Gaseous and particulate-bound oxidized mercury (Hg) compounds (Hg-II) have high solubility in precipitation compared to gaseous elemental Hg (Hg-0). Wet and dry deposition are the primary routes of entry for atmospheric HgII into aquatic ecosystems. Information on how much HgII is removed from the atmosphere to the landscape during precipitation is lacking. In this study, oxidized HgII concentrations were measured with a dual-channel system (DCS) at two sites in the United States, Storm Peak Laboratory (SPL), in Colorado (2021-2022), and Beltsville (MD99) in Maryland (2022-2024), and compared with data from 16 co-located Atmospheric Mercury Network (AMNet) and Mercury Deposition Network (MDN) sites that used a KCl denuder method. At the two DCS sites, gaseous oxidized Hg concentrations were segregated by wet and dry periods from the nearest precipitation gauge to determine values for median dry HgII and median wet HgII concentrations (dry-wet = "HgII washout") for each site. SPL had higher median ambient HgII and higher median HgII washout (90 pg m(-3) and 22 pg m-3, respectively) compared to that for MD99 (43 pg m-3 and 7 pg m-3). This difference could be due to site elevation (3161 vs. 77 m) as there is generally more HgII higher in the atmosphere. In contrast, the ambient HgII/washout Hg-II ratios were more similar, 4.1 for SPL and 5.8 at MD99. The mean ambient HgII/washout HgII ratio for the 16 AMNet sites was 1.8 +/- 0.1. The AMNet HgII data are known to be biased low due to issues with the KCl-denuder method, and this low bias appears to result in lower ambient HgII/washout HgII ratio observed for the AMNet sites. Correction factors for AMNet data using HgII measurements from DCS instruments were found to range from 2-3 and could be used to improve the accuracy of older data.

Most of our knowledge about the global distribution of atmospheric iodine is based on measurements of iodine monoxide (IO) radicals in the marine boundary layer and at high latitudes. Recent evidence of IO in the free troposphere is limited to few available aircraft measurements over oceans. We report the first ground-based Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations of tropospheric IO radicals over the central continental United States. IO vertical columns measured at Storm Peak Laboratory, CO (40.455°N, 106.744°W, 3220 m.a.s.l.) are similar to those over oceans and vary significantly. A priori sensitivity studies indicate that IO mixing ratios increase with altitude. Back trajectory modeling indicates that IO is consistently observed in air masses quickly transported from over the Pacific Ocean. We compare the IO columns and their variability with predictions by a global model and use the observations to constrain a chemical box model to assess the atmospheric implications for ozone and mercury oxidation. Iodine-induced mercury oxidation is currently missing in atmospheric models, understudied, and helps to partially explain the elevated concentrations of oxidized mercury measured at SPL.

Storm Peak Laboratory, located on the Steamboat Springs Ski Resort in Colorado on the west summit of Mount Werner at 10 532 ft (3220 m) MSL, is an internationally recognized high-elevation atmospheric research station that has been in use for over 40 years. This article provides a brief history of the Storm Peak Laboratory and the major research themes it has supported and discusses opportunities to leverage mountain observatory measurements to advance our understanding of the atmospheric processes. This facility provides long-term measurements of meteorology, clouds, aerosols, snow hydrology, and atmospheric gases, and it serves as a "proving ground" for instrument development and testing. Storm Peak Laboratory is part of multiple national and international observational networks. Due to the unique capabilities of Storm Peak Laboratory, there is a long history of targeted field campaigns primarily within the following research areas: mixed-phase cloud microphysics; atmospheric chemistry pertaining to the formation, characterization, and hygroscopicity of aerosols; and the transport and transformation of atmospheric mercury. Research training has been central to the mission of Storm Peak Laboratory (SPL) over the last 40 years. Currently, SPL hosts both undergraduate-and graduate-level courses in atmospheric science and snow hydrology organized by numerous institutions. Examples of these unique research training opportunities are provided. SIGNIFICANCE STATEMENT: This article provides a brief history of the Storm Peak Laboratory and the major research themes it has supported. Furthermore, this article discusses opportunities to leverage mountain observatory measurements to advance our understanding of the atmospheric processes. Located on the Steamboat Springs Ski Resort in northwestern Colorado, Storm Peak Laboratory has been in use for over 40 years and is an internationally recognized high-elevation atmospheric research station. Due to the unique capabilities of Storm Peak Laboratory, there is a long history of targeted field campaigns primarily within the following research areas: mixed-phase cloud microphysics; atmospheric chemistry pertaining to the formation, characterization, and hygroscopicity of aerosols; and the transport and transformation of atmospheric mercury. Research training has been central to the mission of Storm Peak Laboratory (SPL) over the last 40 years. Currently, SPL hosts both undergraduate-and graduate-level courses in atmospheric science and snow hydrology organized by numerous institutions.

Most previous measurements of oxidized mercury were collected using a method now known to be biased low. In this study, a dual-channel system with an oxidized mercury detection limit of 6-12 pg m(-3) was deployed alongside a permeation tube-based automated calibrator at a mountain top site in Steamboat Springs Colorado, USA, in 2021 and 2022. Permeation tubes containing elemental mercury and mercury halides were characterized via an International System of Units (SI)-traceable gravimetric method and gas chromatography/mass spectrometry before deployment in the calibrator. The dual-channel system recovered 97 +/- 4 and 100 +/- 8% (+/- standard deviation) of injected elemental mercury and HgBr2, respectively. Total Hg permeation rates and Hg speciation from the gravimetric method, the chromatography system, the dual-channel system, and an independent SI-traceable measurement method performed at the Jozef Stefan Institute laboratory were all comparable within the respective uncertainties of each method. These are the first measurements of oxidized mercury at low environmental concentrations that have been verified against an SI-traceable calibration system in field conditions while sampling ambient air, and they show that accurate, routinely calibrated oxidized mercury measurements are achievable.

Abstract Previous efforts to measure atmospheric iodine have focused on marine and coastal regions. We report the first ground‐based tropospheric iodine monoxide (IO) radical observations over the central continental United States. Throughout April 2022, IO columns above Storm Peak Laboratory, Colorado (3,220 m.a.s.l.) ranged from 0.7 ± 0.5 to 3.6 ± 0.5 × 1012 (average: 1.9 × 1012 molec cm−2). IO was consistently elevated in air masses transported from over the Pacific Ocean. The observed IO columns were up to three times higher and the range was larger than predicted by a global model, which warrants further investigation into iodine sources, sinks, ozone loss, and particle formation. IO mixing ratios increased with altitude. At the observed levels, iodine may be competitive with bromine as an oxidant of elemental mercury at cold temperatures typical of the free troposphere. Iodine‐induced mercury oxidation is missing in atmospheric models, understudied, and helps explain model underestimation of oxidized mercury measurements.

Mercury (Hg) is a global atmospheric pollutant. In its oxidized form (HgII), it can readily deposit to ecosystems, where it may bioaccumulate and cause severe health effects. High HgII concentrations are reported in the free troposphere, but spatiotemporal data coverage is limited. Underestimation of HgII by commercially available measurement systems hinders quantification of Hg cycling and fate. During spring–summer 2021 and 2022, we measured elemental (Hg0) and oxidized Hg using a calibrated dual-channel system alongside trace gases, aerosol properties, and meteorology at the high-elevation Storm Peak Laboratory (SPL) above Steamboat Springs, Colorado. Oxidized Hg concentrations displayed diel and episodic behavior similar to previous work at SPL but were approximately 3 times higher in magnitude due to improved measurement accuracy. We identified 18 multi-day events of elevated HgII (mean enhancement of 36 pg m−3) that occurred in dry air (mean ± SD of relative humidity = 32 ± 16 %). Lagrangian particle dispersion model (HYSPLIT–STILT, Hybrid Single-Particle Lagrangian Integrated Trajectory–Stochastic Time-Inverted Lagrangian Transport) 10 d back trajectories showed that the majority of transport prior to events occurred in the low to middle free troposphere. Oxidized Hg was anticorrelated with Hg0 during events, with an average (± SD) slope of −0.39 ± 0.14. We posit that event HgII resulted from upwind oxidation followed by deposition or cloud uptake during transport. Meanwhile, sulfur dioxide measurements verified that three upwind coal-fired power plants did not influence ambient Hg at SPL. Principal component analysis showed HgII consistently inversely related to Hg0 and generally not associated with combustion tracers, confirming oxidation in the clean, dry free troposphere as its primary origin.

Mercury (Hg) researchers have made progress in understanding atmospheric Hg, especially with respect to oxidized Hg (Hg-II) that can represent 2 to 20% of Hg in the atmosphere. Knowledge developed over the past similar to 10 years has pointed to existing challenges with current methods for measuring atmospheric Hg concentrations and the chemical composition of Hg-II compounds. Because of these challenges, atmospheric Hg experts met to discuss limitations of current methods and paths to overcome them considering ongoing research. Major conclusions included that current methods to measure gaseous oxidized and particulate-bound Hg have limitations, and new methods need to be developed to make these measurements more accurate. Developing analytical methods for measurement of Hg-II chemistry is challenging. While the ultimate goal is the development of ultrasensitive methods for online detection of Hg-II directly from ambient air, in the meantime, new surfaces are needed on which Hg-II can be quantitatively collected and from which it can be reversibly desorbed to determine Hg-II chemistry. Discussion and identification of current limitations, described here, provide a basis for paths forward. Since the atmosphere is the means by which Hg is globally distributed, accurately calibrated measurements are critical to understanding the Hg biogeochemical cycle.

Quantifying atmospheric loadings of total phosphorus (TP) to freshwater environments is essential to improve understanding of its fate and transport, and to mitigate the effects of excessive levels in freshwater ecosystems. To date, atmospheric deposition of TP in the U.S. is poorly characterized due to the lack of long-term deposition observations. Here, we integrate several historical datasets to develop an estimate of dry and wet deposition to the Great Lakes region. For dry deposition, we use TP concentrations in fine particulate matter (PM2.5) samples from fourteen land-based IMPROVE sites (2013-2020) upwind of the Great Lakes to provide new fine particle phosphorus dry deposition estimates. For wet deposition, we use TP concentrations in wet-only precipitation samples collected at eleven land-based sites (2001-2009) in the Great Lakes region. For both wet and dry deposition, a seasonal cycle is evident with higher concentrations in warmer and wetter months when compared to colder months. Additionally, there is an increasing gradient from north to south in wet deposition, likely driven by both higher precipitation and increased emissions near southern sites. Despite different sampling time periods, these updated observations can provide further constraints on the TP loadings to each of the five Great Lakes. We estimate annual deposition of TP to Lakes Superior, Michigan, Huron, Erie and Ontario at 526, 702, 495, 212, and 185 MTA per year, which is lower than prior estimates for Lakes Superior, Erie and Ontario, comparable for Lake Huron, and about two times greater for Lake Michigan. When considering only the contribution of fine particulate PM to the dry deposition, wet deposition dominated over dry at all lakes except for Lake Huron. However, prior global estimates suggest greater contributions from larger particles (PM10 and PM100), yet observations to validate these estimates over the Great Lakes are not available. Our findings indicate that dry deposition of a range of particle sizes are needed to constrain the total atmospheric deposition of TP over the Great Lakes.

Sublethal exposure to methylmercury (MeHg) can have consequences for the reproductive, neurological, and physiological health of birds. Songbirds, regardless of trophic position, are often exposed to mercury (Hg) and may be at risk for health effects – especially if they inhabit a place that is subject to high Hg atmospheric deposition and/or have local conditions that are prone to methylation. This study investigates Hg concentrations in terrestrial songbirds of Southeast Michigan, where historical and present-day anthropogenic emissions of heavy metals are elevated. We collected tail feather samples from 223 songbirds across four different species during summer and fall of 2018 and 2019. The mean (±SE) Hg concentration across all samples was 103 ± 3.43 ng/g of dry feather weight. Mercury concentration varied significantly among species, and by age and site in some species, but not by sex. Mean concentrations were nearly seven times higher in two omnivore species, American robin (Turdus migratorius) and European starling (Sturnus vulgaris), than in the two granivore species, American goldfinch (Spinus tristus) and house sparrow (Passer domesticus). Juveniles had higher feather Hg concentrations than adults in all species except American goldfinches - which feed their young primarily seeds, further supporting a role of diet in exposure. We also found a negative correlation between Hg concentration and body condition in American robins, but further research is needed to verify this relationship. While our sample concentrations do not exceed the threshold for sublethal effects, our findings provide insight into the patterns of Hg concentrations in terrestrial songbirds, which may help in understanding Hg exposure pathways, bioaccumulation and risks in terrestrial species.

Summertime ozone in the Western United States presents a unique public health challenge. Changes in population, background ozone, wildland fire, and local precursor emissions combined with terrain-induced meteorology can affect surface ozone levels and compliance with the National Ambient Air Quality Standards (NAAQS). While there is considerable research on ozone in the Northern Front Range Metropolitan Area of Colorado, United States, less is known about the Southern Front Range. In Colorado Springs, approximately 100 km south of Denver, summertime maximum daily 8-h average (MDA8) ozone shows no significant (p < .05) trend at the 5th, 50th, or 95th percentile over the past 20 years. However, the region is at risk of nonattainment with the NAAQS based on observations from 2018 to 2020. From June through September 2018, the Colorado Department of Public Health and Environment measured hourly ozone at eight sites to characterize the spatial distribution of ozone in Colorado Springs. Mean ozone (±1σ) ranged from 34 ± 19 to 60 ± 9 ppb. The 95th percentile of hourly ozone increased approximately 1.1 ppb per 100 m of elevation, while the amplitudes of mean diurnal profiles decreased with elevation and distance from the interstate. MDA8 ozone was also highly correlated across all sites, and there is little evidence of local photochemical production or ozone transport from Denver. Further, results from generalized additive modeling show that summertime MDA8 in this region is strongly influenced by regional background air and wildfire, with smoke contributing an average of 4–5 ppb to the MDA8. Enhanced MDA8 values due to wildfires were especially pronounced in 2018 and 2020. Lastly, we find that the permanent monitoring sites represent the lower end of observed ozone in the region, suggesting that additional long-term monitoring for public health may be warranted in populated, higher elevation areas.

Mercury is an environmental toxin that is emitted into the atmosphere as either elemental or oxidized mercury, through natural and anthropogenic sources. Once in the atmosphere

We developed a cation-exchange membrane-based dual-channel system to measure elemental and oxidized mercury and deployed it with an automated calibration system and the University of Nevada, Reno-Reactive Mercury Active System (UNR-RMAS) at a rural/suburban field site in Colorado during the summer of 2018. Unlike oxidized mercury measurements collected via the widely used KCl denuder method, the dual-channel system was able to quantitatively recover HgCl2 and HgBr2 injected by the calibrator into the ambient sample air and compared well with the UNR-RMAS measurements. The system measured at 10 min intervals and had a 3-h average detection limit for oxidized mercury of 33 pg m-3. It was able to detect day-to-day variability and diel cycles in oxidized mercury (0 to 200 pg m-3) and will be an important tool for future studies of atmospheric mercury. We used a gravimetric method to independently determine the total mercury permeation rate from the permeation tubes. Permeation rates derived from the gravimetric method matched the permeation rates observed via mercury measurement devices to within 25% when the mercury permeation rate was relatively high (up to 30 pg s-1), but the agreement decreased for lower permeation rates, probably because of increased uncertainty in the gravimetric measurements.

The atmosphere is a significant global reservoir for mercury (Hg) and its isotopic characterization is important to understand sources, distribution, and deposition of Hg to the Earth's surface. To better understand Hg isotope variability in the remote background atmosphere, we collected continuous 12-h Hg0 samples for 1 week from two high elevation sites, Camp Davis, Wyoming (valley), and Mount Bachelor, Oregon (mountaintop). The samples collected at Camp Davis displayed strong diel variation in δ202Hg values of Hg0, but not in Δ199Hg or Δ200Hg values. We attribute this pattern to nightly atmospheric inversions trapping Hg in the valley and the subsequent nighttime uptake of Hg by vegetation, which depletes Hg from the atmosphere. At Mount Bachelor, the samples displayed diel variation in both δ202Hg and Δ199Hg, but not Δ200Hg. We attribute this pattern to differences in the vertical distribution of Hg in the atmosphere as Mount Bachelor received free tropospheric air masses on certain nights during the sampling period. Near the end of the sampling period at Mount Bachelor, the observed diel pattern dissipated due to the influence of a nearby forest fire. The processes governing the Hg isotopic fractionation differ across sites depending on mixing, topography, and vegetation cover.

We report on the continuous ambient measurements of total gaseous mercury (TGM) and several ancillary air quality parameters that were collected in Colorado Springs, CO. This urban area, which is located adjacent to the Front Range of the Rocky Mountains, is the second largest metropolitan area in Colorado and has a centrally located coal-fired power plant that installed mercury (Hg) emission controls the year prior to our study. There are few other Hg point sources within the city. Our results, which were obtained from a measurement site < 1 km from the power plant, show a distinct diel pattern in TGM, with peak concentrations occurring during the night (1.7 ± 0.3 ng m−3) and minimum concentrations mid-day (1.5 ± 0.2 ng m−3). The TGM concentrations were not correlated with wind originating from the direction of the plant or with sulfur dioxide (SO2) mixing ratios, and they were not elevated when the atmospheric mixing height was above the effective stack height. These findings suggest that the current Hg emissions from the CFPP did not significantly influence local TGM, and they are consistent with the facility’s relatively low reported annual emissions of 0.20 kg Hg per year. Instead, variability in the regional signal, diurnal meteorological conditions, and/or near-surface emission sources appears to more greatly influence TGM at this urban site.

The atmosphere is a key component of the biogeochemical cycle of mercury, acting as a reservoir, transport mechanism, and facilitator of chemical reactions. The chemical and physical behavior of atmospheric mercury determines how, when, and where emitted mercury pollution impacts ecosystems. In this review, we provide current information about what is known and what remains uncertain regarding mercury in the atmosphere. We discuss new ambient, laboratory, and theoretical information about the chemistry of mercury in various atmospheric media. We review what is known about mercury in and on solid- and liquid-phase aerosols. We present recent findings related to wet and dry deposition and spatial and temporal trends in atmospheric mercury concentrations. We also review atmospheric measurement methods that are in wide use and those that are currently under development.

AbstractThe Southeast Atmosphere Studies (SAS), which included the Southern Oxidant and Aerosol Study (SOAS); the Southeast Nexus (SENEX) study; and the Nitrogen, Oxidants, Mercury and Aerosols: Distributions, Sources and Sinks (NOMADSS) study, was deployed in the field from 1 June to 15 July 2013 in the central and eastern United States, and it overlapped with and was complemented by the Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) campaign. SAS investigated atmospheric chemistry and the associated air quality and climate-relevant particle properties. Coordinated measurements from six ground sites, four aircraft, tall towers, balloon-borne sondes, existing surface networks, and satellites provide in situ and remotely sensed data on trace-gas composition, aerosol physicochemical properties, and local and synoptic meteorology. Selected SAS findings indicate 1) dramatically reduced NOx concentrations have altered ozone production regimes; 2) indicators of “biogenic” secondary organic aerosol (SOA), once considered part of the natural background, were positively correlated with one or more indicators of anthropogenic pollution; and 3) liquid water dramatically impacted particle scattering while biogenic SOA did not. SAS findings suggest that atmosphere–biosphere interactions modulate ambient pollutant concentrations through complex mechanisms and feedbacks not yet adequately captured in atmospheric models. The SAS dataset, now publicly available, is a powerful constraint to develop predictive capability that enhances model representation of the response and subsequent impacts of changes in atmospheric composition to changes in emissions, chemistry, and meteorology.

Atmospheric chemistry and transport of mercury play a key role in the global mercury cycle. However, there are still considerable knowledge gaps concerning the fate of mercury in the atmosphere. This is the second part of a model intercomparison study investigating the impact of atmospheric chemistry and emissions on mercury in the atmosphere. While the first study focused on ground-based observations of mercury concentration and deposition, here we investigate the vertical and interhemispheric distribution and speciation of mercury from the planetary boundary layer to the lower stratosphere. So far, there have been few model studies investigating the vertical distribution of mercury, mostly focusing on single aircraft campaigns. Here, we present a first comprehensive analysis based on various aircraft observations in Europe, North America, and on intercontinental flights. The investigated models proved to be able to reproduce the distribution of total and elemental mercury concentrations in the troposphere including interhemispheric trends. One key aspect of the study is the investigation of mercury oxidation in the troposphere. We found that different chemistry schemes were better at reproducing observed oxidized mercury patterns depending on altitude. High concentrations of oxidized mercury in the upper troposphere could be reproduced with oxidation by bromine while elevated concentrations in the lower troposphere were better reproduced by OH and ozone chemistry. However, the results were not always conclusive as the physical and chemical parameterizations in the chemistry transport models also proved to have a substantial impact on model results.