Assessment Indices of Littoral Habitat Condition for Lakes in Maine and New England, USA.

Littoral habitat is critical for lake biota but is adversely affected by residential shoreland development through the loss and reduced structural complexity of lakeshore vegetation. There currently exists no assessment methodology for evaluating littoral habitat condition of individual lakes in northeastern US. We addressed this assessment need by creating multi-metric indices of littoral habitat condition that focus on lakeshore residential development as the primary stressor. We did this by using habitat metrics derived primarily from National Lake Assessment (NLA) Physical Habitat (PHAB) survey field observations to create Linear Discriminant Analysis (LDA) models that assign lakeshore stations into littoral habitat condition categories. Lake PHAB survey data were used from New England NLA surveys as well as state-level surveys completed in Maine, New Hampshire, and Vermont. Prediction success rates in New England models averaged 83%. The Maine LDA models, which used finer scale survey methods, had an average prediction success rate of 89%. We used 95% bootstrapped confidence intervals to make assessment designations of natural (meeting reference quality), diminished (not meeting reference quality), or intermediate (existing between natural and diminished) littoral habitat condition for each lake. Our results show that efficacious single-lake littoral habitat assessments may be completed within the framework of NLA PHAB methodology, but confidence in assessment results, and therefore better-informed management decisions, can be improved with finer-scale observation data.

Controls on the epilimnetic phosphorus concentration in small temperate lakes.

Phosphorus (P) is one of the key limiting nutrients for algal growth in most fresh surface waters. Understanding the determinants of P accumulation in the water column of lakes of interest, and the prediction of its concentration is important to water quality managers and other stakeholders. We hypothesized that lake physicochemical, climate, and watershed land-use attributes control lake P concentration. We collected relevant data from 126 lakes in Maine, USA, to determine the major drivers for summer total epilimnetic P concentrations. Predictive regression-based models featured lake external and internal drivers. The most important land-use driver was the extent of agriculture in the watershed. Lake average depth was the most important physical driver, with shallow lakes being most susceptible to high P concentrations; shallow lakes often stratify weakly and are most subject to internal mixing. The sediment NaOH-extracted aluminum (Al) to bicarbonate/dithionite-extracted P molar ratio was the most important sediment chemical driver; lakes with a high hypolimnetic P release have low ratios. The dissolved organic carbon (DOC) concentration was an important water column chemical driver; lakes having a high DOC concentration generally had higher epilimnetic P concentrations. Precipitation and temperature, two important climate/weather variables, were not significant drivers of epilimnetic P in the predictive models. Because lake depth and sediment quality are fixed in the short-term, the modeling framework serves as a quantitative lake management tool for stakeholders to assess the vulnerability of individual lakes to watershed development, particularly agriculture. The model also enables decisions for sustainable development in the watershed and lake remediation if sediment quality is conducive to internal P release. The findings of this study may be applied to bloom metrics more directly to support lake and watershed management actions.

Predicting anoxia in low-nutrient temperate lakes.

Absence of dissolved oxygen (anoxia) in the hypolimnion of lakes can eliminate habitat for sensitive species and may induce the release of sediment-bound phosphorus. Lake anoxia generally results from decomposition of organic matter, which is exacerbated by high nutrient loads. Total phosphorus (TP) in lakes is regulated by static aspects of the lake's watershed, but lake TP can be readily increased by human activities. In some low-nutrient lakes, basin morphometry may induce naturally occurring anoxia. The occurrence of natural anoxia is especially important to consider in lake water quality assessments that compare observed conditions to expected reference conditions. To investigate the occurrence of natural vs. anthropogenically influenced anoxia, we constructed a logistic regression model to calculate the probability of low-nutrient lakes (TP < 15 µg/L) developing aerial anoxic extent ≥10% by testing the predictive potential of variables related to basin morphometry, depths of lake thermal strata, epilimnetic TP, and dissolved organic carbon (DOC). Maximum lake depth and the proportion of lake area under the top of the metalimnion were the most important variables to predict the likelihood of hypolimnetic anoxia, which correctly predicted anoxic condition in 84% of lakes (Model 1). Adding TP as a third variable to Model 1 produced a significantly improved model (Model 2) but the prediction success rate was comparable (86%). We also present a model for lakes with limited bathymetric data, which predicts anoxia with 81% accuracy based on maximum lake depth and mean thermocline depth at peak stratification. DOC was relatively low (4.3 ± 1.5 mg/L [mean ± SD]) in the study lakes and its inclusion did not improve model performance. In Model 1, lakes with an anoxic extent ≥10% of lake area had significantly higher epilimnetic TP than lakes with oxic hypolimnia, regardless of prediction category or success. Our results indicate that including TP as a variable helps refine models based on morphometry alone, but lake morphometry and stratification dynamics are the most important factors in the development of anoxic extent in low-nutrient temperate lakes. Our approach informs studies concerned with identifying key factors that influence regime shifts in a variety of ecosystems.

The distribution and transport of lead over two centuries as recorded by lake sediments from northeastern North America.

We evaluated anthropogenic Pb deposition along a west-east transect from the Adirondack Mountains, New York, USA (ADIR) region, the Vermont-New Hampshire-Maine, USA (VT-NH-ME) region, and Nova Scotia, Canada (NS) region using 47 210Pb-dated lake sediment records. We used focus-corrected Pb inventories to evaluate cumulative deposition and breakpoint analysis to evaluate possible differences in timings among regions. Peak Pb concentrations decreased from west to east (ADIR region: 52-378 mg kg-1, VT-NH-ME region: 54-253 mg kg-1, NS: 38-140 mg kg-1). Cumulative deposition of anthropogenic Pb also decreased from west to east (ADIR region: 791-1344 mg m-2, VT-NH-ME region: 209-1206 mg m-2, NS: 52-421 mg m-2). The initiation of anthropogenic Pb deposition occurred progressively later along the same transect (ADIR region: 1869-1900, VT-NH-ME region: 1874-1905, NS region: 1901-1930). Previous lead isotope studies suggest that eastern Canadian Pb deposition over the past ~150 years has originated from a mix of both Canadian and U.S. sources. The results of this study indicate that anthropogenic Pb from sources west of the ADIR region were deposited in lesser amounts from west to east and/or Pb sources reflect less population density from west to east. The timing of the initiation of anthropogenic Pb deposition in the NS region suggests that Pb from gasoline may be an important source in this region.

Disruptions and re-establishment of the calcium-bicarbonate equilibrium in freshwaters.

During recent decades, increasing anthropogenic activities have affected natural ionic composition, including the strongest and most common relationship between ionic concentrations in the majority of natural global freshwaters, i.e., the Ca2+-ANC (acid neutralizing capacity) equilibrium. Using long-term monitoring data and MAGIC modelling, we evaluated effects of major present environmental stressors (synthetic fertilizers, liming, acidic deposition, forest disturbances, and climate change) on the Ca2+-ANC equilibrium. We evaluated the effects for three different types of terrestrial ecosystems, a circumneutral lowland agricultural catchment, two acid sensitive mountain forest catchments differing in forest health, and one acid sensitive alpine catchment. All catchments are in a region with the world-largest changes in fertilizing rates and acidic deposition in the 20th century, with increasing impacts until the late 1980s, and their subsequent abrupt, dramatic decreases. These strong changes resulted in a substantial disruption, followed by continuing re-establishment of the Ca2+-ANC relationship in all study waters. The shape of the disruption and the following re-establishment of its new value were dependent on the intensity, duration, and combination of stressors, as well as on catchment characteristics (bedrock composition, soil amount and composition, vegetation status, and hydrology). We conclude that a new equilibrium may deviate from its natural value due to the (1) legacy of fertilizing, acidic deposition and liming, affecting the soil Ca2+ pools, (2) forest disturbances and management practices, and (3) climate change.

Solar Radiation as the Likely Cause of Acid-Soluble Rare-Earth Elements in Sediments of Fresh Water Humic Lakes.

We studied photochemically induced precipitation of rare-earth elements (REEs) in water from a tributary to Plesné Lake and a tributary to Jirická Pond, Czech Republic. Both tributaries had high concentrations of dissolved organic matter (∼1.8 mmol C L-1). Filtered (0.2 µm) samples were exposed to artificial solar radiation of 350 W m-2 for 48 to 96 h, corresponding to 3 to 6 days of natural solar radiation in summer at the sampling locations. Experiments were performed with altered and unaltered pH ranging from 3.8 to 6.0. The formation of particulate REEs occurred in all exposed samples with the fastest formation observed at the original pH. The formation of particulate metals continued in irradiated samples after the end of irradiation, suggesting that photochemically induced reactions and/or continuing precipitation continue in darkness or in deeper water due to mixing. Results were compared with paleolimnological records in the Plesné Lake sediment. At pH 5.0, the photochemically induced sediment flux was 3509 nmol m-2 y-1 for Ce, corresponding to 42% of the REEs' annual sediment flux in recent sediment layers. Combining the formation rates obtained in the laboratory irradiation experiments and known 1 day incident solar radiation enabled the estimation of a possible REE sediment flux. For Plesné Lake, the photochemically induced formation of particulate REEs explained 10-44% of the REE concentrations in the upper sediment layers. Observed photochemically induced sequestration of REEs into sediments can explain a significant part of the REEs' history in the Holocene sediment.

Modeling response of water quality parameters to land-use and climate change in a temperate, mesotrophic lake.

Lake Auburn, Maine, USA, is a historically unproductive lake that has experienced multiple algal blooms since 2011. The lake is the water supply source for a population of ~60,000. We modeled past temperature, and concentrations of dissolved oxygen (DO) and phosphorus (P) in Lake Auburn by considering the catchment and internal contributions of P as well as atmospheric factors, and predicted the change in lake water quality in response to future climate and land-use changes. A stream hydrology and P-loading model (SimplyP) was used to generate input from two major tributaries into a lake model (MyLake-Sediment) to simulate physical mixing, chemical dynamics, and sediment geochemistry in Lake Auburn from 2013 to 2017. Simulations of future lake water quality were conducted using meteorological boundary conditions derived from recent historical data and climate model projections for high greenhouse-gas emission cases. The effects of future land development on lake water quality for the 2046 to 2055 time period under different land-use and climate change scenarios were also simulated. Our results indicate that lake P enrichment is more responsive to extreme storm events than increasing air temperatures, mean precipitation, or windstorms; loss of fish habitat is driven by windstorms, and to a lesser extent an increasing water temperature; and catchment development further leads to water quality decline. All simulations also show that the lake is susceptible to both internal and external P loadings. Simulation of temperature, DO, and P proved to be an effective means for predicting the loss of water quality under changing land-use and climate scenarios.

Chemical controls on dissolved phosphorus mobilization in a calcareous agricultural stream during base flow.

This study explores the sources and mechanisms of dissolved phosphorus (P) mobilization under base flow conditions in a headwater stream. We characterized the relevant chemical species and processes within the watershed to investigate connections between stream sediment, surface water, and groundwater with respect to P dynamics. Waters were monitored monthly during the 2017 snow-free period for temperature, pH, dissolved oxygen, conductivity, soluble reactive P (SRP), total P, strong acid anions, strong base cations, dissolved organic carbon (DOC), Al, Fe, and Mn. Phosphorus speciation within sediment samples was determined by sequential chemical extractions. The emerging groundwater was under-saturated by up to 40% with respect to O2, with pH = 7.24, T = 7.0 °C, and SRP = 3.0 µg L-1. Groundwater PCO2 was up to ~35× the ambient PCO2 (410 ppm). Degassing of CO2 from the emerging groundwater resulted in a significant increase in pH downstream, and an increase in the SRP concentration from 3.0 to a maximum of 40.6 µg L-1. Laboratory experiments, using homogenized stream sediment, identified a reduction in the P adsorption capacity, and an increase in desorption of native P with increasing pH from ~7.25 (emerging groundwater) to ~8.50 (air-equilibrated surface water). These data allow us to identify the pH-dependent desorption from P-laden sediment as the most significant source of dissolved P in the headwater stream under base flow conditions.

Larch Tree Rings as a Tool for Reconstructing 20th Century Central European Atmospheric Mercury Trends.

We propose the tree rings of European Larch ( Larix decidua) as a widely available and reliable geochemical archive of local and regional changes in atmospheric mercury (Hg). Mean Hg concentrations in larch tree rings from 8 background sites across the Czech Republic ranged from 2.2 to 4.8 µg kg-1; the maximum concentrations occurred in the period 1951-1970. At 3 sites impacted by Hg-emission sources [gold amalgamation processing, caustic soda production, and lead (Pb) ore smelting] mean larch tree ring Hg concentrations were significantly elevated relative to background sites. Changes in larch tree ring Hg concentrations were temporally coherent with known activities at the sites that would alter Hg emissions; the nearly simultaneous response in tree rings indicated little or no translocation of Hg within the larch bole. Based on the present-day atmospheric Hg concentration of 1.63 ng m-3 at the intensively monitored Czech Global Mercury Observation System site and the most recent mean tree ring Hg concentration of 2.8 µg kg-1 in co-located larch trees, we developed a simple distribution model of Hg between the atmosphere and larch tree rings. We applied the model using observed changes of Hg in larch tree rings from the countrywide background sites to reconstruct past atmospheric Hg concentrations in central Europe. Modeled Hg concentrations were in agreement with annual means from the European Monitoring and Evaluation Programme observatories.

Climate Change Increasing Calcium and Magnesium Leaching from Granitic Alpine Catchments.

Climate change can reverse trends of decreasing calcium and magnesium [Ca + Mg] leaching to surface waters in granitic alpine regions recovering from acidification. Despite decreasing concentrations of strong acid anions (-1.4 µeq L-1 yr-1) during 2004-2016 in nonacidic alpine lakes in the Tatra Mountains (Central Europe), the average [Ca + Mg] concentrations increased (2.5 µeq L-1 yr-1), together with elevated terrestrial export of bicarbonate (HCO3-; 3.6 µeq L-1 yr-1). The percent increase in [Ca + Mg] concentrations in nonacidic lakes (0.3-3.2% yr-1) was significantly and positively correlated with scree proportion in the catchment area and negatively correlated with the extent of soil cover. Leaching experiments with freshly crushed granodiorite, the dominant bedrock, showed that accessory calcite and (to a lesser extent) apatite were important sources of Ca. We hypothesize that elevated terrestrial export of [Ca + Mg] and HCO3- resulted from increased weathering caused by accelerated physical erosion of rocks due to elevated climate-related mechanical forces (an increasing frequency of days with high precipitation amounts and air temperatures fluctuating around 0 °C) during the last 2-3 decades. These climatic effects on water chemistry are especially strong in catchments where fragmented rocks are more exposed to weathering, and their position is less stable than in soil.

Effects of acidic deposition on in-lake phosphorus availability: a lesson from lakes recovering from acidification.

Lake water concentrations of phosphorus (P) recently increased in some mountain areas due to elevated atmospheric input of P rich dust. We show that increasing P concentrations also occur during stable atmospheric P inputs in central European alpine lakes recovering from atmospheric acidification. The elevated P availability in the lakes results from (1) increasing terrestrial export of P accompanying elevated leaching of dissolved organic carbon and decreasing phosphate-adsorption ability of soils due to their increasing pH, and (2) decreasing in-lake P immobilization by aluminum (Al) hydroxide due to decreasing leaching of ionic Al from the recovering soils. The P availability in the recovering lakes is modified by the extent of soil acidification, soil composition, and proportion of till and meadow soils in the catchment. These mechanisms explain several conflicting observations of the acid rain effects on surface water P concentrations.

Mobilization of metals and phosphorus from intact forest soil cores by dissolved inorganic carbon.

Increased dissolved inorganic carbon (DIC) enhances the mobilization of metals and nutrients in soil solutions. Our objective was to investigate the mobilization of Al, Ca, Fe, and P in forest soils due to fluctuating DIC concentrations. Intact soil cores were taken from the O and B horizons at the Bear Brook Watershed in Maine (BBWM) to conduct soil column transport experiments. Solutions with DIC concentrations (∼20-600 ppm) were introduced into the columns. DIC was reversibly sorbed and its migration was retarded by a factor of 1.2 to 2.1 compared to the conservative sodium bromide tracer, corresponding to a log K (D) = -0.82 to -0.07. Elevated DIC significantly enhanced the mobilization of all Al, Fe, Ca, and P. Particulate (>0.4 µm) Al and Fe were mobilized during chemical and flow transitions, such as increasing DIC and dissolved organic carbon (DOC), and resumption of flow after draining the columns. Calcium and P were primarily in dissolved forms. Mechanisms such as ion exchange (Al, Fe, Ca), ligand- and proton-promoted dissolution (Al and Fe), and ligand exchange (P) were the likely chemical mechanisms for the mobilization of these species. One column was packed with dried and sieved B-horizon soil. The effluent from this column had DOC, Al, and Fe concentrations considerably higher than those in the intact columns, suggesting that these species were mobilized from soil's microporous structure that was otherwise not exposed to the advective flow. Calcium and P concentrations, however, were similar to those in the intact columns, suggesting that these elements were less occluded in soil particles.

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 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 SO4(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.

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 SO4(-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 SO(2). Emissions of NO(x) have not changed substantially, but deposition has declined slightly at BBWM. Base cations, NH4+, 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 NO3- 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 SO4(-2), with consequent acidification (lower pH and higher inorganic Al). Eighteen years of experimental treatment with (NH(4))(2)SO(4) enhanced acidification of West Bear Brook's (WB) watershed. Despite the manipulation, NH4+ concentration remained below detection limits at WB, while leaching of NO3- increased. The seasonal pattern for NO3- concentrations in WB, however, remained similar to EB. Mean monthly concentrations of SO4(-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.

Experimental photochemical release of organically bound aluminum and iron in three streams in Maine, USA.

Laboratory photochemical experiments with stream water were done to characterize the photodegradation of dissolved organic carbon (DOC) and photochemical release of organically bound metals. The samples were collected from Bear Brook Watershed, Hadlock Brook, and Mud Pond Stream in Maine, USA, during January and April 2006. Filtered samples were irradiated in a reactor equipped with 350 nm irradiation lamps. Aliquots of irradiated samples were analyzed for DOC, dissolved aluminum (Al(d)) and iron (Fe(d)), pH, and UV-Vis spectra. Organically bound metals (Fe(o) and Al(o)) were measured after passing the sample through a column filled with a strong cation exchange resin (Dowex HCR-W2). UV radiation resulted in a decrease in DOC concentration and structural changes in DOC composition. UV-Vis spectra showed a decrease in aromaticity and molecular weight of DOC during irradiation. The DOC ranged from 0.1 to 0.35 mmol L(-1) at the beginning of experiments and decreased 5% to 37% after irradiation. Oxidation and structural changes in DOC resulted in the release of organically bound metals. Initial Fe(o) concentrations ranged from 0.16 to 0.79 µmol L(-1) and decreased 56% to 81% during the irradiation. The concentration of Al(o) ranged from 1.0 to 3.85 µmol L(-1) and declined steadily throughout the irradiation, resulting in 8% to 76% decline. Degradation of a small percentage of organically bound Al and Fe occurs rapidly enough so as to be an important process in first- and second-order streams. Irradiation energy absorbed by samples during hours of laboratory experiments equates to days in stream environment. Degradation of more refractory complexes occurs on a time scale that requires longer residence times, such as in lakes. This study demonstrated a strong impact of photochemical degradation of DOC on its metal-complexing ability and capacity. The results also suggest different binding properties of Fe and Al in their organic complexes.

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 (NH(4))(2)SO(4). 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 SO4(2-) to the ANC decline in WB has been increasing linearly since the beginning of watershed treatment, while the role of NO3- 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.

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 (NH(4))(2)SO(4) 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.

Trends in aluminium export from a mountainous area to surface waters, from deglaciation to the recent: effects of vegetation and soil development, atmospheric acidification, and nitrogen-saturation.

We reconstructed the history of terrestrial export of aluminium (Al) to Plesné Lake (Czech Republic) since the lake origin approximately 12,600 year BC, and predicted Al export for 2010-2050 on the basis of previously published and new data on mass budget studies, palaeolimnological data, and MAGIC modelling. We focused on three major Al forms; ionic Al (Al(i)), organically-bound Al (Al(o)), and particulate Al hydroxide [Al(OH)(3)]. In early post-glacial time, Plesné Lake received high terrestrial export of Al, but with a minor proportion of Al(OH)(3) (4-25 microM), and concentrations of Al(i) and Al(o) were negligible. Since the forest and soil development ( approximately 9900-9000 year BC), erosion has declined and soil organic acids increased export of Al(o) from soils. The terrestrial Al(o) leaching ( approximately 7.5 microM) persisted throughout the Holocene until the industrial period. Then, Al(i) concentrations continuously increased (up to 28 microM in the mid-1980s) due to atmospheric acidification; the Al(i) leaching was mostly associated with sulphate. The proportion of Al(i) associated with nitrate has been increasing since the beginning of lake recovery from acidification after approximately 1990 due to reduction in sulphur deposition and nitrogen-saturation of the catchment, leading to persistent nitrate leaching. Currently, nitrate has become the dominant strong acid anion and the major Al(i) carrier. Al(o) (5.5 microM) is predicted to dominate Al concentrations around 2050, but the predicted Al(i) concentrations ( approximately 4 microM) are uncertain because of uncertainty associated with the future nitrate leaching and its effect on soils.