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.     

A Regional Analysis of Lake Acidification Trends for the Northeastern U.S., 1982-1994

Acidic deposition is a regional phenomenon, but its effects have traditionally been studied using site-specific, intensive monitoring. We present trends information for 36 lakes of high-to-moderate acid sensitivity (defined as acid neutralizing capacity [ANC] < 100 eq L-1), and 15 deposition monitoring stations, in the northeastern U.S. for the period 1982-1994. Trends at each site were assessed through use of the Seasonal Kendall tau test; the resulting statistics were combined, through a technique analogous to analysis of variance, to produce quasi-regional estimates of change for key chemical variables. Rates of sulfate deposition declined significantly across all of the northeastern region during this time period, while rates of nitrate and ammonium deposition were unchanged. All lakes exhibited strong decreases in sulfate concentrations in response to declining sulfate deposition, but there was a strong contrast in the response of acid/base status between lakes in New England and lakes in the Adirondacks. As a group, the New England lakes exhibited recovery (ANC = +0.8 eq L-1yr-1, p<0.001), while the Adirondack lakes exhibited either no trend or further acidification (as a group, ANC = -0.5 eq L-1yr-1, p<0.01). This contrast can be attributed to changes in base cation concentrations: New England lakes exhibited base cations declines that were smaller in magnitude than declines in sulfate, producing the observed recovery in ANC; Adirondack lakes showed base cation declines that were very similar to those of sulfate, and no recovery was evident.     

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.     

Estimation of Critical Loads of Acidity for Lakes in Northeastern United States and Eastern Canada

The New England Governors and Eastern Canadian Premiers (NEG/ECP) adopted the Acid Rain Action Plan in June 1998, and issued a series of action items to support its work toward a reduction of sulfur dioxide (SO₂) and nitrogen oxide (NO_x) emissions in northeastern North America. One of these action items was the preparation of an updated critical load map using data from lakes in the NEG/ECP area. Critical load maps provide a more complete index of the surface water sensitivity to acidification. Combined sulfur and nitrogen critical loads and deposition exceedances were computed using Henriksen's Steady-State Water Chemistry (SSWC) model. Results show that 28% of all 2053 lakes studied have a critical load of 20 kg/ha/year or less, making them vulnerable to acid deposition. Emission reductions, and more specifically SO₂ emission reductions have proven beneficial because critical loads were exceeded in 2002 for 12.3% of all studied lakes. Those lakes are located in the more sensitive areas where geology is carbonate-poor. Of these lakes, 2.9% will never recover even with a complete removal of SO₄ deposition. Recovery from acidification for the remaining 9.4% of the lakes will require additional emission SO₂ reductions.     

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.     

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 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.     

Acidification Trends and the Evolution of Neutralization Mechanisms through Time at the Bear Brook Watershed in Maine (BBWM), U.S.A.

The paired catchment study at the forested Bear Brook Watershed in Maine (BBWM) U.S.A. documents interactions among short- to long-term processes of acidification. In 1987–1989, runoff from the two catchments was nearly identical in quality and quantity. Ammonium sulfate has been added bi-monthly since 1989 to the West Bear catchment at 1800 eq ha^-1 a^-1; the East Bear reference catchment is responding to ambient conditions. Initially, the two catchments had nearly identical chemistry (e.g., Ca²⁺, Mg²⁺, SO₄ ^2-, and alkalinity ≈82, 32, 100, and 5 μeq L^-1, respectively). The manipulated catchment responded initially with increased export of base cations, lower pH and alkalinity, and increased dissolved Al,NO₃ ^- and SO₄ ^2-. Dissolved organic carbon and Si have remained relatively constant. After 7 yr of treatment, the chemical response of runoff switched to declining base cations, with the other analytes continuing their trends; the exports of dissolved and particulate Al, Fe, and P increased substantially as base cations declined. The reference catchment has slowly acidified under ambient conditions, caused by the base cation supply decreasing faster than the decrease of SO₄ ², as pollution abates. Export of Al, Fe and, P is mimicking that of the manipulated watershed, but is lower in magnitude and lags in time. Probable increasing SO₄ ^2- adsorption caused by acidification has moderated the longer-term trends of acidification of both watersheds. The trends of decreasing base cations were interrupted by the effects of several short-term events, including severe ice storm damage to the canopy, unusual snow pack conditions, snow melt and rain storms, and episodic input of marine aerosols. These episodic events alter alkalinity by5 to 15 μeq L^-1 and make it more difficult to determine recovery from pollution abatement.     

A European-wide inventory of soil NO emissions using the biogeochemical models DNDC/Forest-DNDC

Soils are a significant source for atmospheric NO. However, due to the limited number of measurements and in view of the high temporal and spatial variability of NO emissions, as originating from dependencies from a series of environmental constraints such as soil properties, meteorology or N fertilization, inventories of soil NO emissions are still highly uncertain. In this work, the agricultural DNDC model was modified and applied on site scale in order to evaluate its capability to simulate soil NO emissions. DNDC captured differences in the magnitude of NO emissions between sites, but was less successful when simulating observed day-by-day variations. However, major peak emission events, e.g. due to fertilizer application or following rainfall events, were mostly simulated. DNDC as well as its forest version Forest-DNDC were finally linked to a GIS to calculate NO emissions from agricultural and forest soils across Europe. Using the same databases for agricultural soils, we also compared our estimate with other commonly used methodologies (Skiba-EMEP/CORINAIR, Yienger and Levy, Stehfest and Bouwman). A canopy reduction factor was not applied in this study. Estimates for NO emissions for agricultural soils for EU15 states varied in a range of 48.9–189.8 kt NO-N for the year 2000 depending on the approach used (Yienger and Levy > DNDC > Stehfest and Bouwman > Skiba-EMEP/CORINAIR). For forests, using the model Forest-DNDC as the only approach, we calculated soil NO emissions to be 75.1 kt NO-N yr^?1. The results show that soils in EU15 states are significant sources of atmospheric NO, though the share of soil NO emissions on total NO_x emissions (incl. NO_x emissions by combustion processes) in EU15 was only 4–6%. Given that soil NO emissions are largely driven by the availability of inorganic nitrogen (fertilization) and temperature, emissions are larger during the vegetation period. Especially during early summer when fertilizer-induced NO emissions from agricultural soils are peaking, the contribution of soil emissions to total NO_x emissions may most likely be well above 10%.