National Trends Network Research Articles

PFAS concentrations and deposition in precipitation: An intensive 5-month study at National Atmospheric Deposition Program – National trends sites (NADP-NTN) across Wisconsin, USA

Atmospheric transport and processing of per- and polyfluoroalkyl substances (PFAS) leads to deposition and accumulation of these compounds in terrestrial and aquatic ecosystems, however, measurements of PFAS flux and deposition rates remain sparse and underdeveloped. In 2020, ninety-one precipitation samples, along with an array of QA/QC samples were collected from eight National Trends Network (NTN) sites across Wisconsin through the National Atmospheric Deposition Program (NADP). Weekly precipitation samples were analyzed for a suite of 34 PFAS compounds to provide measurements of speciated PFAS concentrations and deposition fluxes to in the Upper Great Lakes Region. Perfluoro carboxylates (PFCAs) were detected most frequently and constituted an average of 83% of the total mass quantified across the samples. Summed PFAS mass concentrations in the rainwater ranged from 0.7 to 6.1 ng/L with a median of 1.5 ng/L. Daily flux values ranged from 1.3 to 47.4 ng/m2/day with a median of 5.7 ng/m2/day. From an analysis of variance (ANOVA), significant differences in the average chemical profiles (PFAS fingerprints) were observed among the 8 sampling sites, indicating that nearby sources of PFAS can potentially influence wet-deposition composition of certain species on observed spatial scales. Strict quality control measures were developed and implemented for this study to confirm that the field and laboratory methods met the necessary high data quality standards. These methods and QA/QC protocols are detailed here to provide guidance for future wet deposition sampling of PFAS. This campaign confirms the efficacy of NADP-NTN samplers and protocols for the collection and study of PFAS atmospheric transport, deposition rates, and spatial trends in concentrations and flux.

Biological and chemical recovery of acidified Catskill Mountain streams in response to the Clean Air Act Amendments of 1990

Decades of acidic deposition have adversely affected aquatic and terrestrial ecosystems in acid-sensitive watersheds in parts of the eastern United States. The national Acid Rain Program (Title IV of the 1990 Clean Air Act Amendments - CAAA) helped reduce emissions of sulfur dioxide (SO2) and nitrogen oxides (NOx) and resulted in sharp decreases in the acidity of atmospheric deposition. The decrease in acidic deposition produced a steady decline in the acidity of streams in many poorly buffered waters across the western Adirondacks and parts of the Catskill Mountains of New York. Until recently, however, there has been little evidence of biological recovery in most acid-sensitive streams in both regions. Long-term deposition and stream-chemistry records and fish-community data from quantitative surveys done during 1991–93 and again during 2012–19 at 13 sites in the upper Neversink River and its tributaries were evaluated to determine if chemical and biological recovery were evident in this Catskill Mountain watershed and if they could be linked to regional declines in acidic deposition. Between 1991 and 2019, large decreases in sulfate and nitrate deposition in the basin mirrored declines in total nationwide SO2 and NOx emissions. There were corresponding decreases in sulfate and nitrate concentrations in deposition at a National Trends Network station at Frost Valley (NY68) and coincident declines in sulfate concentrations at four long-term monitoring sites in the Neversink River watershed. Mean acid neutralizing capacity and pH increased and inorganic aluminum (Ali) concentrations from routine summertime samples decreased significantly at most moderately to severely acidified sites between the two study periods. Richness, density, and biomass of fish communities increased at most sites, while the density and biomass of brook trout Salvelinus fontinalis populations increased at fewer sites that were undergoing chemical recovery. Although recovery is far from complete, trends in deposition chemistry, water quality, and fish assemblages in streams of the upper Neversink watershed indicate that the 1990 CAAA is having positive impacts on aquatic ecosystems in the Catskill Mountain region, New York.

A Measurement-Model Fusion Approach for Improved Wet Deposition Maps and Trends.

Air quality models provide spatial fields of wet deposition (WD) and dry deposition that explicitly account for the transport and transformation of emissions from thousands of sources. However, many sources of uncertainty in the air quality model including errors in emissions and meteorological inputs (particularly precipitation) and incomplete descriptions of the chemical and physical processes governing deposition can lead to bias and error in the simulation of WD. We present an approach to bias correct Community Multiscale Air Quality model output over the contiguous United States using observation‐based gridded precipitation data generated by the Parameter‐elevation Regressions on Independent Slopes Model and WD observations at the National Atmospheric Deposition Program National Trends Network sites. A cross‐validation analysis shows that the adjusted annual accumulated WD for NO3 −, NH4 +, and SO4 2− from 2002 to 2012 has less bias and higher correlation with observed values than the base model output without adjustment. Temporal trends in observed WD are captured well by the adjusted model simulations across the entire contiguous United States. Consistent with previous trend analyses, WD NO3 − and SO4 2− are shown to decrease during this period in the eastern half of the United States, particularly in the Northeast, while remaining nearly constant in the West. Trends in WD of NH4 + are more spatially and temporally heterogeneous, with some positive trends in the Great Plains and Central Valley of CA and slightly negative trends in the south.

Simulating lightning NO production in CMAQv5.2: performance evaluations.

This study assesses the impact of the lightning nitric oxide (LNO) production schemes in the Community Multiscale Air Quality (CMAQ) model on ground-level air quality as well as aloft atmospheric chemistry through detailed evaluation of model predictions of nitrogen oxides (NOx) and ozone (O3) with corresponding observations for the US. For ground-level evaluations, hourly O3 and NOx values from the U.S. EPA Air Quality System (AQS) monitoring network are used to assess the impact of different LNO schemes on model prediction of these species in time and space. Vertical evaluations are performed using ozonesonde and P-3B aircraft measurements during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign conducted in the Baltimore– Washington region during July 2011. The impact on wet deposition of nitrate is assessed using measurements from the National Atmospheric Deposition Program’s National Trends Network (NADP NTN). Compared with the Base model (without LNO), the impact of LNO on surface O3 varies from region to region depending on the Base model conditions. Overall statistics suggest that for regions where surface O3 mixing ratios are already overestimated, the incorporation of additional NO from lightning generally increased model overestimation of mean daily maximum 8 h (DM8HR) O3 by 1–2 ppb. In regions where surface O3 is underestimated by the Base model, LNO can significantly reduce the underestimation and bring model predictions close to observations. Analysis of vertical profiles reveals that LNO can significantly improve the vertical structure of modeled O3 distributions by reducing underestimation aloft and to a lesser degree decreasing overestimation near the surface. Since the Base model underestimates the wet deposition of nitrate in most regions across the modeling domain with the exception of the Pacific Coast, the inclusion of LNO leads to reduction in biases and errors and an increase in correlation coefficients at almost all the NADP NTN sites. Among the three LNO schemes described in Kang et al. (2019), the hNLDN scheme, which is implemented using hourly observed lightning flash data from National Lightning Detection Network (NLDN), performs best for comparisons with ground-level values, vertical profiles, and wet deposition of nitrate; the mNLDN scheme (the monthly NLDN-based scheme) performed slightly better. However, when observed lightning flash data are not available, the linear regression-based parameterization scheme, pNLDN, provides an improved estimate for nitrate wet deposition compared to the base simulation that does not include LNO.

Spatial and temporal variation in sources of atmospheric nitrogen deposition in the Rocky Mountains using nitrogen isotopes

Variation in source areas and source types of atmospheric nitrogen (N) deposition to high-elevation ecosystems in the Rocky Mountains were evaluated using spatially and temporally distributed N isotope data from atmospheric deposition networks for 1995-2016. This unique dataset links N in wet deposition and snowpack to mobile and stationary emissions sources, and enhances understanding of the impacts of anthropogenic activities and environmental policies that mitigate effects of accelerated N cycling across the Rocky Mountain region. δ15N−NO3− at 50 U.S. Geological Survey Rocky Mountain Snowpack (Snowpack) sites ranged from −3.3‰ to +6.5‰, with a mean value of +1.4‰. At 15 National Atmospheric Deposition Program (NADP)/National Trends Network wet deposition (NADP Wetfall) sites, summer δ15N−NO3− is significantly lower ranging from −7.6‰ to −1.3‰ while winter δ15N−NO3− ranges from −2.6‰ to +5.5‰, with a mean value of +0.7‰ during the cool season. The strong seasonal difference in NADP Wetfall δ15N−NO3− is due in part to variation in the proportion of N originating from source regions at different times of the year due to seasonal changes in weather patterns. Snowpack NO3− and δ15N−NO3− are significantly related to NADP Wetfall (fall and winter) suggesting that bulk snowpack samples provide a reliable estimate at high elevations. Spatial trends show higher NO3− concentrations and δ15N−NO3− in the Southern Rocky Mountains located near larger anthropogenic N emission sources compared to the Northern Rocky Mountains. NADP Wetfall δ15N−NH4+ ranged from −10‰ to 0‰, with no observed spatial pattern. However, the lowest δ15N−NH4+(−9‰), and the highest NH4+ concentration (35 μeq/L) were observed at a Utah site dominated by local agricultural activities, whereas the higher δ15N−NH4+ observed in Colorado and Wyoming are likely due to mixed sources, including fossil fuel combustion and agricultural sources. These findings show spatial and seasonal variation in N isotope data that reflect differences in sources of anthropogenic N deposition to high-elevation ecosystems and have important implications for environmental policy across the Rocky Mountain region.

Seasonal Patterns of Dry Deposition at a High‐Elevation Site in the Colorado Rocky Mountains

AbstractIn the Colorado Rocky Mountains, high‐elevation barren soils are deficient in carbon (C) and phosphorus (P) and enriched in nitrogen (N). The seasonal variability of dry deposition and its contributions to alpine elemental budgets is critical to understanding how dry deposition influences biogeochemical cycling in high‐elevation environments. In this 2 year study, we evaluated dry and wet deposition inputs to the Niwot Ridge Long Term Ecological Research (NWT LTER) site in the Colorado Rocky Mountains. The total organic C flux in wet + dry (including soluble and particulate C) deposition was >30 kg C ha−1 yr−1 and represents a substantial input for this C‐limited environment. Our side‐by‐side comparison of dry deposition collectors with and without marble insert indicated that the insert improved retention of dry deposition by ~28%. Annual average dry deposition fluxes of water‐soluble organic carbon (4.25 kg C ha−1 yr−1) and other water‐soluble constituents, including ammonium (0.16 kg NH4+ha−1 yr−1), nitrate (1.99 kg NO3− ha−1 yr−1), phosphate (0.08 kg PO43− ha−1 yr−1), and sulfate (1.20 kg SO42− ha−1 yr−1), were comparable to those in wet deposition, with highest values measured in the summer. Backward trajectory analyses implicate air masses passing through the arid west and Four Corners, USA, as dominant source areas for dry deposition, especially in spring months. Synchronous temporal patterns of deposition observed at the NWT LTER site and a distant Rocky Mountain National Park Clean Air Status and Trends Network site indicate that seasonal dry deposition patterns are regional phenomena with important implications for the larger Rocky Mountain region.

Precipitation collector bias and its effects on temporal trends and spatial variability in National Atmospheric Deposition Program/National Trends Network data

Precipitation samples have been collected by the National Atmospheric Deposition Program's (NADP) National Trends Network (NTN) using the Aerochem Metrics Model 301 (ACM) collector since 1978. Approximately one-third of the NTN ACM collectors have been replaced with N-CON Systems, Inc. Model ADS 00-120 (NCON) collectors. Concurrent data were collected over 6 years at 12 NTN sites using colocated ACM and NCON collectors in various precipitation regimes. Linear regression models of the colocated data were used to adjust for relative bias between the collectors. Replacement of ACM collectors with NCON collectors resulted in shifts in 10-year seasonal precipitation-weighted mean concentration (PWMC) trend slopes for: cations (−0.001 to −0.007 mgL−1yr−1), anions (−0.009 to −0.028 mgL−1yr−1), and hydrogen ion (+0.689 meqL-1yr−1). Larger shifts in NO3− and SO4−2 seasonal PWMC trend slopes were observed in the Midwest and Northeast US, where concentrations are generally higher than in other regions. Geospatial analysis of interpolated concentration rasters indicated regions of accentuated variability introduced by incorporation of NCON collectors into the NTN.

Evaluation of atmospheric nitrogen deposition model performance in the context of U.S. critical load assessments

Air quality models are widely used to estimate pollutant deposition rates and thereby calculate critical loads and critical load exceedances (model deposition > critical load). However, model operational performance is not always quantified specifically to inform these applications. We developed a performance assessment approach designed to inform critical load and exceedance calculations, and applied it to the Pacific Northwest region of the U.S. We quantified wet inorganic N deposition performance of several widely-used air quality models, including five different Community Multiscale Air Quality Model (CMAQ) simulations, the Tdep model, and ‘PRISM x NTN’ model. Modeled wet inorganic N deposition estimates were compared to wet inorganic N deposition measurements at 16 National Trends Network (NTN) monitoring sites, and to annual bulk inorganic N deposition measurements at Mount Rainier National Park. Model bias (model – observed) and error (|model – observed|) were expressed as a percentage of regional critical load values for diatoms and lichens. This novel approach demonstrated that wet inorganic N deposition bias in the Pacific Northwest approached or exceeded 100% of regional diatom and lichen critical load values at several individual monitoring sites, and approached or exceeded 50% of critical loads when averaged regionally. Even models that adjusted deposition estimates based on deposition measurements to reduce bias or that spatially-interpolated measurement data, had bias that approached or exceeded critical loads at some locations. While wet inorganic N deposition model bias is only one source of uncertainty that can affect critical load and exceedance calculations, results demonstrate expressing bias as a percentage of critical loads at a spatial scale consistent with calculations may be a useful exercise for those performing calculations. It may help decide if model performance is adequate for a particular calculation, help assess confidence in calculation results, and highlight cases where a non-deterministic approach may be needed.

Changing Regional Emissions of Airborne Pollutants Reflected in the Chemistry of Snowpacks and Wetfall in the Rocky Mountain Region, USA, 1993–2012

Wintertime precipitation sample data from 55 Snowpack sites and 17 National Atmospheric Deposition Program (NADP)/National Trends Network Wetfall sites in the Rocky Mountain region were examined to identify long-term trends in chemical concentration, deposition, and precipitation using Regional and Seasonal Kendall tests. The Natural Resources Conservation Service snow-telemetry (SNOTEL) network provided snow-water-equivalent data from 33 sites located near Snowpack- and NADP Wetfall-sampling sites for further comparisons. Concentration and deposition of ammonium, calcium, nitrate, and sulfate were tested for trends for the period 1993–2012. Precipitation trends were compared between the three monitoring networks for the winter seasons and downward trends were observed for both Snowpack and SNOTEL networks, but not for the NADP Wetfall network. The dry-deposition fraction of total atmospheric deposition, relative to wet deposition, was shown to be considerable in the region. Potential sources of regional airborne pollutant emissions were identified from the U.S. Environmental Protection Agency 2011 National Emissions Inventory, and from long-term emissions data for the period 1996–2013. Changes in the emissions of ammonia, nitrogen oxides, and sulfur dioxide were reflected in significant trends in snowpack and wetfall chemistry. In general, ammonia emissions in the western USA showed a gradual increase over the past decade, while ammonium concentrations and deposition in snowpacks and wetfall showed upward trends. Emissions of nitrogen oxides and sulfur dioxide declined while regional trends in snowpack and wetfall concentrations and deposition of nitrate and sulfate were downward.

Annual variations in wet-deposition chemistry related to changes in climate

National Atmospheric Deposition Program (NADP)/National Trends Network precipitation type, snow-season duration, and annual timing of selected chemical wet-deposition maxima vary with latitude and longitude within a 35-year (1979–2013) data record for the contiguous United States and Alaska. From the NADP data collected within the region bounded by 35.6645°–48.782° north latitude and 124°–68° west longitude, similarities in latitudinal and longitudinal patterns of changing snow-season duration, fraction of annual precipitation recorded as snow, and the timing of chemical wet-deposition maxima, suggest that the chemical climate of the atmosphere is linked to physical changes in climate. Total annual precipitation depth has increased 4–6 % while snow season duration has decreased from approximately 7 to 21 days across most of the USA, except in higher elevation regions where it has increased by as much as 21 days. Snow-season precipitation is increasingly comprised of snow, but annually total precipitation is increasingly comprised of liquid precipitation. Meanwhile, maximum ammonium deposition occurs as much as 27 days earlier, and the maximum nitrate: sulfate concentration ratio in wet-deposition occurs approximately 10–21 days earlier in the year. The maximum crustal (calcium + magnesium + potassium) cation deposition occurs 2–35 days earlier in the year. The data suggest that these shifts in the timing of atmospheric wet deposition are linked to a warming climate, but the ecological consequences are uncertain.

Sources of nitrogen deposition in Federal Class I areas in the US

Abstract. It is desired to control excessive reactive nitrogen (Nr) deposition due to its detrimental impact on ecosystems. Using a three-dimensional atmospheric chemical transport model, GEOS-Chem, Nr deposition in the contiguous US and eight selected Class I areas (Voyageurs (VY), Smoky Mountain (SM), Shenandoah (SD), Big Bend (BB), Rocky Mountain (RM), Grand Teton (GT), Joshua Tree (JT), and Sequoia (SQ)) is investigated. First, modeled Nr deposition is compared with National Trends Network (NTN) and Clean Air Status and Trends Network (CASTNET) deposition values. The seasonality of measured species is generally well represented by the model (R2 > 0.6), except in JT. While modeled Nr is generally within the range of seasonal observations, large overestimates are present in sites such as SM and SD in the spring and summer (up to 0.6 kg N ha month−1), likely owing to model high-biases in surface HNO3. The contribution of non-measured species (mostly dry deposition of NH3) to total modeled Nr deposition ranges from 1 to 55 %. The spatial distribution of the origin of Nr deposited in each Class I area and the contributions of individual emission sectors are estimated using the GEOS-Chem adjoint model. We find the largest role of long-range transport for VY, where 50 % (90 %) of annual Nr deposition originates within 670 (1670) km of the park. In contrast, the Nr emission footprint is most localized for SQ, where 50 % (90 %) of the deposition originates from within 130 (370) km. Emissions from California contribute to the Nr deposition in remote areas in the western US (RM, GT). Mobile NOx and livestock NH3 are found to be the major sources of Nr deposition in all sites except BB, where contributions of NOx from lightning and soils to natural levels of Nr deposition are significant (∼ 40 %). The efficiency in terms of Nr deposition per kg emissions of NH3-N, NOx-N, and SO2-S are also estimated. Unique seasonal features are found in JT (opposing efficiency distributions for winter and summer), RM (large fluctuations in the range of effective regions), and SD (upwind NH3 emissions hindering Nr deposition). We also evaluate the contributions of emissions to the total area of Class I regions in critical load exceedance, and to the total magnitude of exceedance. We find that while it is effective to control emissions in the western US to reduce the area of regions in CL exceedance, it can be more effective to control emissions in the eastern US to reduce the magnitude of Nr deposition above the CL. Finally, uncertainty in the nitrogen deposition caused by uncertainty in the NH3 emission inventory is explored by comparing results based on two different NH3 inventories; noticeable differences in the emission inventories and thus sensitivities of up to a factor of four found in individual locations.

A novel hybrid approach for estimating total deposition in the United States

Atmospheric deposition of nitrogen and sulfur causes many deleterious effects on ecosystems including acidification and excess eutrophication. Assessments to support development of strategies to mitigate these effects require spatially and temporally continuous values of nitrogen and sulfur deposition. In the U.S., national monitoring networks exist that provide values of wet and dry deposition at discrete locations. While wet deposition can be interpolated between the monitoring locations, dry deposition cannot. Additionally, monitoring networks do not measure the complete suite of chemicals that contribute to total sulfur and nitrogen deposition. Regional air quality models provide spatially continuous values of deposition of monitored species as well as important unmeasured species. However, air quality modeling values are not generally available for an extended continuous time period. Air quality modeling results may also be biased for some chemical species. We developed a novel approach for estimating dry deposition using data from monitoring networks such as the Clean Air Status and Trends Network (CASTNET), the National Atmospheric Deposition Program (NADP) Ammonia Monitoring Network (AMoN), and the Southeastern Aerosol Research and Characterization (SEARCH) network and modeled data from the Community Multiscale Air Quality (CMAQ) model. These dry deposition values estimates are then combined with wet deposition values from the NADP National Trends Network (NTN) to develop values of total deposition of sulfur and nitrogen. Data developed using this method are made available via the CASTNET website.

Coupling meteorology, metal concentrations, and Pb isotopes for source attribution in archived precipitation samples

A technique that couples lead (Pb) isotopes and multi-element concentrations with meteorological analysis was used to assess source contributions to precipitation samples at the Bondville, Illinois USA National Trends Network (NTN) site. Precipitation samples collected over a 16month period (July 1994–October 1995) at Bondville were parsed into six unique meteorological flow regimes using a minimum variance clustering technique on back trajectory endpoints. Pb isotope ratios and multi-element concentrations were measured using high resolution inductively coupled plasma‐sector field mass spectrometry (ICP-SFMS) on the archived precipitation samples. Bondville is located in central Illinois, ~250km downwind from smelters in southeast Missouri. The Mississippi Valley Type ore deposits in Missouri provided a unique multi-element and Pb isotope fingerprint for smelter emissions which could be contrasted to industrial emissions from the Chicago and Indianapolis urban areas (~125km north and east, of Bondville respectively) and regional emissions from electric utility facilities. Differences in Pb isotopes and element concentrations in precipitation corresponded to flow regime. Industrial sources from urban areas, and thorogenic Pb from coal use, could be differentiated from smelter emissions from Missouri by coupling Pb isotopes with variations in element ratios and relative mass factors. Using a three endmember mixing model based on Pb isotope ratio differences, industrial processes in urban airsheds contributed 56±19%, smelters in southeast Missouri 26±13%, and coal combustion 18±7%, of the Pb in precipitation collected in Bondville in the mid-1990s.

Stability of organic nitrogen in NADP wet deposition samples

Organic compounds represent an important yet largely uncharacterized component of atmospheric nitrogen deposition. Rapid progress in understanding the sources and spatiotemporal patterns of organic nitrogen (ON) deposition will require the use of existing large-scale monitoring infrastructure, such as the National Atmospheric Deposition Program's National Trends Network (NADP/NTN). The purpose of this study is to investigate the analytical and sampling requirements for adding ON measurements to the NTN, with specific interest in examining ON stability during sampling and storage. The analytical technique for total nitrogen (TN) used by the NADP's Central Analytical Laboratory (CAL) and associated quality assurance data are described. We then compare TN, inorganic nitrogen (IN = NH4+ + NO3−), and ON (ON = TN − IN) concentrations in a field study between standard weekly NADP/NTN samples (unrefrigerated during sampling and storage), daily event samples collected using the Atmospheric Integrated Research Monitoring Network protocol (AIRMoN, unrefrigerated during sampling but refrigerated during storage), and daily event samples that were preserved via refrigeration in the field upon collection (AIRMoN_Ref, refrigerated during sampling and storage). Using AIRMoN_Ref as the reference for comparison, total loss of ON in weekly NTN samples in the field and during laboratory storage is approximately 40%. This bias is likely dominated by losses of ON in the collection bucket. However, additional loss may occur during laboratory storage at room temperature prior to analysis. Loss of ON was also observed in AIRMoN samples, though differences relative to AIRMoN_Ref (10.8%) were less than weekly NTN samples. Biases in ON are more consistently negative at higher ambient temperatures. Storage experiments indicated that refrigeration at 4 °C at the CAL was sufficient to stabilize ON concentrations. We conclude that weekly sampling for ON is feasible if precipitation is refrigerated or frozen immediately upon collection. Samples should be kept refrigerated or frozen prior to analysis. Preliminary results indicate that NO2−, an additional inorganic species not currently measured by the CAL, makes a small contribution to TN (<1%), but if neglected may cause significant negative bias in ON determined as TN − IN. We recommend that CAL include NO2− quantification as a component of IN for bulk ON determination.

Long-term recovery of lakes in the Adirondack region of New York to decreases in acidic deposition

Abstract After years of adverse impacts to the acid-sensitive ecosystems of the eastern United States, the Acid Rain Program and Nitrogen Budget Program were developed to control sulfur dioxide (SO2) and nitrogen oxide (NOx) emissions through market-based cap and trade systems. We used data from the National Atmospheric Deposition Program’s National Trends Network (NTN) and the U.S. EPA Temporally Integrated Monitoring of Ecosystems (TIME) program to evaluate the response of lake-watersheds in the Adirondack region of New York to changes in emissions of sulfur dioxide and nitrogen oxides resulting from the Acid Rain Program and the Nitrogen Budget Program. TIME is a long-term monitoring program designed to sample statistically selected subpopulations of lakes and streams across the eastern U.S. to quantify regional trends in surface water chemistry due to changes in atmospheric deposition. Decreases in wet sulfate deposition for the TIME lake-watersheds from 1991 to 2007 (−1.04 meq m−2-yr) generally corresponded with decreases in estimated lake sulfate flux (−1.46 ± 0.72 meq m−2-yr), suggesting declines in lake sulfate were largely driven by decreases in atmospheric deposition. Decreases in lake sulfate and to a lesser extent nitrate have generally coincided with increases in acid neutralizing capacity (ANC) resulting in shifts in lakes among ANC sensitivity classes. The percentage of acidic Adirondack lakes (ANC

A multi-resolution assessment of the Community Multiscale Air Quality (CMAQ) model v4.7 wet deposition estimates for 2002–2006

Abstract. This paper examines the operational performance of the Community Multiscale Air Quality (CMAQ) model simulations for 2002–2006 using both 36-km and 12-km horizontal grid spacing, with a primary focus on the performance of the CMAQ model in predicting wet deposition of sulfate (SO4=), ammonium (NH4+) and nitrate (NO3−). Performance of the wet deposition estimates from the model is determined by comparing CMAQ predicted concentrations to concentrations measured by the National Acid Deposition Program (NADP), specifically the National Trends Network (NTN). For SO4= wet deposition, the CMAQ model estimates were generally comparable between the 36-km and 12-km simulations for the eastern US, with the 12-km simulation giving slightly higher estimates of SO4= wet deposition than the 36-km simulation on average. The result is a slightly larger normalized mean bias (NMB) for the 12-km simulation; however both simulations had annual biases that were less than ±15 % for each of the five years. The model estimated SO4= wet deposition values improved when they were adjusted to account for biases in the model estimated precipitation. The CMAQ model underestimates NH4+ wet deposition over the eastern US, with a slightly larger underestimation in the 36-km simulation. The largest underestimations occur in the winter and spring periods, while the summer and fall have slightly smaller underestimations of NH4+ wet deposition. The underestimation in NH4+ wet deposition is likely due in part to the poor temporal and spatial representation of ammonia (NH3) emissions, particularly those emissions associated with fertilizer applications and NH3 bi-directional exchange. The model performance for estimates of NO3− wet deposition are mixed throughout the year, with the model largely underestimating NO3− wet deposition in the spring and summer in the eastern US, while the model has a relatively small bias in the fall and winter. Model estimates of NO3− wet deposition tend to be slightly lower for the 36-km simulation as compared to the 12-km simulation, particularly in the spring. The underestimation of NO3− wet deposition in the spring and summer is due in part to a lack of lightning generated NO emissions in the upper troposphere, which can be a large source of NO in the spring and summer when lightning activity is the high. CMAQ model simulations that include production of NO from lightning show a significant improvement in the NO3− wet deposition estimates in the eastern US in the summer. Overall, performance for the 36-km and 12-km CMAQ model simulations is similar for the eastern US, while for the western US the performance of the 36-km simulation is generally not as good as either eastern US simulation, which is not entire unexpected given the complex topography in the western US.

Development and Application of a Multipollutant Model for Atmospheric Mercury Deposition

Abstract A multipollutant model, the Community Multiscale Air Quality model paired with the Model of Aerosol Dynamics, Reaction, Ionization, and Dissolution (CMAQ-MADRID), is extended to include a comprehensive treatment of mercury processes and is applied to the simulation of the atmospheric deposition of sulfate and mercury over the United States during 1996. Model performance is evaluated first by comparison with annual sulfate wet deposition data from the National Atmospheric Deposition Program’s National Trends Network; the coefficient of determination r 2 is 0.77, and the model normalized error and bias are 53% and −8%, respectively. When actual precipitation data are used to scale the deposition fluxes, r 2 improves to 0.91 and the error and bias change to 42% and −41%, respectively. The scaled results underscore a tendency of the model to underestimate sulfate wet deposition. Model performance for mercury wet deposition is then evaluated by comparison with data from the Mercury Deposition Network. For annual mercury wet deposition, r 2 is 0.28 and the normalized error and bias are 81% and 73%, respectively, when the modeled precipitation data are used. Model performance improves when actual precipitation data are used to scale deposition fluxes: r 2 increases to 0.41 and the error and bias decrease to 40% and 29%, respectively. The model reproduces the spatial pattern of sulfate wet deposition adequately with an increasing gradient from the upper Midwest to the Northeast, that is, from upwind to downwind of large sulfur dioxide sources in the Ohio River Valley. However, the model tends to overestimate mercury wet deposition in the Northeast downwind of these sources that also emit significant amounts of mercury. This “Pennsylvania anomaly” may be due to a partial misrepresentation of the mercury reduction–oxidation cycle, uncertainties in the dry deposition of divalent gaseous mercury HgII, incorrect speciation of mercury emissions, and/or uncharacterized emissions in the upper Midwest.

The Effect of Nitrogen Depostition and Edaphic Conditions on Microbial Activity in the Alpine Zone of the Grand Teton National Park

Atmospheric nitrogen (N) deposition rates show increasing N loadings since the 1980s in the western U.S. associated with increasing N emissions from industrial, urban, and agricultural sources (Fenn et al., 2003). Compared to the eastern U.S., the number of NADP/NTN (National Atmospheric Deposition Program/ National Trends Network) and CASTNet (Clean Air Status Network) monitoring sites is much more limited in the west, and they are rarely located in the highest-elevations, where ecosystems are likely to be more sensitive (Bums 2004). Although N deposition tends to increase with elevation in this region (Williams and Tonnesen 2000), there are considerable uncertainties about the actual N deposition levels in the Rocky Mountains. Model-simulations indicate a "hotspot" of N deposition near Grand Teton National Park (GRTE) (Fenn et al., 2003; Nanus et al. 2003), with feedlot and fertilizer N emissions in Southern Idaho, as potential sources impacting the alpine communities in GRTE. However, little data is currently available on the actual atmospheric N inputs to alpine ecosystems in GRTE, either as snow during winter or wet and dry deposition during the short snow-free period.

Spatial and temporal trends of precipitation chemistry in the United States, 1985–2002

A Seasonal Kendall Trend (SKT) test was applied to precipitation-weighted concentration data from 164 National Atmospheric Deposition Program National Trends Network (NADP/NTN) sites operational from 1985 to 2002. Analyses were performed on concentrations of ammonium, sulfate, nitrate, dissolved inorganic nitrogen (DIN, sum of nitrogen from nitrate and ammonium), and earth crustal cations (ECC, sum of calcium, magnesium, and potassium). Over the 18-year period, statistically significant ( p ≤ 0.10) increases in ammonium concentrations occurred at 93 sites (58%), while just three sites had statistically significant ammonium decreases. Central and northern Midwestern states had the largest ammonium increases. The generally higher ammonium concentrations were accompanied by significant sulfate decreases (139 sites, 85%), and only one significant increase which occured in Texas. In the west central United States there were significant nitrate increases (45 sites, 27%), while in the northeastern United States there were significant decreases (25 sites, 15%). Significant DIN decreases were observed in the northeastern United States (11 sites, 7%); elsewhere there were significant increases at 75 sites (46%). ECC decreased significantly at 65 sites (40%), predominately in the central and southern United States, and increased at 11 sites (7%). The concentrations of sulfate, nitrate, and ammonium in precipitation have changed markedly over the time period studied. Such trends indicate changes in the mix of gases and particles scavenged by precipitation, possibly reflecting changes in emissions, atmospheric chemical transformations, and weather patterns.

Investigation of Differences between Field and Laboratory pH Measurements of National Atmospheric Deposition Program/National Trends Network Precipitation Samples

A study was undertaken to investigate differences between laboratoryand field pH measurements for precipitation samples collected from 135 weekly precipitation-monitoring sites in the National Trends Network from 12/30/1986 to 12/28/1999. Differences in pH between field and laboratory measurements occurred for 96% of samples collected during this time period. Differences between the two measurements were evaluated for precipitation samples collected before and after January 1994, when modifications to sample-handling protocol and elimination of the contaminating bucket o-ring used in sample shipment occurred. Median hydrogen-ion and pH differences between field and laboratory measurements declined from 3. 9 μeq L-1 or 0. 10 pH units before the 1994 protocol change to 1. 4 μeq L-1 or 0. 04 pH units after the 1994 protocol change. Hydrogen-ion differences between field and laboratory measurements had a high correlation with the sample pH determined in the field. The largest pH differences between the two measurements occurred for high-pH samples (>5. 6), typical of precipitation collected in Western United States; however low-pH samples (<5. 0) displayed the highest variability in hydrogen-ion differences between field and laboratory analyses. Properly screened field pH measurements are a useful alternative to laboratory pH values for trend analysis, particularly before 1994 when laboratory pH values were influenced by sample-collection equipment.