Altered Soil-soil Water Interactions Inferred from Stream Water Chemistry at an Artificially Acidified Watershed at Bear Brook Watershed, Maine USA

The Bear Brook Watershed in Maine, USA is the site of a paired watershed study. West Bear (WB) catchment is being artificially acidified with 1,800 eq ha-1 y-1 of (NH4)2SO4. East Bear (EB) serves as the control. After six years of artificial acidification, volume-weighted concentrations in WB, normalized to EB, increased approximately as follows, in eq L-1 : H+, 15; Al (umoles), 50; Al (eq L-1), 100; Ca. 50; Mg. 20; Na, 10; K, 2; SO4, 120; NH4, 2; NO3, 80; HCO3 has decreased 10 eq L-1. Based on changing chemistry, several inferences can be made about soil-soil water interactions.1. Various combinations of cation pairs in stream waters from both catchments are significantly correlated on an annual basis. The strongest linear correlations (r2 typically greater than 0.5), with positive slopes, occur for Mg versus Ca. These relationships suggest soil-soil water equilibria of the type:Ca+2 + Mg-X = Mg+2 + Ca-X; KCa-Mg = ([Mg+2]/[Ca+2])/([Mg-X]/[Ca-X]) or, with assumptions:K'Ca-Mg = [Mg+2]/[Ca+2]The value of K'Ca-Mg remains relatively constant through time in both watersheds, except in WB in and after the fourth year of the manipulation of WB. Thereafter there is preferential depletion (Mg>Ca>na>K), primarily along shallow flow paths - thus altering the solid activity ratios of the exchange surfaces. In EB, base cation concentrations decline with increasing discharge (increasing H+), due to dilution and interaction with soils with lower base saturation. In WB the acidification reverses this relationship, perhaps partly because of displacement of cations by NH4 from the amendments. With progressive depletion of Ca and Mg in the quick-flow paths, concentrations start to decline at higher discharge, in spite of lower pH.2. Sulfate concentrations increased in WB to as high as 230 eq L-1 at high flow. The percentage of added SO4 leached to the stream increased to approximately 65% by the end of 1995. Thus, soils along base-flow paths adsorbed about 35% of the added SO4 in 1995.3. Aluminum concentrations in WB have increased from a pre-manipulation maximum of 10 mole/L at high flow to 60 mole/L. The relationship between Al and H+ is:Al = 0.13(H+)2 + 4.35which could result from either desorption or dissolution of Al to a 2+ specie. This relationship has been relatively constant through the manipulation. The Al/Ca molar ratio increased from pre-manipulation values of 0.1 to 0.3 to 0.8, at higher flow.4. The minimum pH in WB, achieved at highest flow, has decreased from about 5.3 to <4.7, an increase of about 15 eq H+ L-1. The increase in H+ has been approximately 2 eq L-1 yr-1. Neutralization of acidity has been initially accommodated by mobilization of Ca>Mg>Al>Na>K>H; by 1995 the neutralization involves the release of Al>Ca>Mg>NaH>K. Thus, the soils are inferred to (1) have reduced base saturation, (2) preferential proportional loss of mg over Ca, (3) increased SO4 saturation, and (4) higher exchangeable acidity.     

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 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.     

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.     

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.     

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.     

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.     

Mineral Soil and Solution Responses to Experimental N and S Enrichment at the Bear Brook Watershed in Maine (BBWM)

Buried mineral soil-bags and natural solutions were studied as indicators of forest ecosystem response to elevated N and S inputs at the Bear Brook Watershed in Maine (BBWM). The BBWM is the site of a paired watershed manipulation experiment in a northern New England forested ecosystem. The study includes two small (10 ha each) catchments dominated by northern hardwood forests with red spruce in the upper elevations. Treatments consist of (NH4)2SO4 applied to the West Bear watershed six times per year, increasing N and S deposition 3× and 2× above ambient values, respectively. Buried mineral soil-bag changes over time reflected both the native soil environment and the treatments. Most of the treatment effects on mineral soils were evident as higher inorganic S found in the treated watershed soils. Adsorbed SO4 in the buried mineral soil-bags increased by approximately 40% under softwood stands and 50% under hardwood stands over the study period. Hardwood soil solutions responded with significant increases in NO3 and SO4 concentrations that resulted in accelerated cation leaching, primarily Ca and Al. Few differences that could be attributed to treatments were evident in soil solutions under softwoods. No treatment effects were evident in throughfall and stemflow chemistry.     

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.     

Streamflow variability and hydroclimatic change at the Bear Brook Watershed in Maine (BBWM), USA

Seasonal variations in streamflow and the associated hydrologic extremes impart significant temporal structure to watershed-scale chemical fluxes. Consequently, a careful characterization of the episodic-to-seasonal and longer-term streamflow variations is a first step toward developing a comprehensive view of the temporal dynamics of watershed processes in a changing climate. Here we analyze a nearly two-decade-long streamflow record for the East Bear subwatershed within the Bear Brook Watershed in Maine (BBWM) (USA) to understand the envelope of streamflow variability by season, with a particular focus on the high flow events that have a disproportionately large impact on the biogeochemical processes and fluxes. Interannual and longer-term variations in a number of derived statistical metrics of hydrologic variability are examined. Our analysis shows substantial interannual and longer-term variability in seasonal flow volumes and peak flows. Furthermore, a long, unimpaired streamflow record for the Narraguagus River (a proximate watershed to the BBWM) is examined with a view to understand the relative coherence in hydrologic variability, as well as quantifying the decadal and longer-term hydrologic variations in this region. We find that the streamflow variability in the two watersheds shows similarity in all seasons. A moving window analysis to assess the changing flood potential over time indicates upward trends in the recent decades. Spring season (March–May) flood estimates show a near-monotonic trend over the 1949–2008 record. Finally, empirical relationships between streamflow and large-scale atmospheric circulation patterns highlight the regional and global climatic drivers of hydrologic extremes in this region, including impacts from remnants of Atlantic hurricanes.     

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.     

Impacts of Ammonium Sulfate Treatment on the Foliar Chemistry of Forest Trees at the Bear Brook Watershed in Maine

Foliar chemistry was examined in mature sugar maple (Acer saccharum Marsh), red maple (Acer rubrum L.), American beech (Fagus grandifolia Ehrh.), and red spruce (Picea rubens Sarg.) in response to chronic, watershed-level additions of ammonium sulfate [(NH4)2SO4]. Following four years of treatment, N concentrations were significantly higher in foliage from the treated watershed for all four species, with increases ranging from 6% in American beech to 33% in sugar maple. Sugar maple foliage from the treated watershed had significantly lower Ca concentrations (18%). Concentrations of K were significantly lower in beech (13%) and red spruce (9%) from the treated watershed. Foliar Mg was not different between watersheds. Aluminum concentrations were significantly higher in the foliage from the treated watershed for beech (18%), red maple (33%), and sugar maple (65%), but no differences in Al concentration occurred in current year red spruce foliage. Red spruce foliage resampled following a fifth year of treatment contained higher concentrations of N and Al and lower concentrations of Ca and Mg in the treated watershed. Despite these differences in red spruce foliar chemistry, wood production and density did not appear to be affected by the treatment.Differences in the foliar chemistry between the treated and untreated watershed may reflect the temporal and spatial integration of changes taking place in the soil of the treated watershed. Increased N is likely directly due to the N contained in the (NH4)2SO4 treatment. Labile Ca and other cations in the treated watershed would be expected to initially increase and then decrease in response to the treatment, with these changes beginning at the top of the forest floor. Thus, lower cation concentrations in foliage from the treated watershed may reflect the fact that cations in the uppermost portions of the soil were rapidly depleted, even though deeper soil layers were experiencing increased Ca release due to cation exchange effect of the acidification. The generally higher Al in foliage from the treated watershed is likely due to the mobilization of inorganic Al in the soil as has been reported previously for the treated watershed. Collectively these results suggest that the long-term deposition of acidifying substances containing N and S not only influence the cycling of N within these systems, but may also alter the cycling of other important nutrients and Al.     

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.     

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.     

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.     

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.     

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.     

Watershed Nitrogen and Mercury Geochemical Fluxes Integrate Landscape Factors in Long-term Research Watersheds at Acadia National Park, Maine, USA

This paper is an overview of this special issue devoted to watershed research in Acadia National Park (Acadia NP). The papers address components of an integrated research program on two upland watersheds at Acadia NP, USA (44° 20′ N latitude; 68° 15′ E longitude). These watersheds were instrumented in 1998 to provide a long-term foundation for regional ecological and watershed research. The research was initiated as part of EPA/NPS PRIMENet (Park Research and Intensive Monitoring of Ecosystems Network), a system of UV-monitoring stations and long-term watershed research sites located in US national parks. The initial goals at Acadia NP were to address research questions about mercury, acid rain, and nitrogen saturation developed from prior research. The project design was based on natural differences in forests and soils induced by an intense wildfire in one watershed in 1947. There is no evidence of fire in the reference watershed for several hundred years. We are testing hypotheses about controls on surface water chemistry, and bioavailability of contaminants in the contrasting watersheds. The unburned 47-ha Hadlock Brook watershed is 70% spruce-fir mature conifer forest. In contrast, burned 32-ha Cadillac Brook watershed, 4 km northeast of the Hadlock watershed, is 20% regenerating mixed northern hardwoods and 60% shrub/rocky balds. Differences in atmospheric deposition are controlled primarily by forest stand composition and age. The watersheds are gauged and have water chemistry stations at 122 m (Cadillac) and 137 m (Hadlock); watershed maximum elevations are 468 and 380 m, respectively. The stream water chemistry patterns reflect, in part, the legacy of the intense fire, which, in turn, controls differences in forest vegetation and soil characteristics. These factors result in higher nitrogen and mercury flux from the unburned watershed, reflecting differences in atmospheric deposition, contrasting ecosystem pools of nitrogen and mercury, and inferred differences in internal cycling and bioavailabilty.     

N isotopes and N cycle in the TieShanPing subtropical forest ecosystem, Southwestern China

Nitrogen is essential for forest growth and forest stand development. It is commonly a limited factor for forest productivity. We examined delta (15)N values in soils and plants by studying the sources of N used by vegetation and cycles of N in a 43-year-old plantation of the TieShanPing forest ecosystem in southwestern China, dominated by massone pine (Pinus massoniana). The N concentration of plant materials ranges from 1.1% to 2.2%. The nitrogen concentration of P. massoniana was 1.3% while soils showed the concentration of 0.04-0.15%. Regarding natural abundance of (15)N, large significant variation (-6.0 per thousand to -3.8 per thousand) in delta (15)N values was observed among shrub and tree leaves. delta (15)N values were also significantly varied from -4.7 per thousand to -3.8 per thousand among the pioneer species in the plantation. Soil delta (15)N values (3.1-6.3 per thousand) were significantly enriched compared to those values in plant samples. Despite the negative delta (15)N values of the vegetation cover, the high delta (15)N values in the topsoil indicate that return of N to soils by litter-fall is minimal on TieShanPing and the present forests do not change very much the soil (15)N signals at the surface layer. The positive delta (15)N values may also indicate large N losses from the soil system vial leaching, volatilization and plant uptake.     

Long-term relationships between SO2 and NOx emissions and SO4(2-) and NO3- concentration in bulk deposition at the Hubbard Brook Experimental Forest, NH

A highly significant second-order polynomial relation between SO(2) emissions and SO(4)(2-) concentrations during 1970-2000 (r(2)= 0.80, p= <0.001), and a linear relation between NO(x) and NO(3)(-) concentrations during 1991-2000 (r(2)= 0.67, p= 0.004) in bulk precipitation were found for the Hubbard Brook Experimental Forest, NH based on emissions from a 24 h, back-trajectory determined source area. Earlier periods (1965-1980) for SO(2)ratio SO(4)(2-) and longer periods (1965-2000) for NO(x)ratio NO(3)(-) had poorer linear relations, r(2)= 0.03, p= 0.51 and r(2)= 0.22, p= 0.004, respectively. Methodology by the US Environmental Protection Agency for calculating emissions data during this period has changed significantly and frequently, making trend analysis difficult. Given the large potential for errors in estimating emissions and to a lesser extent, deposition, the robust relations between SO(2) emissions and SO(4)(2-) concentrations in bulk precipitation at the Hubbard Brook Experimental Forest show that careful, long-term measurements from a single monitoring site can provide sound and reasonable data on trends in air pollution.