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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Mass Balances of Mercury and Nitrogen in Burned and Unburned Forested Watersheds at Acadia National Park, Maine, USA

Precipitation and streamwater samples were collected from 16 November 1999 to 17 November 2000 in two watersheds at Acadia National Park, Maine, and analyzed for mercury (Hg) and dissolved inorganic nitrogen (DIN, nitrate plus ammonium). Cadillac Brook watershed burned in a 1947 fire that destroyed vegetation and soil organic matter. We hypothesized that Hg deposition would be higher at Hadlock Brook (the reference watershed, 10.2 μg/m²/year) than Cadillac (9.4 μg/m²/year) because of the greater scavenging efficiency of the softwood vegetation in Hadlock. We also hypothesized the Hg and DIN export from Cadillac Brook would be lower than Hadlock Brook because of elemental volatilization during the fire, along with subsequently lower rates of atmospheric deposition in a watershed with abundant bare soil and bedrock, and regenerating vegetation. Consistent with these hypotheses, Hg export was lower from Cadillac Brook watershed (0.4 μg/m²/year) than from Hadlock Brook watershed (1.3 μg/m²/year). DIN export from Cadillac Brook (11.5 eq/ha/year) was lower than Hadlock Brook (92.5 eq/ha/year). These data show that ∼50 years following a wildfire there was lower atmospheric deposition due to changes in forest species composition, lower soil pools, and greater ecosystem retention for both Hg and DIN.     

在同一消解液中同时测定总磷和总氮

探讨了在同一消解液中同时测定总磷、总氮的分析方法。实验结果表明,选用合适的氢氧化钠和过硫酸钾的加入量,可在同一消解液中同时测定总磷和总氮,并能克服消解液保存时间短的缺点。应用本文所拟最佳条件对标样和水样进行分析,结果准确,方法实用。