despite these differences, there is evidence that mechanisms of response in base cation leaching and other processes are similar among all four watersheds. In both cases, the history to date of two decades of research and monitoring has provided new insights into ecosystem response not evident in more traditional short-term research.     

The Bear Brook Watershed, Maine (BBWM), USA

The Bear Brook Watershed Manipulation project in Maine is a paired calibrated watershed study funded by the U. S. EPA. The research program is evaluating whole ecosystem response to elevated inputs of acidifying chemicals. The project consists of a 2.5 year calibration period (1987-1989), nine years of chemical additions of (NH4)2SO4 (15N- and 34S-enriched for several years) to West Bear watershed (1989-1998), followed by a recovery period. The other watershed, East Bear, serves as a reference. Dosing is in six equal treatments/yr of 1800 eq SO4 and NH4/ha/yr, a 200% increase over 1988 loading (wet plus dry) for SO4 and 300% for N (wet NO3 + NH4). The experimental and reference watersheds are forested with mixed hard- and softwoods, and have thin acidic soils, areas of 10.2 and 10.7 ha, and relief of 210 m. Thin till of variable composition is underlain by metasedimentary pelitic rocks and calc-silicate gneiss intruded by granite dikes and sills. For the period 1987-1995, precipitation averaged 1.4 m/yr, had a mean pH of 4.5, with SO4, NO3, and NH4 concentrations of 26, 14, and 7 eq/L, respectively. The nearly perrenial streams draining each watershed have discharges ranging from 0 (East Bear stops flowing for one to two months per year) to 150 L/sec. Prior to manipulation, East Bear and West Bear had a volume weighted annual mean pH of approximately 5.4, alkalinity = 0 to 4 eq/L, total base cations = 184 eq/L (sea-salt corrected = 118 eq/L), and SO4 = 100 to 111 eq/L. Nitrate ranged from 0 to 30 eq/L with an annual mean of 6 to 25 eq/L; dissolved organic carbon (DOC) ranged from 1 to 7 mg/L but was typically less than 3. Episodic acidification occurred at high discharge and was caused by dilution of cations, slightly increased DOC, significantly higher NO3, and the sea-salt effect. Depressions in pH were accompanied by increases in inorganic Al. The West Bear catchment responded to the chemical additions with increased export of base cations, Al, SO4, NO3, and decreased pH, ANC, and DOC. Silica remained relatively constant. Neutralization of the acidifying chemicals occurred dominantly by cation desorption and mobilization of Al.     

Nitrogen and Sulfur Input-Output Budgets in the Experimental and Reference Watersheds, Bear Brook Watershed in Maine (BBWM)

Dry (NH4)2SO4 (1,800 eq-1 ha-1 yr-1) has been applied to the western of two contiguous 10 ha catchments at the Bear Brook Watershed in Maine (BBWM) since November, 1989. The initial rapid and significant response in both S and N in West Bear, compared to the reference East Bear, slowed after three years. Annual S retention of the total experimental treatment decreased from 86 to 34%, with a seven year cumulative retention of 59%. Hydrology influences the export flux of S; S is retained more in dry seasons and dry years. The annual retention of N has decreased from 96 to 81%, with a cumulative retention of 82%. The export of N from the reference watershed has declined from 178 to 23 eq-1 ha-1 yr-1 during the treatment period. The treatment N (as NH4) initially stimulated nitrification, and caused pre-existing N to be lost in runoff, rather than the treatment N. Retention of the treatment N has decreased to approximately 80%. The majority of the retained N is stored in the soil, but the reasons for the decreased flux from the reference watershed are not known.     

Linkages of P and Al Export at High Discharge at the Bear Brook Watershed in Maine

Phosphorus chemistry in streams was evaluated at the paired watershed study at the Bear Brook Watershed, Maine. The West Bear catchment has been treated bimonthly since 1989 with 1,800 eq (NH4)2SO4 ha-1 yr-1. East Bear was the untreated reference watershed. During 1993, concentration of total phosphorus (P) in weekly samples from East and West Bear Brook ranged from 0 to 15 g L-1. The median values were 2 and 4 g L-1 for East and West Bear, respectively. During a high discharge event in January of 1995, the concentration of dissolved P remained relatively constant ( 3 g L-1) as pH decreased from 5.63 to 5.08 and from 5.14 to 4.75 in East and West Bear, respectively. The concentration of total P increased to ca. 60 g L-1 during the rising limb of the hydrograph in West Bear, four times the value in East Bear, total P then declined rapidly as discharge remained high followed by an increase. Dissolved Al increased in both streams during the episodic acidification. West Bear, the more acidic, had concentrations of dissolved Al four times those of East Bear (maximum of 1.1 mg L-1 versus 0.25 mg L-1). Acid-soluble particulate Al increased to 0.2 and 4.2 mg L-1 for East and West Bear, respectively, in parallel to total P (but was 102 greater than total P) and then declined in parallel to total P while discharge remained high. Total P, dissolved P, and particulate Al did not relate to pH. Total P and particulate Al and Fe were strongly correlated. Concurrently, base cations remained relatively constant or decreased slightly. Particulate acid-soluble Al exceeded particulate acid-soluble base cations. We hypothesize that the particulate P was occluded in, or adsorbed on, acid-soluble particulate Al(OH)3. This Al(OH)3. This Al(OH)3 precipitates as emerging acidic groundwater degasses CO2 and pH rises. The export of Al and P is greater from the treated watershed because the induced acidification is translocating more Al from soils to the stream. Most of the export of P is related to acid-soluble Al particulate material.     

Using Ion-Exchange Resins to Study Soil Response to Experimental Watershed Acidification

Ion-exchange resins (IER) offer alternative approaches to measuring ionic movement in soils that may have advantages over traditional approaches in some settings, but more information is needed to understand how IER compare with traditional methods of measurement in forested ecosystems. At the Bear Brook Watershed in Maine (BBWM), one of two paired, forested watersheds is treated bi-monthly with S and N (28.8 and 25.2kgha⁻¹yr⁻¹ of S and N, respectively). Both IER and ceramic cup tension lysimeters were used to study soil solution responses after ∼11 years of treatment. Results from both methods showed treatments resulted in the mobilization of base cations and Al, and higher SO₄—S and inorganic N in the treated watershed. Both methods indicated similar differences in results associated with forest type (hardwoods versus softwoods), a result of differences in litter quality and atmospheric aerosol interception capacity. The correlation between lysimeter and IER data for individual analytes varied greatly. Significant correlations were evident for Na (r=0.75), Al (r=0.65), Mn (r=0.61), Fe (r=0.57), Ca (r=0.49), K (r=0.41) and NO₃—N (r=0.59). No correlation was evident between IER and soil solution data for NH₄—N and Pb. Both IER and soil solution techniques suggested similar interpretations of biogeochemical behavior in the watershed.     

Effects of chronic ammonium sulfate treatment on the forest at the Bear Brook Watershed in Maine

At the Bear Brook Watershed in Maine (BBWM), the forest tree composition was characterized and the effects of the chronic ammonium sulfate ((NH₄)₂SO₄) treatment on basal area growth, foliar chemistry, and gas exchange were investigated on forest species. The BBWM is a paired watershed forest ecosystem study with one watershed, West Bear (WB), treated since 1989 with 26.6 kg N ha^???1 year^???1 and 30 kg S ha^???1 year^???1applied bimonthly as (NH₄)₂SO₄, while the other watershed, East Bear (EB), serves as a reference. Tree species richness, density, and mortality were found to be similar between watersheds. Basal area increment was estimated from red spruce and sugar maple, showing that, for the first 7 years of treatment, it was significantly higher for sugar maple growing in WB compared to EB, but no differences were observed for red spruce between watersheds. However, the initial higher sugar maple basal area growth in WB subsequently decreased after 8 years of treatment. Foliar chemical analysis performed in trees, saplings, and ground flora showed higher N concentrations in the treated WB compared to the reference EB. But, foliar cation concentrations, especially Ca and Mg, were significantly lower for most of the species growing in WB compared with those growing in EB. For sugar maple, foliar N was higher on WB, but there were no differences in foliar Ca and Mg concentrations between treated and reference watersheds. In addition, only sugar maple trees in the treated WB showed significantly higher photosynthetic rates compared to reference EB trees.     

Soil chemical and physical properties at the Bear Brook Watershed in Maine, USA

Acidic deposition leads to the acidification of waters and accelerated leaching and depletion of soil base cations. The Bear Brook Watershed in Maine has used whole-watershed chemical manipulations to study the effects of elevated N and S on forest ecosystem function on a decadal time scale. The objectives of this study were to define the chemical and physical characteristics of soils in both the reference and treated watersheds after 17 years of treatment and assess evidence of change in soil chemistry by comparing soil studies in 1998 and 2006. Results from 1998 confirmed depletion of soil base cation pools and decreased pH due to elevated N and S within the treated watershed. However, between 1998 and 2006, during a period of declining SO $_{4}^{\,\,2-}$ deposition and continued whole-watershed experimental acidification on the treated watershed, there was little evidence of continued soil exchangeable base cation concentration depletion or recovery. The addition of a pulse of litterfall and accelerating mineralization from a severe ice storm in 1998 may have had significant effects on forest floor nutrient pools and cycling between 1998 and 2006. Our findings suggest that mineralization of additional litter inputs from the ice storm may have obscured temporal trends in soil chemistry. The physical data presented also demonstrate the importance of coarse fragments in the architecture of these soils. This study underscores the importance of long-term, quantitative soil monitoring in determining the trajectories of change in forest soils and ecosystem processes over time.     

Effects of acid deposition on watershed ecosystems of national parks in the great lakes basin

Legally protected national parks provide an appropriate substrate for essential long-term study of ecosystem structure and function, and for detecting trends in natural and human-induced stress. The absence of unplanned site manipulation in such areas is especially valuable for such research. Our present research has two major components. The first is the long-term ecosystem-level study of the effects of atmospheric contaminants on ecosystem processes. The overall objective is to evaluate ecosystem aquatic/terrestrial linkages and their role in establishing aquatic ecosystem sensitivity to anthropic atmospheric inputs. Four watershed/lake ecosystems, representative of much of the region's diversity, are under study. Two mature boreal sites on Isle Royale are characterized by first-order perennial surface stream input and lake outflow. Two additional mainland northern hardwood sites, one with shallow soils and one with soils derived from glacial till, are characterized by sensitive aquatic systems. One site is in a private reserve and the other in Pictured Rocks National Lakeshore. Surface outflow is gaged by Parshall flume and stage height recorder. Meteorological stations record variables for estimating evapotranspiration. One-tenth ha plots have been established in all watersheds and three sites have had intensive study of precipitation modification by canopy and forest soil. Five-year mean maximum and minimum lake pH varies from 6.85 to 4.94, Ca²⁺ from 1070 to 54 eq l^-1, K⁺ from 5.42 to 8.35 eq l^-1, NH ₄ ⁺ from 10.12 to 3.23 eq l^-1, HCO ₃ ^sup- from 635 to 24 eq l^-1, NO ₃ ^sup- from 3.27 to 1.54 eq l^-1, and SO ₄ ^sup2- from 110 to 52.7 eq l^-1. The relatively high NO ₃ ^sup- values observed in one lake are the result of stream drainage from a watershed dominated by Alnus rugosa, and another has high seasonal NO ₃ ^sup- inputs during spring runoff. However, owing to periodic winter thaws, significant snowpack release of nutrients generally precedes maximum spring stream runoff. Water chemistry in both sensitive and non-sensitive lakes appears to be primarily reflecting how the conterminous terrestrial system is retaining atmospheric inputs more than the quality of direct lake atmospheric input. This is especially evident for H⁺, NO ₃ ^sup- and SO ₄ ^sup2- .The second component is the assessment of watershed acidification, SO ₄ ^sup2- output and soil retention across an input gradient. An anthropic deposition gradient provides the opportunity for intersite time-trend analyses as to the effects of inputs. Our study objective was to see if the decreasing west to east input/output values for SO ₄ ^sup2- , noted in small first-order watersheds in national parks from Minnesota to Ohio, might be related to present atmospheric inputs, potential and total soil SO ₄ ^sup2- adsorption, or soil SO ₄ ^sup2- desorption from earlier higher inputs. Precipitation pH ranged from 5.05 at Fernberg, Minnesota to 4.24 at Wooster, Ohio. Minimum and maximum concentrations of NH ₄ ⁺ , NO ₃ ^sup- , SO ₄ ^sup2- and Cl^- were also found at these stations. Stream water concentrations of NO ₃ ^sup- and SO ₄ ^sup2- increase in a similar but sharper gradient. Streams are well buffered. Cation, HCO ₃ ^sup- , NO ₃ ^sup- and especially SO ₄ ^sup2- output increase west to east, but H⁺ output decreases. At the eastern site stream SO ₄ ^sup2- concentration and output exceed HCO ₃ ^sup- . Potential soil SO ₄ ^sup2- adsorption capacity increases eastward, but this capacity is filled. Crystalline Fe hydrous oxides appear more effective than amorphous Fe hydrous oxides at adsorbing SO ₄ ^sup2- . High anthropic anion inputs, inability of forest soil to adsorb additional inputs and perhaps SO ₄ ^sup2- desorption appear responsible for the replacement of HCO ₃ ^sup- by SO ₄ ^sup2- in stream water. The major cation accompanying SO ₄ ^sup2- is Ca²⁺.Contribution from Fourth World Wilderness Congress—Acid Rain Symposium, Denver (Estes Park), Colorado, September 11–18, 1987.     

Controls on N Retention and Exports in a Forested Watershed

We conducted a 15N-tracer study in a fertilized, forested catchment at the Bear Brook Watersheds in Maine (BBWM), USA, in order to characterize N cycling processes, identify sinks for ammonium-N additions, and determine the contribution of the experimental ammonium additions to nitrate exports from the treated catchment. Distributions of 15N in plant tissues, soils, precipitation and streamwater collected before adding tracers showed that nitrate-N (the dominant form of inorganic N deposition at the site) inputs under ambient conditions were depleted in 15N relative to plants and that soil was enriched in 15N relative to plants. The 15N content of streamwater nitrate was within the range of 15N contents in natural plant tissues, suggesting that nitrate deposited from the atmosphere is reduced and assimilated into soil and plant N pools before being leached as nitrate from the catchment. Variations in 15N natural abundances also suggested that most N uptake by trees is from the forest floor and that nitrification occurs in soils at this catchment under ambient conditions. Changes in 15N contents of plant tissues, soils and streamwater after adding a 15N tracer to the ammonium sulfate fertilizer applied to the treated catchment showed that soils were the dominant sink for the labeled ammonium. Surface soils (Oca horizon plus any underlying mineral soil to 5cm depth) assimilated 19 to 31 percent of the 42 kg ha-1 of 15N-labelled ammonium-N during the tracer study. Aboveground biomass assimilated 8 to 17 percent of the labeled ammonium-N additions. Of the three forest types on the catchment, the soil:biomass assimilation ratio of labeled-N was highest in the spruce forest, intermediate in the beech-dominated hardwood forest and lowest in the mixed hardwood-spruce forest. Although ammonium sulfate additions led to increases in streamwater nitrate, only 2 of the 13 kg ha-1 of nitrate-N exported from the catchment during the 2 years of tracer additions was derived from the 42 kg ha-1 of labeled ammonium-N additions.     

Dynamic Hydrologic Simulation of the Bear Brook Watershed in Maine (BBWM)

Bear Brook Watershed in Maine (BBWM) consists of a pair of research watersheds, East Bear Brook (EBB) and West Bear Brook (WBB). Years of research and observations have shown both watersheds have high similarity in geographic and hydrologic characteristics; a simple comparison of hydrographs from these two watersheds further substantiates this similarity. The Object Watershed Link Simulation (OWLS) model was developed and used to simulate the hydrological processes within the BBWM. The OWLS model is a 3-dimensional, vector-based, visualized, physically-based, distributed watershed hydrologic model. Simulation results not only provide a close examination of hydrologic processes within a watershed, but also dynamically visualize the processes of flow separations and Variable Source Areas (VSA). Results from flow separations suggest that surface flow from riparian area is the predominate component for the flood rising limb and that macropore flow from riparian area dominates during the falling limb. Soil matrix flow has little effect flood period but is a persistent contributor to base flow. Results from VSA visualization demonstrate 3-D dynamic changes in surface flow distribution and suggest that downstream riparian areas are the major contributing area for peak flow. As water chemistry is highly relevant to the flow paths within a watershed, simulations have provided valuable information about source of stream flow and the water migration dynamics to support the study of watershed chemistry in the BBWM. More specific linkages between the chemistry behavior and the dynamic hydrologic processes should become the next simulation effort in the watershed study. There are many questions that are critical to watershed chemistry studies like: which flow component (surface flow, macropore flow, soil matrix flow) predominates during peak flows? How do the flow components distribute during a flood event? How do flow contributions differ between these two watersheds? Which portion of the watershed contributes the most to the peak flows? These questions remain unknown from previous observations and only can be addressed with a physically-based distributed model.     

The evolution of the science of Bear Brook Watershed in Maine, USA

The Bear Brook Watershed in Maine (BBWM), USA is a paired watershed study with chemical manipulation of one watershed (West Bear = WB) while the other watershed (East Bear = EB) serves as a reference. Characterization of hydrology and chemical fluxes occurred in 1987–1989 and demonstrated the similarity of the ca. 10 ha adjacent forested watersheds. From 1989–2010, we have added 1,800 eq (NH₄)₂SO₄ ha^???1 y^???1 to WB. EB runoff has slowly acidified even as atmospheric deposition of SO $_{4}^{2-}$ has declined. EB acidification included decreasing pH, base cation concentrations, and alkalinity, and increasing inorganic Al concentration, as SO $_{4}^{2-}$ declined. Organic Al increased. WB has acidified more rapidly, including a 6-year period of increasing leaching of base cations, followed by a long-term decline of base cations, although still elevated over pretreatment values, as base saturation declined in the soils. Sulfate in WB has not increased to a new steady state because of increased anion adsorption accompanying soil acidification. Dissolved Al has increased dramatically in WB; increased export of particulate Al and P has accompanied the acidification in both watersheds, WB more than EB. Nitrogen retention in EB increased after 3 years of study, as did many watersheds in the northeastern USA. Nitrogen retention in WB still remains at over 80%, in spite of 20+ years of N addition. The 20-year chemical treatment with continuous measurements of critical variables in both watersheds has enabled the identification of decadal-scale processes, including ecosystem response to declining SO $_{4}^{-2}$ in ambient precipitation in EB and evolving mechanisms of treatment response in WB. The study has demonstrated soil mechanisms buffering pH, declines in soil base saturation, altered P biogeochemistry, unexpected mechanisms of storage of S, and continuous high retention of treatment N.     

Accumulation of different sulfur fractions in Chinese forest soil under acid deposition

Atmogenic sulfur (S) deposition loading by acid rain is one of the biggest environmental problems in China. It is important to know the accumulated S stored in soil, because eventually the size (and also the "desorption" rate) determines how rapidly the soil water pH responds to decrease in S deposition. The S fractions and the ratio of total carbon/total sulfur (C/S) of forest soil in 9 catchments were investigated by comparing soils at the rural and urban sites in China. The S fractions included water-soluble sulfate-S (SO(4)-S), adsorbed SO(4)-S, insoluble SO(4)-S and organic S. The ratio of C/S in soil at the rural site was significantly (p < 0.05) greater than that at the urban site. C/S of soil in the A horizon was significantly (p < 0.05) and negatively correlated with the wet S-deposition rate. The ratio of C/S presents a better indicator for atmogenic S loading. Organic S was the dominant form in soils at rural sites; contributing more than 69% of the total S in the uppermost 30 cm soil. Organic S and adsorbed SO(4)-S were the main forms of S in soil at urban sites. High contents of water-soluble SO(4)-S and adsorbed SO(4)-S were found in uppermost 30 cm soils at urban sites but not at rural sites. Decades of acid rain have caused accumulation of inorganic SO(4)-S in Chinese forest soil especially at the urban sites. The soil at urban sites had been firstly acidified, and the impacts on the forest ecosystem in these areas should be noticed.     

Drivers and evolution of episodic acidification at the Bear Brook Watershed in Maine, USA

Despite decades of research about episodic acidification in many regions of the world, the understanding of what controls the transient changes in stream water chemistry occurring during rain and snow melt events is still limited. Here, we use 20 years of hydrological and stream chemical data from the paired watershed study at Bear Brook Watershed in Maine (BBWM), USA to improve the understanding of the effects of acid deposition on the causes, drivers, and evolution of episodic acidification. The long-term experimental study at BBWM includes 18 years of chemical treatment of the West Bear Brook (WB) watershed with (NH₄)₂SO₄. East Bear Brook (EB) serves as reference. The treatment started in 1989 following a 2-year pretreatment period. We analyzed 212 hydrological episodes using an episode model that can separate and quantify individual drivers of the transient change in acid-neutralizing capacity (ANC) during hydrological events. The results suggest that 18 years of N and S addition have not affected the natural drivers of episodic acidification of base-cation dilution, marine sea salt episodes, or organic acidity during rain and snow melt events. The contribution of SO $_{4}^{2-}$ to the ANC decline in WB has been increasing linearly since the beginning of watershed treatment, while the role of NO $_{3}^{-}$ has remained relatively constant after an initial increase. This is contradictory to many previous shorter-term studies and illustrates the need for a more mechanistic understanding of the causes and drivers of episodic acidification during rain- and snow melt-driven hydrological events.     

Twenty-year inter-annual trends and seasonal variations in precipitation and stream water chemistry at the Bear Brook Watershed in Maine, USA

Mean annual concentration of ${\textrm{SO}}_{4}^{2-}$ in wet-only deposition has decreased between 1988 and 2006 at the paired watershed study at Bear Brook Watershed in Maine, USA (BBWM) due to substantially decreased emissions of SO₂. Emissions of NO_x have not changed substantially, but deposition has declined slightly at BBWM. Base cations, ${\textrm{NH}}_{4}^{+}$ , and Cl^??? concentrations were largely unchanged, with small irregular changes of <1 μeq L^???1 per year from 1988 to 2006. Precipitation chemistry, hydrology, vegetation, and temperature drive seasonal stream chemistry. Low flow periods were typical in June–October, with relatively greater contributions of deeper flow solutions with higher pH; higher concentrations of acid-neutralizing capacity, Si, and non-marine Na; and low concentrations of inorganic Al. High flow periods during November–May were typically dominated by solutions following shallow flow paths, which were characterized by lower pH and higher Al and DOC concentrations. Biological activity strongly controlled ${\textrm{NO}}_{3}^{-}$ and K^?+?. They were depressed during the growing season and elevated in the fall. Since 1987, East Bear Brook (EB), the reference stream, has been slowly responding to reduced but still elevated acid deposition. Calcium and Mg have declined fairly steadily and faster than ${\textrm{SO}}_{4}^{2-}$ , with consequent acidification (lower pH and higher inorganic Al). Eighteen years of experimental treatment with (NH₄)₂SO₄ enhanced acidification of West Bear Brook’s (WB) watershed. Despite the manipulation, ${\textrm{NH}}_{4}^{+}$ concentration remained below detection limits at WB, while leaching of ${\textrm{NO}}_{3}^{-}$ increased. The seasonal pattern for ${\textrm{NO}}_{3}^{-}$ concentrations in WB, however, remained similar to EB. Mean monthly concentrations of ${\textrm{SO}}_{4}^{2-}$ have increased in WB since 1989, initially only during periods of high flow, but gradually also during base flow. Increases in mean monthly concentrations of Ca^2?+?, Mg^2?+?, and K^?+? due to the manipulation occurred from 1989 until about 1995, during the depletion of base cations in shallow flow paths in WB. Progressive depletion of Ca and Mg at greater soil depth occurred, causing stream concentrations to decline to pre-manipulation values. Mean monthly Si concentrations did not change in EB or WB, suggesting that the manipulation had no effect on mineral weathering rates. DOC concentrations in both streams did not exhibit inter- or intra-annual trends.     

Nitrification,soil acidification and streamwater chemistry following deglaciation,glacier bay national park and preserve

A major tool used in the assessment of anthropic atmospheric effects on aquatic and terrestrial ecosystems is biogeochemical nutrient cycling and budgets. However, to be most effective such study should be done in an ecosystem context. Also some assessment of natural variation in factors affecting nutrient cycling must be in place before trends, often subtle and long-term, attributable to man can be statistically quantified. The input and output balance of chemical species in watershed ecosystems is considerably influenced by ecosystem succession. It is hypothesized that during primary ecosystem succession chemical element output is initially relatively high due to rapid acidification and lack of plant uptake. Outputs decline during the period of high ecosystem productivity and biomass accumulation, and they again rise during late successional stages to approximate inputs from precipitation weathering, and aerosol capture. Glacier Bay provides a unique opportunity to quantify many mechanisms responsible for variation in nutrient cycles without the need for site manipulation. This is especially true for quantifying the rate and magnitude of natural acidification in ecosystems. The park has a spectrum of watersheds differing in stage of primary and secondary succession following deglaciation. These sites are not now subjected to or altered by anthropic atmospheric inputs. The objectives of this research were (1) determine the rate of soil chemical change which occurs following deglaciation, (2) relate soil acidification to presence of organic matter, soil NO _inf3 ^sup- , and total N, (3) estimate the downward movement of ionic species within the soil profiles with increasing acidification from advancing plant succession, and (4) determine if such processes and ionic movements might be reflected in watershed stream ionic outputs. We studied five watersheds ranging from 40–350 years since deglaciation. Soil samples were collected and lysimeters installed in seven vegetation successional stages following deglaciation. An anion of ecological importance and a common air contaminant is NO _inf3 ^sup- , and its discharge in streamflow from early successional ecosystems was found to be high. The terrestrial biota in such systems was dominated by Alnus sinuata, a major nitrogen fixer. Stream discharge of NO _inf3 ^sup- suggested that early successional ecosystem N fixation exceeded biotic uptake. This was confirmed by examining NO _inf3 ^sup- in soil extractions and lysimeters. This process was particularly evident beneath >20-year old Alnus (forty years since deglaciation). concurrent with increased NO _inf3 ^sup- concentrations below the rooting zone was increased H⁺ which increased 100x during 25 years of primary succession. This natural acidification from a mobile NO _inf3 ^sup- ion resulted in an pronounced increase in soil base cation leaching and mobilization of aluminium in the soil profile. The magnitude and short time required for such acidification greatly exceeded anything projected or modeled for systems impacted by anthropic inputs. Stream SO _inf4 ^sup2- concentrations also were high relative to precipitation inputs suggesting mineralization of sulfur within the ecosystem and/or poor soil adsorption of SO _inf4 ^sup2- . This is an important finding in such ecosystems where cation nutrient ion levels are often very low. Should atmospheric inputs of SO _inf4 ^sup2- increase additional loss of cations appears imminent. These data suggest that most early successional ecosystems at Glacier Bay would be sensitive to anthropic inputs of both NO _inf3 ^sup- and SO _inf4 ^sup2- . This is unusual in other ecosystems where many conserve ionic NO _inf3 ^sup- inputs, and older systems have considerable SO _inf4 ^sup2- adsorption capacity. The effect of any increased atmospheric inputs of these ions would be accelerated cation leaching and ecosystem acidification.Contribution from Fourth World Wilderness Congress—Acid Rain Symposium, Denver (Estes Park), Colorado, September 11–18, 1987.     

Stream ecosystem response to chronic deposition of N and acid at the Bear Brook Watershed, Maine

The Bear Brook Watershed in Maine (BBWM) is a long-term, paired watershed experiment that addresses the effects of acid and nitrogen (N) deposition on whole watersheds. To examine stream response at BBWM, we synthesized data on organic matter dynamics, including leaf breakdown rates, organic matter inputs and standing stocks, macroinvertebrate secondary production, and nutrient uptake in treated and reference streams at the BBWM. While N concentrations in stream water and leaves have increased, the input, standing stocks, and breakdown rates of leaves, as well as macroinvertebrate production, were not responsive to acid and N deposition. Both chronic and acute increases of N availability have saturated uptake of nitrate in the streams. Recent experimental increases in phosphorus (P) availability enhanced stream capacity to take up nitrate and altered the character of N saturation. These results show how the interactive effects of multiple factors, including environmental flow regime, acidification, and P availability, may constrain stream response to chronic N deposition.