Long-term monitoring of Vermont's forest soils: early trends and efforts to address innate variability.

Long-term monitoring of forest soils is necessary to understand the effects of continued environmental change, including climate change, atmospheric deposition of metals, and, in many regions, recovery from acidic precipitation. A monitoring program was initiated in 2002 at five protected forest sites, primarily Spodosol soils, in Vermont, northeastern USA. Every 5 years, ten soil pits were sampled from random subplots in a 50 × 50-m plot at each site. Samples were taken by genetic horizon and, to reduce variability and improve comparability, from four specific layers: the combined Oi/Oe layer, the combined Oa/A layer, the top 10 cm of the B horizon, and 60-70 cm below the soil surface (usually the C horizon). The samples were archived and a subset analyzed for carbon, nitrogen, and exchangeable cations. After four sampling campaigns, the average coefficients of variation (CVs) at each site had a broad range, 10.7% for carbon in the Oa/A horizon to 84.3% for exchangeable Ca2+ in the B horizon. An investigation of variability within the upper 10 cm of the B horizon across a 90-cm soil pit face showed similar CVs to the entire site, emphasizing the need for consistent and careful sampling. After 15 years, temporal trends were significant in the Oa/A and B horizons at two of the five sites, with one site showing an increase in carbon concentration in both layers along with increases in both exchangeable Ca2+ and Al3+ in the B horizon, perhaps linked to recovery from acidification. The monitoring program plans to continue at 5-year intervals for the next century.

Resolving a paradox-high mercury deposition, but low bioaccumulation in northeastern Puerto Rico.

At a "clean air" trade winds site in northeastern Puerto Rico, we found an apparent paradox: atmospheric total mercury (THg) deposition was highest of any site in the USA Mercury Deposition Network, but assimilation into the local food web was quite low. Avian blood THg concentrations (n = 31, from eight species in five foraging guilds) ranged widely from 0.2 to 32 ng g-1 (median of 4.3 ng g-1). Within this population, THg was significantly greater at a low-elevation site near a wetland compared to an upland montane site, even when the comparison was limited to a single species. Overall, however, THg concentrations were approximately an order of magnitude lower than comparable populations in the continental U.S. In surface soil and sediment, potential rates of demethylation were 3 to 9-fold greater than those for Hg(II)-methylation (based on six radiotracer amendment incubations), but rates of change of ambient MeHg pools showed a slight net positive Hg(II)-methylation. Thus, the resolution of the paradox is that MeHg degradation approximately keeps pace with MeHg production in this landscape. Further, any net production of MeHg is subject to frequent flushing by high rainfall on chronically wet soils. The interplay of these microbial processes and hydrology appears to shield the local food web from adverse effects of high atmospheric mercury loading. This scenario may play out in other humid tropical ecosystems as well, but it is difficult to evaluate because coordinated studies of Hg deposition, methylation, and trophic uptake have not been conducted at other tropical sites.

Unprocessed Atmospheric Nitrate in Waters of the Northern Forest Region in the U.S. and Canada.

Little is known about the regional extent and variability of nitrate from atmospheric deposition that is transported to streams without biological processing in forests. We measured water chemistry and isotopic tracers (δ18O and δ15N) of nitrate sources across the Northern Forest Region of the U.S. and Canada and reanalyzed data from other studies to determine when, where, and how unprocessed atmospheric nitrate was transported in catchments. These inputs were more widespread and numerous than commonly recognized, but with high spatial and temporal variability. Only 6 of 32 streams had high fractions (>20%) of unprocessed atmospheric nitrate during baseflow. Seventeen had high fractions during stormflow or snowmelt, which corresponded to large fractions in near-surface soil waters or groundwaters, but not deep groundwater. The remaining 10 streams occasionally had some (<20%) unprocessed atmospheric nitrate during stormflow or baseflow. Large, sporadic events may continue to be cryptic due to atmospheric deposition variation among storms and a near complete lack of monitoring for these events. A general lack of observance may bias perceptions of occurrence; sustained monitoring of chronic nitrogen pollution effects on forests with nitrate source apportionments may offer insights needed to advance the science as well as assess regulatory and management schemes.

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.

Modeled ecohydrological responses to climate change at seven small watersheds in the northeastern United States.

A cross-site analysis was conducted on seven diverse, forested watersheds in the northeastern United States to evaluate hydrological responses (evapotranspiration, soil moisture, seasonal and annual streamflow, and water stress) to projections of future climate. We used output from four atmosphere-ocean general circulation models (AOGCMs; CCSM4, HadGEM2-CC, MIROC5, and MRI-CGCM3) included in Phase 5 of the Coupled Model Intercomparison Project, coupled with two Representative Concentration Pathways (RCP 8.5 and 4.5). The coarse resolution AOGCMs outputs were statistically downscaled using an asynchronous regional regression model to provide finer resolution future climate projections as inputs to the deterministic dynamic ecosystem model PnET-BGC. Simulation results indicated that projected warmer temperatures and longer growing seasons in the northeastern United States are anticipated to increase evapotranspiration across all sites, although invoking CO2 effects on vegetation (growth enhancement and increases in water use efficiency (WUE)) diminish this response. The model showed enhanced evapotranspiration resulted in drier growing season conditions across all sites and all scenarios in the future. Spruce-fir conifer forests have a lower optimum temperature for photosynthesis, making them more susceptible to temperature stress than more tolerant hardwood species, potentially giving hardwoods a competitive advantage in the future. However, some hardwood forests are projected to experience seasonal water stress, despite anticipated increases in precipitation, due to the higher temperatures, earlier loss of snow packs, longer growing seasons, and associated water deficits. Considering future CO2 effects on WUE in the model alleviated water stress across all sites. Modeled streamflow responses were highly variable, with some sites showing significant increases in annual water yield, while others showed decreases. This variability in streamflow responses poses a challenge to water resource management in the northeastern United States. Our analyses suggest that dominant vegetation type and soil type are important attributes in determining future hydrological responses to climate change.

High Mercury Wet Deposition at a "Clean Air" Site in Puerto Rico.

Atmospheric mercury deposition measurements are rare in tropical latitudes. Here we report on seven years (April 2005 to April 2012, with gaps) of wet Hg deposition measurements at a tropical wet forest in the Luquillo Mountains, northeastern Puerto Rico, U.S. Despite receiving unpolluted air off the Atlantic Ocean from northeasterly trade winds, during two complete years the site averaged 27.9 µg m(-2) yr(-1) wet Hg deposition, or about 30% more than Florida and the Gulf Coast, the highest deposition areas within the U.S. These high Hg deposition rates are driven in part by high rainfall, which averaged 2855 mm yr(-1). The volume-weighted mean Hg concentration was 9.8 ng L(-1), and was highest during summer and lowest during the winter dry season. Rainout of Hg (decreasing concentration with increasing rainfall depth) was minimal. The high Hg deposition was not supported by gaseous oxidized mercury (GOM) at ground level, which remained near global background concentrations (<10 pg m(-3)). Rather, a strong positive correlation between Hg concentrations and the maximum height of rain detected within clouds (echo tops) suggests that droplets in high convective cloud tops scavenge GOM from above the mixing layer. The high wet Hg deposition at this "clean air" site suggests that other tropical areas may be hotspots for Hg deposition as well.

Atmospheric mercury and its deposition during the phasing out of an amalgam electrolysis plant: temporal, seasonal, and spatial patterns.

Large amounts of mercury (Hg) were consumed and emitted into the atmosphere during the process of amalgam electrolysis used to produce chlorine and caustic soda since the nineteenth century. In Europe, amalgam electrolysis has been gradually replaced by advanced Hg-free technologies. In this work, we describe changes in atmospheric Hg and bulk Hg wet deposition during the phasing out of an amalgam electrolytic production line of a chlor-alkali plant in Neratovice, Czech Republic, central Europe. Bulk wet deposition Hg near the chlor-alkali plant was low at 3.6 ± 0.8 µg m-2 year-1 due in part to low annual precipitation amounts (486 ± 97 mm) in the period 2015-2021. Nevertheless, Hg deposition was elevated relative to a nearby reference site both before and after decommissioning of the electrolytic line. Switching off the amalgam electrolytic line did not notably affect bulk wet deposition Hg near the chlor-alkali plant. Levels of gaseous elemental Hg (GEM) and particle-bound Hg (PBM) monitored seasonally four times per year over 24-h time periods indicated rapid declines in four nearby settlements set in cardinal directions from the Hg emission source. Mean atmospheric GEM and PBM concentrations decreased rapidly from 9.0 ± 2.1 ng m-3 and 243 ± 255 pg m-3 in the period 2013-2017 when amalgam electrolysis was operating to 3.3 ± 0.4 ng m-3 and 32 ± 6 pg m-3 in the period 2018-2021 after its decommissioning in November 2017. Seasonal changes of GEM coincided with changes in temperature with the highest concentrations in summer, while PBM air levels were lowest in summer due to the highest seasonal precipitation amount. GEM concentrations at the four monitored settlements at Neratovice remained elevated at 2.8 ng m-3 with respect to regional background, but PBM levels decreased to background levels.

MERGANSER: an empirical model to predict fish and loon mercury in New England lakes.

MERGANSER (MERcury Geo-spatial AssessmeNtS for the New England Region) is an empirical least-squares multiple regression model using mercury (Hg) deposition and readily obtainable lake and watershed features to predict fish (fillet) and common loon (blood) Hg in New England lakes. We modeled lakes larger than 8 ha (4404 lakes), using 3470 fish (12 species) and 253 loon Hg concentrations from 420 lakes. MERGANSER predictor variables included Hg deposition, watershed alkalinity, percent wetlands, percent forest canopy, percent agriculture, drainage area, population density, mean annual air temperature, and watershed slope. The model returns fish or loon Hg for user-entered species and fish length. MERGANSER explained 63% of the variance in fish and loon Hg concentrations. MERGANSER predicted that 32-cm smallmouth bass had a median Hg concentration of 0.53 µg g(-1) (root-mean-square error 0.27 µg g(-1)) and exceeded EPA's recommended fish Hg criterion of 0.3 µg g(-1) in 90% of New England lakes. Common loon had a median Hg concentration of 1.07 µg g(-1) and was in the moderate or higher risk category of >1 µg g(-1) Hg in 58% of New England lakes. MERGANSER can be applied to target fish advisories to specific unmonitored lakes, and for scenario evaluation, such as the effect of changes in Hg deposition, land use, or warmer climate on fish and loon mercury.

Mercury in the pelagic food web of Lake Champlain.

Lake Champlain continues to experience mercury contamination resulting in public advisories to limit human consumption of top trophic level fish such as walleye. Prior research suggested that mercury levels in biota could be modified by differences in ecosystem productivity as well as mercury loadings. We investigated relationships between mercury in different trophic levels in Lake Champlain. We measured inorganic and methyl mercury in water, seston, and two size fractions of zooplankton from 13 sites representing a range of nutrient loading conditions and productivity. Biomass varied significantly across lake segments in all measured ecosystem compartments in response to significant differences in nutrient levels. Local environmental factors such as alkalinity influenced the partitioning of mercury between water and seston. Mercury incorporation into biota was influenced by the biomass and mercury content of different ecosystem strata. Pelagic fish tissue mercury was a function of fish length and the size of the mercury pool associated with large zooplankton. We used these observations to parameterize a model of mercury transfers in the Lake Champlain food web that accounts for ecosystem productivity effects. Simulations using the mercury trophic transfer model suggest that reductions of 25-75% in summertime dissolved eplimnetic total mercury will likely allow fish tissue mercury concentrations to drop to the target level of 0.3 µg g(-1) in a 40-cm fish in all lake segments. Changes in nutrient loading and ecosystem productivity in eutrophic segments may delay any response to reduced dissolved mercury and may result in increases in fish tissue mercury.

A systematic increase in the slope of the concentration discharge relation for dissolved organic carbon in a forested catchment in Vermont, USA.

The production, mobilization and fluvial transport of dissolved organic carbon (DOC) in temperate forests are important components of the carbon cycle that are influenced by ongoing changes in climate. Numerous studies have reported temporal trends in stream water DOC concentrations and have attributed changes in concentrations to climatic and hydrologic variables. Fewer studies have reported trends in concentration-discharge (C-Q) relations for DOC. The goal of this study was to detect and quantify changes in DOC concentration and slope of the C-Q relation from 1991 to 2018 in an intensively sampled forested research watershed in northern Vermont. Stream water DOC concentration and slope of the C-Q relation increased over time as did precipitation, stream discharge, and air temperature. The increases in DOC concentration and slope of the C-Q were substantially greater in the summer and fall (autumn) than in winter and spring. The largest increases in the magnitude of C-Q slopes occurred in the December, October and September. The increases in slope of the C-Q relation in summer and fall were larger for baseflow than for storm flow. The increases in DOC concentration and slope of the C-Q relation over time may be related to increasing temperature, longer growing seasons, and associated increases in production and microbial decomposition of soil organic matter that supplies DOC for mobilization to streams. The results suggest that in a changing climate, C-Q relations may not necessarily be stationary and therefore analyses that attempt to estimate future DOC concentrations and loads should consider potentially changing C-Q relations over time.

Recent advances in understanding and measurement of mercury in the environment: Terrestrial Hg cycling.

This review documents recent advances in terrestrial mercury cycling. Terrestrial mercury (Hg) research has matured in some areas, and is developing rapidly in others. We summarize the state of the science circa 2010 as a starting point, and then present the advances during the last decade in three areas: land use, sulfate deposition, and climate change. The advances are presented in the framework of three Hg "gateways" to the terrestrial environment: inputs from the atmosphere, uptake in food, and runoff with surface water. Among the most notable advances: These and other advances reported here are of value in evaluating the effectiveness of the Minamata Convention on reducing environmental Hg exposure to humans and wildlife.

Decreasing litterfall mercury deposition in central European coniferous forests and effects of bark beetle infestation.

We evaluated a 14-year trend (2003-2017) in mercury (Hg) concentrations and fluxes in six litterfall categories (needles, bark, twigs, cones, lichen, and a mixture of unidentified fragments) at six research plots situated in two central European unmanaged mountain forest stands, dominated by mature Norway spruce. One of the stands (catchment of Plesné Lake, PL) was infested by bark beetle and all mature spruces died at three of four research plots during the study. One PL plot and two plots in the second stand (catchment of Certovo Lake, CT) were intact and used as a control. At the intact plots, the litterfall Hg deposition averaged 45 and 32 µg/m2/year in the PL and CT catchments, respectively, while bulk precipitation Hg deposition was an order of magnitude lower (2.6 µg/m2/year). In the individual litter categories, Hg concentrations averaged 223, 195, 126, 81, 79 and 30 µg/kg in lichen, unidentified fragments, bark, twigs, needles and cones, respectively. As a result of decreasing European Hg emissions, Hg concentrations in most litter categories decreased from 2003 to 2017. Consequently, the litter-associated Hg flux to the forest floor decreased from 66 to 23 µg/m2/year during 2003-2017. The litterfall mass fluxes exhibited no trends at the intact plots. In contrast, the litter-associated Hg flux increased 5-fold after tree dieback due to elevated litterfall, averaging 218 µg/m2/year Hg at the PL infested plots during 2004-2009. The relative contribution of individual litter categories to the total Hg flux shifted from needle to bark and twig dominance. Starting in 2010, Hg flux decreased to pre-disturbance levels for the following decade. The tree mortality in the PL catchment provided a unique opportunity to evaluate changes in litter-associated Hg fluxes to the forest floor during and after natural tree dieback.

Seasonal and event variations in delta34S values of stream sulfate in a Vermont forested catchment: implications for sulfur sources and cycling.

Stable sulfur (S) isotope ratios can be used to identify the sources of sulfate contributing to streamwater. We collected weekly and high-flow stream samples for S isotopic analysis of sulfate through the entire water year 2003 plus the snowmelt period of 2004. The study area was the 41-ha forested W-9 catchment at Sleepers River Research Watershed, Vermont, a site known to produce sulfate from weathering of sulfide minerals in the bedrock. The delta(34)S values of streamwater sulfate followed an annual sinusoidal pattern ranging from about 6.5 per thousand in early spring to about 10 per thousand in early fall. During high-flow events, delta(34)S values typically decreased by 1 to 3 per thousand from the prevailing seasonal value. The isotopic evidence suggests that stream sulfate concentrations are controlled by: (1) an overall dominance of bedrock-derived sulfate (delta(34)S approximately 6-14 per thousand); (2) contributions of pedogenic sulfate (delta(34)S approximately 5-6 per thousand) during snowmelt and storms with progressively diminishing contributions during base flow recession; and (3) minor effects of dissimilatory bacterial sulfate reduction and subsequent reoxidation of sulfides. Bedrock should not be overlooked as a source of S in catchment sulfate budgets.

Comparison of total mercury and methylmercury cycling at five sites using the small watershed approach.

The small watershed approach is well-suited but underutilized in mercury research. We applied the small watershed approach to investigate total mercury (THg) and methylmercury (MeHg) dynamics in streamwater at the five diverse forested headwater catchments of the US Geological Survey Water, Energy, and Biogeochemical Budgets (WEBB) program. At all sites, baseflow THg was generally less than 1ng L(-1) and MeHg was less than 0.2ng L(-1). THg and MeHg concentrations increased with streamflow, so export was primarily episodic. At three sites, THg and MeHg concentration and export were dominated by the particulate fraction in association with POC at high flows, with maximum THg (MeHg) concentrations of 94 (2.56)ng L(-1) at Sleepers River, Vermont; 112 (0.75)ng L(-1) at Rio Icacos, Puerto Rico; and 55 (0.80)ng L(-1) at Panola Mt., Georgia. Filtered (<0.7microm) THg increased more modestly with flow in association with the hydrophobic acid fraction (HPOA) of DOC, with maximum filtered THg concentrations near 5ng L(-1) at both Sleepers and Icacos. At Andrews Creek, Colorado, THg export was also episodic but was dominated by filtered THg, as POC concentrations were low. MeHg typically tracked THg so that each site had a fairly constant MeHg/THg ratio, which ranged from near zero at Andrews to 15% at the low-relief, groundwater-dominated Allequash Creek, Wisconsin. Allequash was the only site with filtered MeHg consistently above detection, and the filtered fraction dominated both THg and MeHg. Relative to inputs in wet deposition, watershed retention of THg (minus any subsequent volatilization) was 96.6% at Allequash, 60% at Sleepers, and 83% at Andrews. Icacos had a net export of THg, possibly due to historic gold mining or frequent disturbance from landslides. Quantification and interpretation of Hg dynamics was facilitated by the small watershed approach with emphasis on event sampling.

The history of mercury pollution near the Spolana chlor-alkali plant (Neratovice, Czech Republic) as recorded by Scots pine tree rings and other bioindicators.

We assessed >100years of mercury (Hg) pollution recorded in the tree rings of Scots Pine near a Czech chlor-alkali plant operating since 1941. Hg concentrations in tree rings increased with the launching of plant operations and decreased when Hg emissions decreased in 1975 due to an upgrade in production technology. Similar to traditional bioindicators of pollution such as pine needles, bark and forest floor humus, Hg concentrations in Scots Pine boles decreased with distance from the plant. Mean Hg in pine bole in the 1940s ranged from 32.5µg/kg Hg at a distance of 0.5km from the plant to 5.4µg/kg at a distance of >4.7km, where tree ring Hg was the same as at a reference site, and other bioindicators also suggest that the effect of the plant was no longer discernible. Tree ring Hg concentrations decreased by 8-29µg/kg since the 1940s at all study sites including the reference site. The lack of exact correspondence between changes at the plant and tree ring Hg indicated some smearing of the signal due to lateral translocation of Hg from sapwood to heartwood. Bole Hg concentrations reflected local and regional atmospheric Hg concentrations, and not Hg wet deposition.

Rapid regional recovery from sulfate and nitrate pollution in streams of the western Czech Republic--comparison to other recovering areas.

Hydrochemical changes between 1991 and 2001 were assessed based on two synoptic stream surveys from the 820-km2 region of the Slavkov Forest and surrounding area, western Czech Republic. Marked declines of sulfate, nitrate, chloride, calcium and magnesium in surface waters were compared with other areas of Europe and North America recovering from acidification. Declines of sulfate concentration in the Slavkov Forest (-30 microeq L(-1) yr(-1)) were more dramatic than declines reported from other sites. However, these dramatic declines of strong acid anions did not generate a widespread increase of stream water pH in the Slavkov Forest. Only the most acidic streams experienced a slight increase of pH by 0.5 unit. An unexpected decline of stream water pH occurred in slightly alkaline streams.

Streamwater fluxes of total mercury and methylmercury into and out of Lake Champlain.

From 2000 to 2004, we sampled for total mercury (THg) and methylmercury (MeHg) in inlet streams to Lake Champlain, targeting high flow periods to capture increases in THg and MeHg concentrations with increasing flow. We used these data to model stream THg and MeHg fluxes for Water Years 2001 through 2009. In this mountainous forested basin with a high watershed-to-lake area ratio of 18, fluvial export from the terrestrial watershed was the dominant source of Hg to the lake. Unfiltered THg and MeHg fluxes were dominated by the particulate fraction; about 40% of stream THg was in the filtered (<0.4 µm) phase. THg flux from the watershed to the lake averaged 2.37 µg m(-2) yr(-1), or about 13% of atmospheric Hg wet and dry deposition to the basin. THg export from the lake represented only about 3% of atmospheric Hg input to the basin.

Ultraviolet absorbance as a proxy for total dissolved mercury in streams.

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg(d)), DOC concentration and DOC composition, and UV(254) absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg(d) to DOC (r(2)=0.87), but progressively stronger correlations of THg(d) with the hydrophobic acid fraction (HPOA) of DOC (r(2)=0.91) and with UV(254) absorbance (r(2)=0.92). The strength of the UV(254) absorbance-THg(d) relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg(d) concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg(d) flux in drainage waters.

Flow-specific trends in river-water quality resulting from the effects of the Clean Air Act in three mesoscale, forested river basins in the northeastern United States through 2002.

Two new methods for assessing temporal trends in stream-solute concentrations at specific streamflow ranges were applied to long (40 to 50-year) but sparse (bi-weekly to quarterly sampling) stream-water quality data collected at three forested mesoscale basins along an atmospheric deposition gradient in the northeastern United States (one in north-central Pennsylvania, one in southeastern New York, and one in eastern Maine). The three data sets span the period since the implementation of the Clean Air Act in 1970 and its subsequent amendments. Declining sulfate (O4(2-)) trends since the mid 1960s were identified for all 3 rivers by one or more of the 4 methods of trend detection used. Flow-specific trends were assessed by segmenting the data sets into 3-year and 6-year blocks, then determining concentration-discharge relationships for each block. Declining sulfate (O4(2-)) trends at median flow were similar to trends determined using a Seasonal Kendall Tau test and Sen slope estimator. The trend of declining O4(2-) concentrations differed at high, median and low flow since the mid 1980s at YWC and NR, and at high and low flow at WR, but the trends leveled or reversed at high flow from 1999 through 2002. Trends for the period of record at high flows were similar to medium- and low-flow trends for Ca2++ Mg2+ concentrations at WR, non-significant at YWC, and were more negative at low flow than at high flow at NR; trends in nitrate (NO3-), and alkalinity (ALK) concentrations were different at different flow conditions, and in ways that are consistent with the hydrology and deposition history at each watershed. Quarterly sampling is adequate for assessing average-flow trends in the chemical parameters assessed over long time periods (approximately decades). However, with even a modest effort at sampling a range of flow conditions within each year, trends at specified flows for constituents with strong concentration-discharge relationships can be evaluated and may allow early detection of ecosystem response to climate change and pollution management strategies.

Mass balance assessment for mercury in Lake Champlain.

A mass balance model for mercury in Lake Champlain was developed in an effort to understand the sources, inventories, concentrations, and effects of mercury (Hg) contamination in the lake ecosystem. To construct the mass balance model, air, water, and sediment were sampled as a part of this project and other research/monitoring projects in the Lake Champlain Basin. This project produced a STELLA-based computer model and quantitative apportionments of the principal input and output pathways of Hg for each of 13 segments in the lake. The model Hg concentrations in the lake were consistent with measured concentrations. Specifically, the modeling identified surface water inflows as the largest direct contributor of Hg into the lake. Direct wet deposition to the lake was the second largest source of Hg followed by direct dry deposition. Volatilization and sedimentation losses were identified as the two major removal mechanisms. This study significantly improves previous estimates of the relative importance of Hg input pathways and of wet and dry deposition fluxes of Hg into Lake Champlain. It also provides new estimates of volatilization fluxes across different lake segments and sedimentation loss in the lake.