National Atmospheric Deposition Program

emissions over the last decades have affected atmospheric composition on a regional and global scale with large impact on air quality, atmospheric deposition and the radiative forcing of sulfate aerosols. Reproduction of historical atmospheric pollution levels based on global aerosol models and emission changes is crucial to prove that such models are able to predict future scenarios. Here, we analyze consistency of trends in observations of sulfur components in air and precipitation from major regional networks and estimates from six different global aerosol models from 1990 until 2015. There are large interregional differences in the sulfur trends consistently captured by the models and observations, especially for North America and Europe. Europe had the largest reductions in sulfur emissions in the first part of the period while the highest reduction came later in North America and East Asia. The uncertainties in both the emissions and the representativity of the observations are larger in Asia. However, emissions from East Asia clearly increased from 2000 to 2005 followed by a decrease, while in India a steady increase over the whole period has been observed and modelled. The agreement between a bottom-up approach, which uses emissions and process-based chemical transport models, with independent observations gives an improved confidence in the understanding of the atmospheric sulfur budget.

Dry deposition is a major component of total atmospheric nitrogen deposition and thus an important source of bioavailable nitrogen to ecosystems. However, relative to wet deposition, less is known regarding the sources and spatial variability of dry deposition. This is in part due to difficulty in measuring dry deposition and associated deposition velocities. Passive sampling techniques offer potential for improving our understanding of the spatial distribution and sources of gaseous and aerosol N species, referred to here as dry deposition. We report dual nitrate isotopic composition ( δ 15 N and δ 18 O) in actively collected dry and wet deposition across the high‐deposition region of Ohio, New York, and Pennsylvania. We also present results from initial tests to examine the efficacy of using passive nitric acid collectors as a collection medium for isotopic analysis at a site in New York. Isotopic values in actively collected dry deposition, including particulate nitrate and gaseous nitric acid, are compared with those in wet nitrate deposition and surrounding NO x emission sources. δ 15 N values in dry and wet fractions are highest at the westernmost sites and lowest at the easternmost sites, and stationary source NO x emissions (e.g., power plants and incinerators) appear to be the primary control on δ 15 N spatial variability. In contrast, δ 18 O values show a less consistent spatial pattern in dry deposition. Both δ 15 N and δ 18 O show strong seasonality, with higher values in winter than summer. Seasonal variations in stationary source NO x emissions appear to be the most likely explanation for seasonal variations in δ 15 N, whereas seasonal variations in air temperature and solar radiation indicate variable chemical oxidation pathways control δ 18 O patterns. Additionally, we demonstrate the utility of passive samplers for collecting the nitric acid (HNO 3 ) component of dry deposition suitable for isotopic analysis. We observe slight differences in δ 15 N‐HNO 3 values between simultaneous samples collected actively and passively (0.6‰). However, we observe a larger offset in δ 18 O values between actively and passively collected samples; the causes for this offset warrant further investigation. Nonetheless, passive sample collection represents a significant cost savings over active sampling techniques and could allow a more extensive understanding of patterns of dry deposition and associated insights to nitrogen sources across landscapes.

Abstract. The National Atmospheric Deposition Program (NADP) developed and operates a collaborative network of atmospheric-mercury-monitoring sites based in North America – the Atmospheric Mercury Network (AMNet). The justification for the network was growing interest and demand from many scientists and policy makers for a robust database of measurements to improve model development, assess policies and programs, and improve estimates of mercury dry deposition. Many different agencies and groups support the network, including federal, state, tribal, and international governments, academic institutions, and private companies. AMNet has added two high-elevation sites outside of continental North America in Hawaii and Taiwan because of new partnerships forged within NADP. Network sites measure concentrations of atmospheric mercury fractions using automated, continuous mercury speciation systems. The procedures that NADP developed for field operations, data management, and quality assurance ensure that the network makes scientifically valid and consistent measurements. AMNet reports concentrations of hourly gaseous elemental mercury (GEM), two-hour gaseous oxidized mercury (GOM), and two-hour particulate-bound mercury less than 2.5 microns in size (PBM2.5). As of January 2012, over 450 000 valid observations are available from 30 stations. AMNet also collects ancillary meteorological data and information on land use and vegetation, when available. We present atmospheric mercury data comparisons by time (3 yr) at 21 individual sites and instruments. Highlighted are contrasting values for site locations across the network: urban versus rural, coastal versus high elevation and the range of maximum observations. The data presented should catalyze the formation of many scientific questions that may be answered through further in-depth analysis and modeling studies of the AMNet database. All data and methods are publically available through an online database on the NADP website (http://nadp.sws.uiuc.edu/amn/). Future network directions are to foster new network partnerships and continue to collect, quality assure, and post data, including dry deposition estimates, for each fraction.

Concentrations of sulfate (SO42-) and free hydrogen ions (H+) in precipitation decreased from 10% to 25% over a large area of the Eastern United States from 1995 through 1997 as compared to the previous 12-year (1983−1994) reference period. These decreases were unprecedented in magnitude and spatial extent. In contrast, nitrate (NO3-) concentrations generally did not change over this period. The largest decreases in both H+ and SO42- concentrations, which nearly mimicked one another, occurred in and downwind of the Ohio River Valley, the same area where Title IV of the 1990 Clean Air Act Amendments (CAAA) set limitations on sulfur dioxide (SO2) emissions from a large number of utility-owned coal-fired sources. Phase I of the CAAA required that these limitations be met by January 1, 1995. On the basis of our analysis of precipitation chemistry and emissions data, we conclude that significant declines in acid rain occurred in many parts of the Eastern United States from 1995 through 1997 because of large reductions in SO2 emissions in this region and a corresponding reduction in SO42- concentrations in precipitation.

In 2005, weekly rain samples collected at 124 National Atmospheric Deposition Program/National Trends Network (NADP/NTN) sites in the eastern and central United States were screened for Asian soybean rust (ASR; Phakopsora pachyrhizi) urediniospores. Application of a quantitative polymerase chain reaction method detected P. pachyrhizi DNA in the filter residue of rain samples collected during the week of 19 to 26 July 2005 in Minnesota, Missouri, and South Dakota. To determine the geographic origin of ASR urediniospores in those weekly composite samples, back air trajectories of the lifted condensation and mixed boundary layers were calculated for each rain event within the week, by sampling site. The calculations, based on the hybrid single-particle lagrangian integrated trajectory model, pointed to source areas in eastern and southern Texas. In a separate case, DNA of P. pachyrhizi was detected in a 28 June to 5 July 2005 rain sample from an eastern Texas site. Back trajectories pointed to southern Texas and the Yucatan Peninsula in Mexico as potential source areas of ASR urediniospores. Vertical motions of those back trajectories indicated a ventilation of the boundary layer in the upwind areas, suggesting the possible injection of urediniospores into the free troposphere where they can be transported for long distances before wet deposition.

Using the infrastructure of the National Atmospheric Deposition Program (NADP), numerous measurements of radionuclide wet deposition over North America were made for 167 NADP sites before and after the Fukushima Dai-ichi Nuclear Power Station incident of March 12, 2011. For the period from March 8 through April 5, 2011, wet-only precipitation samples were collected by NADP and analyzed for fission-product isotopes within whole-water and filterable solid samples by the United States Geological Survey using gamma spectrometry. Variable amounts of (131)I, (134)Cs, or (137)Cs were measured at approximately 21% of sampled NADP sites distributed widely across the contiguous United States and Alaska. Calculated 1- to 2-week individual radionuclide deposition fluxes ranged from 0.47 to 5100 Becquerels per square meter during the sampling period. Wet deposition activity was small compared to measured activity already present in U.S. soil. NADP networks responded to this complex disaster, and provided scientifically valid measurements that are comparable and complementary to other networks in North America and Europe.

Atmospheric concentrations of ammonia (NH3) are not well characterized in the United States due to the sparse number of monitors, the relatively short lifetime of NH3 in the atmosphere, and the difficulty in measuring non-point source emissions such as fertilized agricultural land. In this study, we compare measured weekly concentrations of NH3 collected by two denuder systems with a bi-weekly passive NH3 sampler used by the National Atmospheric Deposition Program's (NADP) Ammonia Monitoring Network (AMoN). The purpose of the study was to verify the passive samplers used by AMoN and characterize any uncertainties introduced when using a bi-weekly versus weekly sampling time period. The study was conducted for 1 year at five remote Clean Air Status and Trends Network (CASTNET) sites. Measured ambient NH3 concentrations ranged from 0.03 μg NH3 m(-3) to 4.64 μg NH3 m(-3) in upstate New York and northwest Texas, respectively, while dry deposition estimates ranged from 0.003 kg N ha(-1) wk(-1) to 0.47 kg N ha(-1) wk(-1). Results showed that the bi-weekly passive samplers performed well compared to annular denuder systems (ADS) deployed at each of the five CASTNET sites, while the MetOne Super SASS Mini-Parallel Plate Denuder System (MPPD) was biased low when compared to the ADS. The mean relative percent difference (MRPD) between the ADS and MPPD and the ADS and AMoN sampler was -38% and -9%, respectively. Precision of the ADS and MPPD was 5% and 13%, respectively, while the precision of the passive samplers was 5%. The results of this study demonstrate that the NH3 concentrations measured by AMoN are comparable to the ADS and may be used to supplement the high-time resolution measurements to gain information on spatial gradients of NH3, long-term trends and seasonal variations in NH3 concentrations.

Mexico City Metropolitan Area (MCMA), one of the most populous cities in the world, has historically represented a challenge in terms of air pollution. Particulates and sulfur dioxide. (SO2) were identified as the main atmospheric pollutants three decades ago. In order to reduce emissions of these pollutants, replacing of fuel oil by natural gas in power plants was carried out in the late 1980s. This strategy resulted in the reduction of ambient air concentrations of both pollutants. SO2 no longer exceeds its ambient air quality standard; however, acid rain remains a significant issue, with sulfate remaining as the principal component in the wet atmospheric deposition. In this study, spatial and temporal variations in the chemical composition of precipitation (sulfate and nitrate ions, and pH) were obtained weekly at 16 sampling stations, as well as atmospheric SO2 and nitrogen oxides (NOx) from an air quality monitoring network from 2003 to 2018 in the MCMA. Some indicators were applied to evaluate wet atmospheric deposition: SO42−/NO3− and NH4+/NO3− ratios, fractional acidity as well as neutralization factors. SO2 ambient air concentrations have decreased from 2003 to 2018 by more than 70%, while NOx has decreased by 20%. The SO2/NOx ratio has declined about 60%, indicating more effective strategies in reducing SO2 than for NOx emissions. The NOx emission sources are more diverse than for SO2, and NOx has more complex mechanisms of atmospheric deposition and photochemistry. The pH values of the samples at the stations located in the south were more acidic than the samples for the stations in the north. This result is in line with meteorological conditions, where prevailing winds blow from north to south, as well as emission sources located in the north sector, both inside and outside MCMA. For SO42−/NO3− ratio, all sampling sites present current values in the same magnitude order, around 1.4, which is higher compared with urban sites in USA. The 2018 NH4+/NO3− ratio was 1.98 for the southern sampling site, while all northern sampling sites were approximately 2.28. These results are on the same order that urban sites in USA. It was concluded that ammonium was a very important neutralizing agent of pH within the MCMA precipitation. It is recommended to apply strategies for the emissions reduction of acid rain precursors in external sources to the North the MCMA, and to establish a Network for Urban Atmospheric Nitrogen Chemistry.

Abstract. The National Atmospheric Deposition Program (NADP) developed and operates a collaborative network of atmospheric mercury monitoring sites based in North America – the Atmospheric Mercury Network (AMNet). The justification for the network was growing interest and demand from many scientists and policy makers for a robust database of measurements to improve model development, assess policies and programs, and improve estimates of mercury dry deposition. Many different agencies and groups support the network, including federal, state, tribal, and international governments, academic institutions, and private companies. AMNet has added two high elevation sites outside of continental North America in Hawaii and Taiwan because of new partnerships forged within NADP. Network sites measure concentrations of atmospheric mercury fractions using automated, continuous mercury speciation systems. The procedures that NADP developed for field operations, data management, and quality assurance ensure that the network makes scientifically valid and consistent measurements. AMNet reports concentrations of hourly gaseous elemental mercury (GEM), two-hour gaseous oxidized mercury (GOM), and two-hour particulate-bound mercury less than 2.5 microns in size (PBM2.5). As of January 2012, over 450 000 valid observations are available from 30 stations. The AMNet also collects ancillary meteorological data and information on land-use and vegetation, when available. We present atmospheric mercury data comparisons by time (3 yr) at 22 unique site locations. Highlighted are contrasting values for site locations across the network: urban versus rural, coastal versus high-elevation and the range of maximum observations. The data presented should catalyze the formation of many scientific questions that may be answered through further in-depth analysis and modeling studies of the AMNet database. All data and methods are publically available through an online database on the NADP website (http://nadp.isws.illinois.edu/amn/). Future network directions are to foster new network partnerships and continue to collect, quality assure, and post data, including dry deposition estimates, for each fraction.

km 2 , cubic meter per second per square kilometer; MT/yr, metric ton per year; -, not applicable

Ozone effects on plant water relations have been reported to be similar to those of water‐deficit. The objective was to identify ozone‐inducible (OI) clones from Atriplex canescens (saltbush) and determine if they were also responsive to water‐deficit as well as SO 2 . cDNA clones derived from four different polyA RNAs which accumulate in 8‐month‐old shrub leaves exposed to ozone (0.2 μl I −1 , 6 h day −1 , 7 days) were isolated by differential screening, analyzed by northern blots, sequenced, and gene product homologies with other plant genes were determined. Clone OI12A‐3 has homology with wound‐inducible proteinase inhibitors, whereas clone OI8–3 protein is homologous to thiol proteases. Clones OI2–2 and OI14–3 putatively code for glycine‐rich proteins with repeated motifs (Gly‐Gly‐Gly‐Tyr‐Gly‐His) n and putative cell‐wall‐targeting signal peptides. Clone OI2–2 and particularly clone OI14–3 were also induced by both SO 2 and water‐deficit. These data indicate that woody plant genes associated with cell wall protein production and whose expression is induced by several stress factors may be responding to common oxidative stress pathways.

Abstract Atmospheric dust is an important mass transfer and nutrient supply process in Earth surface ecosystems. For decades, Saharan dust has been hypothesized as a supplier of nutrients to the Amazon rainforest and eastern North America. However, isotope studies aimed at detecting Saharan dust in the American sedimentary record have been ambiguous. A large Saharan dust storm emerged off the coast of Africa in June 2020 and extended into the southeastern United States. This storm provided a means to evaluate the influence of Saharan dust in North America confirmed by independent satellite and ground observations. Precipitation samples from 17 sites within the National Atmospheric Deposition Program (NADP) were obtained from throughout the southeastern United States prior to, during, and after the arrival of Saharan dust. Precipitation samples were measured for their lead (Pb) isotopic composition, total Pb content, and 210 Pb activity using multicollector inductively coupled plasma mass spectrometry. We measured a significant isotopic shift (approximately 0.7% in the 208 Pb/ 206 Pb relative to the 207 Pb/ 206 Pb) in precipitation that peaked in late June 2020 when the dust blanketed the southeastern United States. However, the magnitude and short time period of the isotopic shift would make it difficult to detect in sedimentary records.

Approximately 80 different crop species are grown in the United States in widely differing geographic areas, climatic and edaphic conditions, and management practices. Although the majority of cultivated acreage in the United States is planted with only about 10 primary crops, uncertainties associated with trace gas emissions arise from: (1) limited data availability, (2) inaccurate estimates because of large temporal and spatial variability in trace gas composition and magnitude of trace gas emissions from agricultural activities, (3) differing characteristics of pollutant emissions from highly dispersed animal feed-lots, and (4) limited understanding of the emissions of semi-volatile organic compounds (SVOCs) associated with agriculture. Although emission issues are of concern, so also is atmospheric deposition to cropping systems, including wet and dry nitrogen, minerals, and organic compounds. These can have feedback effects on trace gas emissions. Overall, the many gaps in our understanding of these aspects of agricultural systems deserve serious attention.

Black carbon (BC) aerosols from burning biomass, fossil fuels, and waste are transported over large distances in the Earth's atmosphere, absorbing sunlight, altering climate, and impacting air quality. These aerosols are relatively short-lived in the troposphere and are returned to the surface by wet and dry deposition processes. Although wet deposition is considered the primary mechanism for removing BC from the atmosphere, published data is exceptionally scarce. In this study, we investigated the feasibility of determining BC wet deposition on a national/international scale using samples from the US National Atmospheric Deposition Program (NADP). The study investigated BC concentrations in precipitation by single-particle laser-induced incandescence (SP2). An intra-instrumental comparison with Thermal Optical Analysis (TOA). From October 26th to December 1st, 2020, we analyzed 478 NADP wet deposition samples from 209 locations, including sites in the United States, Canada and US territories, Puerto Rico, and the US Virgin Islands. Wet deposition BC concentrations varied from less than 0.3 µg L-1 to 38.7 µg L-1 with a median of 3.50 µg L-1. Associated BC wet deposition fluxes ranged from near zero to 9.1 g ha-1 wk-1, with a median of 0.87 g ha-1 wk-1. An analysis of the spatial variability indicated a pattern of higher BC deposition through the central United States consistent with BC transport from biomass burning during the sampling period.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Supplemental Table 1: Observations of GEM (ng m -3 ) and GOM, and PBM 2.5 (pg m -3 ), by 42 site and year, including valid-only number, means, medians and data ranges.Data are 43 inclusive for valid samples January 2009 through December 2011.Several sites were 44 unavailable for this study.