Inter-comparison of measurements of inorganic chemical components in precipitation from NADP and CAPMoN at collocated sites in the USA and Canada during 1986-2019.

Wet deposition monitoring is a critical part of the long-term monitoring of acid deposition, which aims to assess the ecological impact of anthropogenic emissions of SO2 and NOx. In North America, long-term wet deposition has been monitored through two national networks: the Canadian Air and Precipitation Monitoring Network (CAPMoN) and the US National Atmospheric Deposition Program (NADP), for Canada and the USA, respectively. In order to assess the comparability of measurements from the two networks, collocated measurements have been made at two sites, one in each country, since 1986 (Sirois et al., in Environmental Monitoring and Assessment, 62, 273-303, 2000; Wetherbee et al., in Environmental Monitoring and Assessment, 1995-2004, 2010). In this study, we compared the measurements from NADP and CAPMoN instrumentation at the collocated sites at the Pennsylvania State University (Penn State), USA, from 1989 to 2016, and Frelighsburg, Quebec, Canada, from 2002 to 2019. We also included in the study the collocated daily-vs-weekly measurements by the CAPMoN network during 1999-2001 and 2016-2017 in order to evaluate the differences in wet concentration of ions due to sampling frequency alone. The study serves as an extension to two previous CAPMoN-NADP inter-comparisons by Sirois et al. (Environmental Monitoring and Assessment, 62, 273-303, 2000) and Wetherbee et al., in (Environmental Monitoring and Assessment, 1995-2004, 2010). At the Penn State University site, for 1986-2019, CAPMoN was higher than NADP for all ions, in terms of weekly concentration, precipitation-weighted annual mean concentration, and annual wet deposition. The precipitation-weighted annual mean concentrations were higher for SO42- (2%), NO3- (12%), NH4+ (16%), H+ (6%), and base cations and Cl- (11-15%). For annual wet deposition, CAPMoN was higher for SO4-2, NO3-, NH4+ and H+ (5-17%), and base cations and Cl- (12-17%) during 1986-2019. At the Frelighsburg site, NADP changed the sample collector in October 2011. For 2002-2011, the relative differences at the Frelighsburg site were positive and similar in magnitude to those at the Penn State site. For 2012-2019, the precipitation-weighted annual mean concentrations were 5-27% lower than NADP, except for H+, which was 23% higher. The change in sample collector by NADP had the largest effect on between-network biases. The comparisons of daily-vs-weekly measurements conducted by the CAPMoN network during 1999-2001 and 2016-2017 show that the weekly measurements were higher than the daily measurements by 1-3% for SO42-, NO3-, and NH4+; 3-9% for Ca2+, Mg2+, Na+, and Cl-; 10-24% for K+; and lower for H+ by 8-30% in terms of precipitation-weighted mean concentration. Thus, differences in sampling frequencies did not contribute to the systematically higher CAPMoN measurements. Understanding the biases in the data for these networks is important for interpretation of continental scale deposition models and transboundary comparison of wet deposition trends.

Nitrogen isotopes indicate vehicle emissions and biomass burning dominate ambient ammonia across Colorado's Front Range urban corridor.

Urban ammonia (NH3) emissions contribute to poor local air quality and can be transported to rural landscapes, impacting sensitive ecosystems. The Colorado Front Range urban corridor encompasses the Denver Metropolitan Area, rural farmland/rangeland and montane forest between the city and the Rocky Mountains. Reactive nitrogen emissions from the corridor are partly responsible for increased N deposition to the wildland-urban interface (WUI) in this region. To determine the significance of individual NH3 sources to WUI ecosystems, we measured the concentration and isotopic composition (δ15N-NH3) of ambient NH3(g) from April to October 2018 across a five-site urban to rural gradient in the corridor. The urban sites had higher NH3 concentrations and δ15N-NH3 values than the rural/suburban sites. Based on isotope mixing models, NH3 emission source contributions for all sites were fertilizer (12 ± 5.7%), livestock waste (18 ± 12%), vehicles (37 ± 23%), and biomass burning (34 ± 20%). Vehicle contributions were consistent across all months with an average of 35% and summer months showed a peak in biomass burning contributions (40%). As wildfires are projected to increase due to climate change, we stress a need for constraints on the isotopic signature of NH3 emitted from wildfires. Vehicle emissions contributed the greatest amount of NH3 (40%) at the urban sites while rural/suburban sites had higher agricultural contributions (41%). Had 2018 not had an anomalously high wildfire season, 46% and 60% of the NH3 would have been attributed to vehicle emissions at the WUI site and urban sites, respectively. NH3 emissions have historically been ascribed to agricultural activities but these findings illustrate the universal significance of vehicle emissions and the potential for sustained wildfire activity to be a primary contributor to NH3. Air quality (e.g., particulate matter) and nitrogen deposition reduction plans may benefit by including management practices that address vehicle NH3 emissions.

Inorganic nitrogen wet deposition gradients in the Denver-Boulder metropolitan area and Colorado Front Range - Preliminary implications for Rocky Mountain National Park and interpolated deposition maps.

For the first time in the 40-year history of the National Atmospheric Deposition Program/National Trends Network (NADP/NTN), a unique urban-to-rural transect of wet deposition monitoring stations was operated as part of the NTN in 2017 to quantify reactive inorganic nitrogen wet deposition for adjacent urban and rural, montane regions. The transect of NADP stations (sites) was used to collect continuous precipitation depth and weekly wet-deposition samples in the Denver - Boulder, Colorado, urban corridor. Gradients in reactive inorganic nitrogen (Nr) concentrations and wet deposition were identified along the transect, which included Rocky Mountain National Park. Back trajectory modeling and stable isotopes suggested contribution of agricultural ammonia (NH3) to urban Nr wet deposition in Denver, but apportionment of wet-deposited Nr to agricultural versus urban mobile sources was not possible for this study. The results demonstrate the importance of multiple monitoring sites across an urban area in defining fine-scale geographic patterns in atmospheric deposition and its sources. Data from new sites located within 50 km of the urban area demonstrate that the urban influence does not extend as far as the inverse distance weighting would have suggested without such empirical monitoring data. It is important to determine the radius of influence of urban emissions and associated deposition on the interpolated deposition raster, which is constrained by a paucity of monitoring sites east of Denver.

RETRACTED: Trends in bromide wet deposition concentrations in the contiguous United States, 2001-2016.

This article has been retracted: please see Elsevier Policy on Article Withdrawal (https://www.elsevier.com/about/our-business/policies/article-withdrawal). This article has been retracted at the request of the authors due to the results of a detailed investigation of the data quality conducted by the Central Analytical Laboratory (CAL) after relocation to the University of Wisconsin (UW) ­ Wisconsin State Laboratory of Hygiene. Using a subset of the 30 samples with the highest bromide ion (Br-) concentrations, the CAL at UW found 6 samples that could not be verified or were incorrect. Because the extent of the incorrect data is unknown, the NADP Executive Committee voted unanimously in May 2019 to discontinue public access to these data, and they decided to sequester all Br- data prior to June 2018. These issues were not obvious to the authors when the paper was written. The authors apologize for the inconvenience caused.

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.

Links between N deposition and nitrate export from a high-elevation watershed in the Colorado Front Range.

Long-term patterns of stream nitrate export and atmospheric N deposition were evaluated over three decades in Loch Vale, a high-elevation watershed in the Colorado Front Range. Stream nitrate concentrations increased in the early 1990 s, peaked in the mid-2000s, and have since declined by over 40%, coincident with trends in nitrogen oxide emissions over the past decade. Similarities in the timing and magnitude of N deposition provide evidence that stream chemistry is responding to changes in atmospheric deposition. The response to deposition was complicated by a drought in the early 2000s that enhanced N export for several years. Other possible explanations, including forest disturbance, snow depth, or permafrost melting, could not explain patterns in N export. Our results show that stream chemistry responds rapidly to changes in N deposition in high-elevation watersheds, similar to the response observed to changes in sulfur deposition.

Wet deposition of fission-product isotopes to North America from the Fukushima Dai-ichi incident, March 2011.

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.

Comparison of precipitation chemistry measurements obtained by the Canadian Air and Precipitation Monitoring Network and National Atmospheric Deposition Program for the period 1995-2004.

Precipitation chemistry and depth measurements obtained by the Canadian Air and Precipitation Monitoring Network (CAPMoN) and the US National Atmospheric Deposition Program/National Trends Network (NADP/NTN) were compared for the 10-year period 1995-2004. Colocated sets of CAPMoN and NADP instrumentation, consisting of precipitation collectors and rain gages, were operated simultaneously per standard protocols for each network at Sutton, Ontario and Frelighsburg, Ontario, Canada and at State College, PA, USA. CAPMoN samples were collected daily, and NADP samples were collected weekly, and samples were analyzed exclusively by each network's laboratory for pH, H(+), Ca(2+), Mg(2+), Na(+), K(+), NH4(+), Cl(-), NO3(-), and SO4(2-). Weekly and annual precipitation-weighted mean concentrations for each network were compared. This study is a follow-up to an earlier internetwork comparison for the period 1986-1993, published by Alain Sirois, Robert Vet, and Dennis Lamb in 2000. Median weekly internetwork differences for 1995-2004 data were the same to slightly lower than for data for the previous study period (1986-1993) for all analytes except NO3(-), SO4(2-), and sample depth. A 1994 NADP sampling protocol change and a 1998 change in the types of filters used to process NADP samples reversed the previously identified negative bias in NADP data for hydrogen-ion and sodium concentrations. Statistically significant biases (alpha = 0.10) for sodium and hydrogen-ion concentrations observed in the 1986-1993 data were not significant for 1995-2004. Weekly CAPMoN measurements generally are higher than weekly NADP measurements due to differences in sample filtration and field instrumentation, not sample evaporation, contamination, or analytical laboratory differences.

Estimated variability of National Atmospheric Deposition Program/Mercury Deposition Network measurements using collocated samplers.

The National Atmospheric Deposition Program/Mercury Deposition Network (MDN) provides long-term, quality-assured records of mercury in wet deposition in the USA and Canada. Interpretation of spatial and temporal trends in the MDN data requires quantification of the variability of the MDN measurements. Variability is quantified for MDN data from collocated samplers at MDN sites in two states, one in Illinois and one in Washington. Median absolute differences in the collocated sampler data for total mercury concentration are approximately 11% of the median mercury concentration for all valid 1999-2004 MDN data. Median absolute differences are between 3.0% and 14% of the median MDN value for collector catch (sample volume) and between 6.0% and 15% of the median MDN value for mercury wet deposition. The overall measurement errors are sufficiently low to resolve between NADP/MDN measurements by +/-2 ng.l(-1) and +/-2 microg.m(-2).year(-1), which are the contour intervals used to display the data on NADP isopleths maps for concentration and deposition, respectively.

Spatial and temporal variability of the overall error of National Atmospheric Deposition Program measurements determined by the USGS collocated-sampler program, water years 1989-2001.

Data from the U.S. Geological Survey (USGS) collocated-sampler program for the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) are used to estimate the overall error of NADP/NTN measurements. Absolute errors are estimated by comparison of paired measurements from collocated instruments. Spatial and temporal differences in absolute error were identified and are consistent with longitudinal distributions of NADP/NTN measurements and spatial differences in precipitation characteristics. The magnitude of error for calcium, magnesium, ammonium, nitrate, and sulfate concentrations, specific conductance, and sample volume is of minor environmental significance to data users. Data collected after a 1994 sample-handling protocol change are prone to less absolute error than data collected prior to 1994. Absolute errors are smaller during non-winter months than during winter months for selected constituents at sites where frozen precipitation is common. Minimum resolvable differences are estimated for different regions of the USA to aid spatial and temporal watershed analyses.