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Estimates of ion sources in deciduous and coniferous throughfall

Estimates of external and internal sources of ions in net througfall deposition were derived for a deciduous and coniferous canopy by use of multiple regression. The external source component appears to be dominated by dry deposition of Ca 2+ , SO 2 and NO 3 − during dormant and growing seasons for the two canopy types. Increases in the leaching rates of K + and Mg 2+ during the growing season reflect the presence of leaves in the deciduous canopy and increased physiological activity in both canopies. Internal leaching rates for SO 4 2− doubled during the growing season presumably caused by increased physiological activity and uptake of SO 2 through stomates. Net deposition of SO 4 2− in throughfall during the growing season appears highly dependent on stomatal uptake of SO 2 . Estimates of SO 2 deposition velocities were 0.06 cm s −1 and 0.13 cm s −1 for the deciduous and coniferous canopies, respectively, during the dormant seasons, and 0.30 cm s −1 and 0.43 cm s −1 for the deciduous and coniferous canopies, respectively, during the growing season. For the ions of major interest with respect to ecosystem effects, namely H + , NO 3 − and SO 4 2− , precipitation inputs generally outweighed estimates of dry deposition input. However, net throughfall deposition of NO 3 − and SO 4 2− accounted for 20–47 and 34–50 per cent, respectively, of total deposition of those ions. Error estimates of ion sources were at least 50–100 per cent and the method is subject to several assumptions and limitations.

Virginia

Precipitation-chemistry measurements from the California Acid Deposition Monitoring Program, 1985-1990

The configuration of the California Acid Deposition Monitoring Program (CADMP) precipitation network is described and quality assurance results summarized. Comparison of CADMP and the National Acid Deposition Program/National Trends Network (NADP/NTN) data at four parallel sites indicated that mean depth-weighted differences were less than 3 μeq ℓ −1 for all ions, being statistically significant for ammonium, sulfate and hydrogen ion. These apparently small differences were 15–30% of the mean concentrations of ammonium, sulfate and hydrogen ion. Mean depth-weighted concentrations and mass deposition rates for the period 1985–1990 are summarized; the latter were highest either where concentrations or precipitation depths were relatively high.

Atmospheric Environment

The influence of mountain meteorology on precipitation chemistry at low and high elevations of the Colorado Front Range, USA

We explored the seasonal characteristics in wet deposition chemistry for two sites located at different elevations along the east slope of the Colorado Front Range in Rocky Mountain National Park. Seasonally separated precipitation was stratified into highly concentrated (high salt), dilute (low salt), or acid-dominated precipitation groups. These groups and unstratified precipitation data were related to mean easterly or westerly zonal winds to determine direction of local transport. Strong acid anion associations were also determined for the stratified and unstratified precipitation data sets. We found that strong acid anions, acidity, ammonium, and high salt concentrations originate to the east of Rocky Mountain National Park, and are transported via up-valley funneling winds or convective instability from differential heating of the mountains and the plains to the east. These influence the composition of precipitation at Beaver Meadows, the low elevation site, throughout the year, while their effect on precipitation at Loch Vale, the high elevation site, is felt most strongly during the summer. During the winter, Loch Vale precipitation is very dilute, and occurs in conjunction with westerly winds resulting from the southerly location of the jet stream.

Colorado

A possible deficiency in estimates of wet deposition obtained from data generated by the NADP/NTN network

A conventional precipitation scavenging model is used to evaluate the effect of the performance of a wet-deposition collector on the reported deposition amounts. Three National Atmospheric Deposition Program/National Trends Network sites in semi arid western Colorado were chosen to evaluate chloride and sulfate wet deposition. Observations of the performance of a wet-deposition collector have demonstrated a delay in opening and cycling during a precipitation event. A significant fraction of wet deposition may be excluded when small amounts of initial precipitation are not sampled and a potentially large fraction of annual wet deposition may be excluded if a majority of precipitation events are small. The actual amount missed depends on the precipitation intensity, variability of intensity with time, raindrop or snowflake size and the individual performance characteristics of the collector. Detailed performance data are needed for individual wet-deposition collectors before accurate estimates of wet deposition can be expected.

Atmospheric Environment

Variations of weekly atmospheric deposition for multiple collectors at a site on the shore of Lake Okeechobee, Florida

Eight wet/dry precipitation collectors were modified to house four additional dryfall collectors and one bulk precipitation collector to sample atmospheric deposition for 12 weeks in a small area on the southwestern shore of Lake Okeechobee; sample contamination, primarily by insects, reduced the comparison to the last nine weeks. The deposition was determined for Ca2+, Na+, Cl-, and SO42- and nutrients including total phosphorus, orthophosphate, total ammonia plus organic nitrogen, and nitrite plus nitrate. In general, deposition was lower and less variable in wet precipitation than in bulk precipitation. The higher variability of the bulk precipitation was attributed to local contamination, particularly by dust and insects. Each wet/dry precipitation collector was fitted with dryfall collectors that consisted of the dry-side bucket on a wet/dry collector, which was preloaded with distilled and deionized water, and four glass dish collectors; two of the glass dishes were preloaded with water and the other two remained dry. The deposition to the dry dish collectors was not comparable in adjacent collectors for any constituent; however, the deposition in the adjacent water-loaded dishes was comparable for most major constituents, except nutrients. A comparison of Ortho-P deposition with Total-P indicated that the P collected by the dryfall collectors was predominantly reactive, which also was reflected in the bulk deposition, whereas that in the wet deposition was mostly nonreactive. The large variability in deposition of P among the bulk and dryfall collectors suggests that alternative methods must be used to evaluate the P sources and processes of atmospheric transfer.

Atmospheric Environment

Particulate carbonate matter in snow from selected sites in the south-central Rocky Mountains

Trends in snow acidity reflect the balance between strong acid inputs and reactions with neutralizing materials. Carbonate dust can be an important contributor of buffering capacity to snow however, its concentration in snow is difficult to quantify because it dissolves rapidly in snowmelt. In snow with neutral or acidic pH, most calcite would dissolve during sample melting if snow samples were processed using standard techniques. Here a method is described for separating particulate carbonate matter from snow. Snow samples were melted in solutions close to saturation with calcite, decreasing the dissolution rate by a factor of 100-200 compared with natural melting of snow. Particulate matter larger than 0.45 ??m in diameter was then filtered from solution and analysed for carbonate content. Particulate carbonate matter concentrations are reported for 25 sites in the south-central Rocky Mountains. Results are compared with Ca2+ and H+ concentrations and regional trends are evaluated. In Colorado, mean particulate carbonate in snow was 43 ??g kg-1 at sampling sites in the southern mountains and only 4 ??g kg-1 at sites in the northern mountains. The higher calcite concentrations in the south probably are related to the proximity of sampling sites to major outcrops of limestone. Particulate carbonate at sampling sites in Utah and Wyoming ranged from 3-35 ??g kg-1. The levels of particulate calcite measured in snow samples are sufficient to neutralize an average of 0.4 ??eq H+ kg-1 snow. Strong acid anion concentrations in samples from east of Craig, Colorado, were 30-50% higher than in samples from the Colorado Front Range, but H+ concentrations were 400-600% higher east of Craig. Relatively low Ca2+ concentrations in the samples from east of Craig indicate that the difference in snow acidity was due mostly to lower concentrations of neutralizing materials.Trends in snow acidity reflect the balance between strong acid inputs and reactions with neutralizing materials. Carbonate dust can be an important contributor of buffering capacity to snow; however, its concentration in snow is difficult to quantify because it dissolves rapidly in snowmelt. In snow with neutral or acidic pH, most calcite would dissolve during sample melting if snow samples were processed using standard techniques. Here a method is described for separating particulate carbonate matter from snow. Snow samples were melted in solutions close to saturation with calcite, decreasing the dissolution rate by a factor of 100-200 compared with natural melting of snow. Particulate matter larger than .45 micrometers in diameter was then filtered from solution and analyzed for carbonate content.

Atmospheric Environment

The precision of wet atmospheric deposition data from national atmospheric deposition program/national trends network sites determined with collocated samplers

A collocated, wet-deposition sampler program has been operated since October 1988 by the U.S. Geological Survey to estimate the overall sampling precision of wet atmospheric deposition data collected at selected sites in the National Atmospheric Deposition Program and National Trends Network (NADP/NTN). A duplicate set of wet-deposition sampling instruments was installed adjacent to existing sampling instruments at four different NADP/NTN sites for each year of the study. Wet-deposition samples from collocated sites were collected and analysed using standard NADP/NTN procedures. Laboratory analyses included determinations of pH, specific conductance, and concentrations of major cations and anions. The estimates of precision included all variability in the data-collection system, from the point of sample collection through storage in the NADP/NTN database. Sampling precision was determined from the absolute value of differences in the analytical results for the paired samples in terms of median relative and absolute difference. The median relative difference for Mg2+, Na+, K+ and NH4+ concentration and deposition was quite variable between sites and exceeded 10% at most sites. Relative error for analytes whose concentrations typically approached laboratory method detection limits were greater than for analytes that did not typically approach detection limits. The median relative difference for SO42- and NO3- concentration, specific conductance, and sample volume at all sites was less than 7%. Precision for H+ concentration and deposition ranged from less than 10% at sites with typically high levels of H+ concentration to greater than 30% at sites with low H+ concentration. Median difference for analyte concentration and deposition was typically 1.5-2-times greater for samples collected during the winter than during other seasons at two northern sites. Likewise, the median relative difference in sample volume for winter samples was more than double the annual median relative difference at the two northern sites. Bias accounted for less than 25% of the collocated variability in analyte concentration and deposition from weekly collocated precipitation samples at most sites.A collocated, wet-deposition sampler program has been operated since OCtober 1988 by the U.S Geological Survey to estimate the overall sampling precision of wet atmospheric deposition data collected at selected sites in the National Atmospheric Deposition Program and National Trends Network (NADP/NTN). A duplicate set of wet-deposition sampling instruments was installed adjacent to existing sampling instruments four different NADP/NTN sites for each year of the study. Wet-deposition samples from collocated sites were collected and analysed using standard NADP/NTN procedures. Laboratory analyses included determinations of pH, specific conductance, and concentrations of major cations and anions. The estimates of precision included all variability in the data-collection system, from the point of sample collection through storage in the NADP/NTN database.

Atmospheric Environment

Concentrations and co-occurrence correlations of 88 volatile organic compounds (VOCs) in the ambient air of 13 semi-rural to urban locations in the United States

The ambient air concentrations of 88 volatile organic compounds were determined in samples taken at 13 semi-rural to urban locations in Maine, Massachusetts, New Jersey, Pennsylvania, Ohio, Illinois, Louisiana, and California. The sampling periods ranged from 7 to 29 months, yielding a large data set with a total of 23,191 individual air concentration values, some of which were designated "ND" (not detected). For each compound at each sampling site, the air concentrations (ca, ppbV) are reported in terms of means, medians, and means of the detected values. The analytical method utilized adsorption/thermal desorption with air-sampling cartridges. The analytes included numerous halogenated alkanes, halogenated alkenes, ethers, alcohols, nitriles, esters, ketones, aromatics, a disulfide, and a furan. At some sites, the air concentrations of the gasoline-related aromatic compounds and the gasoline additive methyl tert-butyl ether were seasonally dependent, with concentrations that maximized in the winter. For each site studied here, the concentrations of some compounds were highly correlated one with another (e.g., the BTEX group (benzene, toluene, ethylbenzene, and the xylenes). Other aromatic compounds were also all generally correlated with one another, while the concentrations of other compound pairs were not correlated (e.g., benzene was not correlated with CFC-12). The concentrations found for the BTEX group were generally lower than the values that have been previously reported for urbanized and industrialized areas of other nations. ?? 2003 Elsevier Ltd. All rights reserved.

Atmospheric Environment

Atmospheric dry deposition in the vicinity of the Salton Sea, California - II: Measurement and effects of an enhanced evaporation system

A study was conducted to determine the effects of salt spray drift from pilot technologies employed by the US Bureau of Reclamation on deposition rates of various air-born ions. An enhanced evaporation system (EES) was tested in the field at the Salton Sea, California. Dry deposition of NO3-, NH4+, SO42-, Cl-, Ca2+, Na+, K+ and Se was assessed by using nylon filters and branches of natural vegetation exposed for one-week long periods. The simultaneous exposure of both lyophilized branches and branches of live plants offered important information highlighting the dynamics of deposited ions on vegetation. The EES significantly increased the deposition rates of Cl-, SO42- and Na+ in an area of about 639-1062 m surrounding the sprayers. Similarly, higher deposition of Ca 2+ and K+ caused by the EES was detected only when deposition was assessed using nylon filters or lyophilized branches. Deposition fluxes of NO3-, NH4+ and Se were not affected by the spraying system. Techniques for measuring dry deposition and calculating landscape-level depositional loads in non-forested systems need further development. ?? 2005 Elsevier Ltd. All rights reserved.

Atmospheric Environment

Feasibility of a simple laboratory approach for determining temperature influence on SPMD–air partition coefficients of selected compounds

Semipermeable membrane devices (SPMDs) are a widely used passive sampling methodology for both waterborne and airborne hydrophobic organic contaminants. The exchange kinetics and partition coefficients of an analyte in a SPMD are mediated by its physicochemical properties and certain environmental conditions. Controlled laboratory experiments are used for determining the SPMD–air ( K sa 's) partition coefficients and the exchange kinetics of organic vapors. This study focused on determining a simple approach for measuring equilibrium K sa 's for naphthalene (Naph), o -chlorophenol ( o -CPh) and p -dichlorobenzene ( p -DCB) over a wide range of temperatures. SPMDs were exposed to test chemical vapors in small, gas-tight chambers at four different temperatures (−16, −4, 22 and 40 °C). The exposure times ranged from 6 h to 28 d depending on test temperature. K sa 's or non-equilibrium concentrations in SPMDs were determined for all compounds, temperatures and exposure periods with the exception of Naph, which could not be quantified in SPMDs until 4 weeks at the −16 °C temperature. To perform this study the assumption of constant and saturated atmospheric concentrations in test chambers was made. It could influence the results, which suggest that flow through experimental system and performance reference compounds should be used for SPMD calibration.

Atmospheric Environment

Trends in snowpack chemistry and comparison to National Atmospheric Deposition Program results for the Rocky Mountains, US, 1993-2004

Seasonal snowpack chemistry data from the Rocky Mountain region of the US was examined to identify long-term trends in concentration and chemical deposition in snow and in snow-water equivalent. For the period 1993-2004, comparisons of trends were made between 54 Rocky Mountain Snowpack sites and 16 National Atmospheric Deposition Program wetfall sites located nearby in the region. The region was divided into three subregions: Northern, Central, and Southern. A non-parametric correlation method known as the Regional Kendall Test was used. This technique collectively computed the slope, direction, and probability of trend for several sites at once in each of the Northern, Central, and Southern Rockies subregions. Seasonal Kendall tests were used to evaluate trends at individual sites. Significant trends occurred during the period in wetfall and snowpack concentrations and deposition, and in precipitation. For the comparison, trends in concentrations of ammonium, nitrate, and sulfate for the two networks were in fair agreement. In several cases, increases in ammonium and nitrate concentrations, and decreases in sulfate concentrations for both wetfall and snowpack were consistent in the three subregions. However, deposition patterns between wetfall and snowpack more often were opposite, particularly for ammonium and nitrate. Decreases in ammonium and nitrate deposition in wetfall in the central and southern rockies subregions mostly were moderately significant (p<0.11) in constrast to highly significant increases in snowpack (p<0.02). These opposite trends likely are explained by different rates of declining precipitation during the recent drought (1999-2004) and increasing concentration. Furthermore, dry deposition was an important factor in total deposition of nitrogen in the region. Sulfate deposition decreased with moderate to high significance in all three subregions in both wetfall and snowpack. Precipitation trends consistently were downward and significant for wetfall, snowpack, and snow-telemetry data for the central and southern rockies subregions (p<0.03), while no trends were noted for the Northern Rockies subregion.

Atmospheric Environment

Uptake rate constants and partition coefficients for vapor phase organic chemicals using semipermeable membrane devices (SPMDs)

To fully utilize semipermeable membrane devices (SPMDs) as passive samplers in air monitoring, data are required to accurately estimate airborne concentrations of environmental contaminants. Limited uptake rate constants (k ua ) and no SPMD air partitioning coefficient (K sa ) existed for vapor-phase contaminants. This research was conducted to expand the existing body of kinetic data for SPMD air sampling by determining k ua and K sa for a number of airborne contaminants including the chemical classes: polycyclic aromatic hydrocarbons, organochlorine pesticides, brominated diphenyl ethers, phthalate esters, synthetic pyrethroids, and organophosphate/organosulfur pesticides. The k ua s were obtained for 48 of 50 chemicals investigated and ranged from 0.03 to 3.07??m 3 ??g -1 ??d -1 . In cases where uptake was approaching equilibrium, K sa s were approximated. K sa values (no units) were determined or estimated for 48 of the chemicals investigated and ranging from 3.84E+5 to 7.34E+7. This research utilized a test system (United States Patent 6,877,724 B1) which afforded the capability to generate and maintain constant concentrations of vapor-phase chemical mixtures. The test system and experimental design employed gave reproducible results during experimental runs spanning more than two years. This reproducibility was shown by obtaining mean k ua values (n??=??3) of anthracene and p,p???-DDE at 0.96 and 1.57??m 3 ??g -1 ??d -1 with relative standard deviations of 8.4% and 8.6% respectively.

Atmospheric Environment

Historical deposition of mercury and selected trace elements to high-elevation National Parks in the Western U.S. inferred from lake-sediment cores

Atmospheric deposition of Hg and selected trace elements was reconstructed over the past 150 years using sediment cores collected from nine remote, high-elevation lakes in Rocky Mountain National Park in Colorado and Glacier National Park in Montana. Cores were age dated by 210 Pb, and sedimentation rates were determined using the constant rate of supply model. Hg concentrations in most of the cores began to increase around 1900, reaching a peak sometime after 1980. Other trace elements, particularly Pb and Cd, showed similar post-industrial increases in lake sediments, confirming that anthropogenic contaminants are reaching remote areas of the Rocky Mountains via atmospheric transport and deposition. Preindustrial (pre-1875) Hg fluxes in the sediment ranged from 5.7 to 42 μg m −2 yr −1 and modern (post-1985) fluxes ranged from 17.7 to 141 μg m −2 yr −1 . The average ratio of modern to preindustrial fluxes was 3.2, which is similar to remote lakes elsewhere in North America. Estimates of net atmospheric deposition based on the cores were 3.1 μg m −2 yr −1 for preindustrial and 11.7 μg m −2 yr −1 for modern times. Current-day measurements of wet deposition range from 5.0 to 8.6 μg m −2 yr −1 , which are lower than the modern sediment-based estimate of 11.7 μg m −2 yr −1 , perhaps owing to inputs of dry-deposited Hg to the lakes.

Atmospheric Environment

Short-term nitrogen additions can shift a coastal wetland from a sink to a source of N 2 O

Coastal salt marshes sequester carbon at high rates relative to other ecosystems and emit relatively little methane particularly compared to freshwater wetlands. However, fluxes of all major greenhouse gases (N 2 O, CH 4 , and CO 2 ) need to be quantified for accurate assessment of the climatic roles of these ecosystems. Anthropogenic nitrogen inputs (via run-off, atmospheric deposition, and wastewater) impact coastal marshes. To test the hypothesis that a pulse of nitrogen loading may increase greenhouse gas emissions from salt marsh sediments, we compared N 2 O, CH 4 and respiratory CO 2 fluxes from nitrate-enriched plots in a Spartina patens marsh (receiving single additions of NaNO 3 equivalent to 1.4 g N m −2 ) to those from control plots (receiving only artificial seawater solutions) in three short-term experiments (July 2009, April 2010, and June 2010). In July 2009, we also compared N 2 O and CH 4 fluxes in both opaque and transparent chambers to test the influence of light on gas flux measurements. Background fluxes of N 2 O in July 2009 averaged −33 μmol N 2 O m −2 day −1 . However, within 1 h of nutrient additions, N 2 O fluxes were significantly greater in plots receiving nitrate additions relative to controls in July 2009. Respiratory rates and CH 4 fluxes were not significantly affected. N 2 O fluxes were significantly higher in dark than in transparent chambers, averaging 108 and 42 μmol N 2 O m −2 day −1 respectively. After 2 days, when nutrient concentrations returned to background levels, none of the greenhouse gas fluxes differed from controls. In April 2010, N 2 O and CH 4 fluxes were not significantly affected by nitrate, possibly due to higher nitrogen demands by growing S. patens plants, but in June 2010 trends of higher N 2 O fluxes were again found among nitrate-enriched plots, indicating that responses to nutrient pulses may be strongest during the summer. In terms of carbon equivalents, the highest average N 2 O and CH 4 fluxes observed, exceeded half the magnitude of typical daily net carbon sequestration rates by salt marshes. Thus, anthropogenic additions of nitrate to coasts can substantially alter N 2 O fluxes from marshes, although substantial temporal variation in these fluxes was observed. To better assess the climatic roles of salt marshes, greenhouse gas emissions need to be studied in the context of chronic nitrogen loads that impact many coastal ecosystems.

Atmospheric Environment

PAH volatilization following application of coal-tar-based pavement sealant

Coal-tar-based pavement sealants, a major source of PAHs to urban water bodies, have recently been identified as a source of volatile PAHs to the atmosphere. We tracked the volatilization of PAHs for 1 year after application of a coal-tar-based pavement sealant by measuring gas-phase PAH concentrations above the pavement surface and solid-phase PAH concentrations in sealant scraped from the surface. Gas-phase concentrations at two heights (0.03 and 1.28 m) and wind speed were used to estimate volatilization flux. The sum of the concentrations of eight frequently detected PAHs (&Sigma;PAH 8 ) in the 0.03-m sample 1.6 h after application (297,000 ng m -3 ) was about 5000 times greater than that previously reported for the same height above unsealed parking lots (66 ng m -3 ). Flux at 1.6 h after application was estimated at 45,000 &mu;g m -2 h -1 and decreased rapidly during the 45 days after application to 160 &mu;g m -2 h -1 . Loss of PAHs from the adhered sealant also was rapid, with about a 50% decrease in solid-phase &Sigma;PAH 8 concentration over the 45 days after application. There was general agreement, given the uncertainties, in the estimated mass of &Sigma;PAH 8 lost to the atmosphere on the basis of air sampling (2&ndash;3 g m -2 ) and adhered sealant sampling (6 g m -2 ) during the first 16 days after application, translating to a loss to the atmosphere of one-quarter to one-half of the PAHs in the sealcoat product. Combining the estimated mass of &Sigma;PAH 8 released to the atmosphere with a national-use estimate of coal-tar-based sealant suggests that PAH emissions from new coal-tar-based sealcoat applications each year (~1000 Mg) are larger than annual vehicle emissions of PAHs for the United States.

Atmospheric Environment

A radiogenic isotope tracer study of transatlantic dust transport from Africa to the Caribbean

Many studies have suggested that long-range transport of African desert dusts across the Atlantic Ocean occurs, delivering key nutrients and contributing to fertilization of the Amazon rainforest. Here we utilize radiogenic isotope tracers – Sr, Nd and Pb – to derive the provenance, local or remote, and pathways of dust transport from Africa to the Caribbean. Atmospheric total suspended particulate (TSP) matter was collected in 2008 on quartz fibre filters, from both sides of the Atlantic Ocean at three different locations: in Mali (12.6°N, 8.0°W; 555 m a.s.l.), Tobago (11.3°N, 60.5°W; 329 m a.s.l.) and the U.S. Virgin Islands (17.7°N, 64.6°W; 27 m a.s.l.). Both the labile phase, representative of the anthropogenic signal, and the refractory detrital silicate fraction were analysed. Dust deposits and soils from around the sampling sites were measured as well to assess the potential contribution from local sources to the mineral dust collected. The contribution from anthropogenic sources of Pb was predominant in the labile, leachate phase. The overall similarity in Pb isotope signatures found in the leachates is attributed to a common African source of anthropogenic Pb, with minor inputs from other sources, such as from Central and South America. The Pb, Sr and Nd isotopic compositions in the silicate fraction were found to be systematically more radiogenic than those in the corresponding labile phases. In contrast, Nd and Sr isotopic compositions from Mali, Tobago, and the Virgin Islands are virtually identical in both leachates and residues. Comparison with existing literature data on Saharan and Sahelian sources constrains the origin of summer dust transported to the Caribbean to mainly originate from the Sahel region, with some contribution from northern Saharan sources. The source regions derived from the isotope data are consistent with 7-day back-trajectory analyses, demonstrating the usefulness of radiogenic isotopes in tracing dust provenance and atmospheric transport.

Africa;Atlantic Ocean;Caribbean;Sahara;Sahel

A Great Lakes atmospheric mercury monitoring network: evaluation and design

As many as 51 mercury (Hg) wet-deposition-monitoring sites from 4 networks were operated in 8 USA states and Ontario, Canada in the North American Great Lakes Region from 1996 to 2010. By 2013, 20 of those sites were no longer in operation and approximately half the geographic area of the Region was represented by a single Hg-monitoring site. In response, a Great Lakes Atmospheric Mercury Monitoring (GLAMM) network is needed as a framework for regional collaboration in Hg-deposition monitoring. The purpose of the GLAMM network is to detect changes in regional atmospheric Hg deposition related to changes in Hg emissions. An optimized design for the network was determined to be a minimum of 21 sites in a representative and approximately uniform geographic distribution. A majority of the active and historic Hg-monitoring sites in the Great Lakes Region are part of the National Atmospheric Deposition Program (NADP) Mercury Deposition Network (MDN) in North America and the GLAMM network is planned to be part of the MDN. To determine an optimized network design, active and historic Hg-monitoring sites in the Great Lakes Region were evaluated with a rating system of 21 factors that included characteristics of the monitoring locations and interpretations of Hg data. Monitoring sites were rated according to the number of Hg emissions sources and annual Hg emissions in a geographic polygon centered on each site. Hg-monitoring data from the sites were analyzed for long-term averages in weekly Hg concentrations in precipitation and weekly Hg-wet deposition, and on significant temporal trends in Hg concentrations and Hg deposition. A cluster analysis method was used to group sites with similar variability in their Hg data in order to identify sites that were unique for explaining Hg data variability in the Region. The network design included locations in protected natural areas, urban areas, Great Lakes watersheds, and in proximity to areas with a high density of annual Hg emissions and areas with high average weekly Hg wet deposition. In a statistical analysis, relatively strong, positive correlations in the wet deposition of Hg and sulfate were shown for co-located NADP Hg-monitoring and acid-rain monitoring sites in the Region. This finding indicated that efficiency in regional Hg monitoring can be improved by adding new Hg monitoring to existing NADP acid-rain monitoring sites. Implementation of the GLAMM network design will require Hg-wet-deposition monitoring to be: (a) continued at 12 MDN sites active in 2013 and (b) restarted or added at 9 NADP sites where it is absent in 2013. Ongoing discussions between the states in the Great Lakes Region, the Lake Michigan Air Directors Consortium (a regional planning entity), the NADP, the U.S. Environmental Protection Agency, and the U.S. Geological Survey are needed for coordinating the GLAMM network.

Great Lakes

Spatial patterns of atmospheric deposition of nitrogen and sulfur using ion-exchange resin collectors in Rocky Mountain National Park, USA

Lakes and streams in Class 1 wilderness areas in the western United States (U.S.) are at risk from atmospheric deposition of nitrogen (N) and sulfur (S), and protection of these resources is mandated under the Federal Clean Air Act and amendments. Assessment of critical loads, which are the maximum exposure to pollution an area can receive without adverse effects on sensitive ecosystems, requires accurate deposition estimates. However, deposition is difficult and expensive to measure in high-elevation wilderness, and spatial patterns in N and S deposition in these areas remain poorly quantified. In this study, ion-exchange resin (IER) collectors were used to measure dissolved inorganic N (DIN) and S deposition during June 2006&ndash;September 2007 at approximately 20 alpine/subalpine sites spanning the Continental Divide in Rocky Mountain National Park. Results indicated good agreement between deposition estimated from IER collectors and commonly used wet + dry methods during summer, but poor agreement during winter. Snowpack sampling was found to be a more accurate way of quantifying DIN and S deposition during winter. Summer DIN deposition was significantly greater on the east side of the park than on the west side (25&ndash;50%; p &le; 0.03), consistent with transport of pollutants to the park from urban and agricultural areas to the east. Sources of atmospheric nitrate (NO 3 &minus; ) were examined using N isotopes. The average &delta; 15 N of NO 3 &minus; from IER collectors was 3.5&permil; higher during winter than during summer ( p < 0.001), indicating a seasonal shift in the relative importance of regional NO x sources, such as coal combustion and vehicular sources of atmospheric NO 3 &minus; . There were no significant differences in &delta; 15 N of NO 3 &minus; between east and west sides of the park during summer or winter ( p = 0.83), indicating that the two areas may have similar sources of atmospheric NO 3 &minus; . Results from this study indicate that a combination of IER collectors and snowpack sampling can be used to characterize spatial variability in DIN and S deposition in high-elevation wilderness areas. These data can improve our ability to model critical loads by filling gaps in geographic coverage of deposition monitoring/modeling programs and thus may enable policy makers to better protect sensitive natural resources in Class 1 Wilderness areas.

Colorado