The City of Baltimore, MD has a history of problems with environmental justice (EJ), air pollution, and the urban heat island (UHI) effect. Current chemical transport models lack the resolution to simulate concentrations on the scale needed, about 100 m, to identify the neighborhoods with anomalously high air pollution levels. In this paper we introduce the capabilities of a mobile laboratory and an initial survey of several pollutants in Baltimore to identify which communities are exposed to disproportionate concentrations of air pollution and to which species. High concentrations of black carbon (BC) stood out at some locations - near major highways, downtown, and in the Curtis Bay neighborhood of Baltimore. Results from the mobile lab are confirmed with longer-term, low-cost monitoring. In Curtis Bay, higher concentrations of BC were measured along Pennington Ave. (mean [5th to 95th percentiles] = 2.08 [2.0-10.9] μg m-3) than along Curtis Ave. just ~ 150 m away (0.67[0.1 - 1.8] μg m-3). Other species, including criteria pollutants ozone (O3), carbon monoxide (CO), nitrogen dioxide (NO2), sulfur dioxide (SO2), and fine particulate matter (PM2.5), showed little gradient. Observations with high spatial and temporal resolution help isolate the mechanisms leading to locally high pollutant concentrations. The difference in BC appears to result not from heavier truck traffic or slower dispersion but from the interruptions in traffic flow. Pennington Ave. has three stoplights while Curtis Ave. has none. As heavy-duty diesel-powered vehicles accelerate, they experience turbo-lag and the resulting rich air-fuel mixture exacerbates BC emissions. Immediate mediation might be achieved through smoother traffic flow, and the long-term solution through replacing heavy-duty trucks with electric vehicles.Implications: We present results documenting the locations within Baltimore of high concentrations of Black Carbon pollution and identify the likely source - diesel exhaust emissions exacerbated by stop-and-go traffic and associated turbo-lag. This suggests solutions (smoother traffic, retrofit particulate filters, replacement of diesel with electric vehicles) that would enhance Environmental Justice (EJ) and could be applied to other cities with EJ problems.Synopsis: This paper presents observations of atmospheric black carbon aerosol showing impacts on environmental justice, then identifies causes and suggests solutions.

Our investigation seeks to uncover the intricate nature of mercury dynamics in the free troposphere through analysis of the isotopic composition of total gaseous elemental mercury (TGM) at the high altitude Mauna Loa Observatory (MLO, 3397 m) in Hawaii, USA. By focusing on this unique site, we aim to provide essential insights into the behavior and cycling of mercury, contributing valuable data to a deeper understanding of its global distribution and environmental impacts. Forty-eight hours of TGM sampling from January to September 2022 revealed significant variations in δ202Hg (-1.86 % to -0.32 %; mean = -1.17 ± 0.65 %, 2 SD, n = 34) and small variations in Δ199Hg (-0.27 % to 0.04 %; mean = -0.13 ± 0.14 %, 2 SD, n = 34) and Δ200Hg (-0.20 % to 0.06 %; mean = -0.05 ± 0.13 %, 2 SD, n = 34). During the sampling period, GEM was negatively correlated with gaseous oxidized mercury (GOM). However, the GOM/GEM ratio was not -1, suggesting that GEM oxidation and subsequent scavenging occurred previously. The δ202Hg isotopic compositions of TGM at MLO were different from those of reported values of high-altitude mountains; the δ202Hg of TGM at MLO was lower than the isotopic ratios that were obtained from other mountain regions. The unique atmospheric conditions at Mauna Loa, with (upslope winds during the day and downslope winds at night, likely result in the) possibly mixing of GEMs from terrestrial (and possibly oceanic GEM emission) sources with and tropospheric sources, influencing and affect the isotopic composition. During the late summer to early fall (September 14-28), negative correlations were found between relative humidity and GOM and between particle number concentrations and Δ199Hg, indicating the gas-to-particle partitioning of the atmospheric mercury during this period. This study will improve our understanding on mercury dynamics of marine origin and high altitudes and shed light on its complex interactions with environmental factors.

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In coastal environments like the Chesapeake Bay, the presence of the sea/bay breeze circulation can contribute to poor air quality and makes modeling the meteorological and chemical impacts of the sea/bay breeze in air quality forecast models a challenge. The Ozone Water-Land Environmental Transition Study 2 field campaign aimed to better quantify the mechanisms affecting surface, profile, and columnar trace gas amounts between the land and water. Using HYSPLIT back trajectory modeling, the meteorological variability affecting Pandora NO2 and surface O3 was quantified. Clustered back trajectories showed that westerly and north-northwesterly winds resulted in the highest MDA8 ozone values over the study domain. An analysis of multiday ozone event, demonstrated how TROPOMI can capture the spatial variability of NO2 observed by the Pandora network, including the accumulation of NO2 over the Chesapeake Bay. VOC measurements during multiday ozone event were analyzed and sources of ozone precursors, such as a coal fire power plant, were identified. Further investigation of the surface ozone data at HMI revealed that significant amounts of ozone were maintained over the Chesapeake Bay at night. Using a combination of ozone lidar, Pandora, in situ O3 and NO2, and wind lidar measurements, a lofted plume of NO2 was detected over water. Additionally, the same suite of observations found significant differences in the horizontal and vertical extent of ozone on the highest exceedance day of the event. Surface measurements of trace gases (NO2 and O3) can vary significantly from remote sensing (Pandora, TROPOMI, O3lidar), highlighting the need for sensitive profile, columnar, and in situ measurements in complex urban, marine environments for future geostationary air quality validation.

Land-sea recirculation such as bay and sea-breezes are important local circulations that facilitate pollution events. Measurements over a marine site in the Chesapeake Bay revealed the evolution of two bay-breeze events and associated ozone vertical structure. The horizontal and vertical structure of the bay-breeze was detailed using scanning Doppler wind lidar measurements and a ground-based ozone lidar was used to characterize the vertical distribution of ozone. The two bay-breeze events on 29–30 June 2018 observed during the Ozone Water-Land Environmental Transition Study Phase 2 (OWLETS-2) campaign showed distinct differences in the horizontal and vertical evolution of wind as well as the accompanying vertical structure of ozone. The analysis of the wind circulation showed that the intensity of the offshore flow plays an important role in the initiation time, development, and strength of the bay-breeze on both days. Results showed increased surface ozone concentrations during times of relatively low or decreasing bay-breeze height and weak upwards vertical motion. Upwards vertical motions were significantly enhanced on 30 June 2018 and presented with a decrease in surface ozone concentrations, yet enhanced ozone values were lofted above the surface near the lofted offshore flow. This study shows that both the vertical structure and evolution of pollutants can be impacted by the bay-breeze events through dilution and transport.

Atmospheric mercury species (including gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate-bound mercury (PBM)), trace pollutants (including O3, SO2, CO, NO, NOY and black carbon), and meteorological parameters have been continuously monitored since 2007 at an Atmospheric Mercury Network (AMNet) site located on the northern coast of the Gulf of Mexico at the Grand Bay National Estuarine Research Reserve (NERR) in Moss Point, Mississippi. For the data collected between 2007 and 2018, the average concentrations and standard deviations were 1.39 ± 0.22 ng m-3 for GEM, 5.1 ± 10.2 pg m-3 for GOM, 5.9 ± 13.0 pg m-3 for PBM, and 309 ± 407 ng m-2 wk-1 for mercury wet deposition, with interannual trends of -0.009 ng m-3 yr-1 for GEM, -0.36 pg m-3 yr-1 for GOM, 0.18 pg m-3 yr-1 for PBM, and 2.8 ng m-2 wk-1 yr-1 for mercury wet deposition. The trends are statistically significant for GEM and GOM, but not statistically significant for PBM and mercury wet deposition. Diurnal variation of GEM shows lower concentrations in the early morning due to GEM depletion likely due to plant uptake in high humidity events and slight elevation during the day likely due to downward mixing of higher concentrations of GEM in the air aloft to the surface. Seasonal variation of GEM shows higher levels in winter and spring and lower levels in summer and fall. Diurnal variations of both GOM and PBM show broad peaks in the afternoon likely due to photochemical oxidation of GEM. Seasonally, PBM measurements exhibit higher levels in winter and early spring and lower levels in summer, while GOM measurements show high levels in late spring/early summer and late fall and low levels in winter. The seasonal variation of mercury wet deposition shows higher values in summer and lower values in winter due to higher precipitation amounts in summer than in winter. As expected, anticorrelation between Hg wet deposition and the sum of GOM and PBM but positive correlation between Hg wet deposition and rainfall were observed. Correlation among GOM, ozone, and SO2 suggests two possible GOM sources: direct emissions and photochemical oxidation of GEM with the possible influence of boundary dynamics and seasonal variability. This study indicates that the monitoring site, which is located in a coastal environment of the Gulf of Mexico, might experience impacts from mercury sources that are both local and regional in nature.

Mercury is a toxic element that is dispersed globally through the atmosphere. Accurately measuring airborne mercury concentrations aids understanding of the pollutant’s sources, distribution, cycling, and trends. We deployed MerPAS® passive air samplers (PAS) for ~4 weeks during each season, from spring 2019 to winter 2020, to determine gaseous elemental mercury (GEM) levels at six locations along the northern Gulf of Mexico, where the pollutant is of particular concern due to high mercury wet deposition rates and high concentrations in local seafood. The objective was to (1) evaluate spatial and seasonal trends along the Mississippi and Alabama coast, and (2) compare active and passive sampling methods for GEM at Grand Bay National Estuarine Research Reserve, an Atmospheric Mercury Network site. We observed higher GEM levels (p < 0.05) in the winter (1.53 ± 0.03 ng m−3) compared to other seasons at all sites; with the general pattern being: winter > spring > summer ≈ fall. Average GEM levels (all deployment combined) were highest at Bay St. Louis (1.36 ± 0.05 ng m−3), the western-most site nearest the New Orleans metropolitan area, and lowest at Cedar Point (1.07 ± 0.09 ng m−3), a coastal marsh with extensive vegetation that can uptake GEM. The MerPAS units compared reasonably well with the established active monitoring system, but gave slightly lower concentrations, except in the winter when the two methods were statistically similar. Both the passive and active sampling methods showed the same seasonal trends and the difference between them for each season was <15%, acceptable for evaluating larger spatial and temporal trends. Overall, this work demonstrates that PASs can provide insight into GEM levels and the factors affecting them along coastal regions.

Atmospheric mercury species (gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM)), trace pollutants (O3, SO2, CO, NO, NOY, and black carbon), and meteorological parameters have been continuously measured since 2007 at an Atmospheric Mercury Network (AMNet) site that is located on the northern coast of the Gulf of Mexico in Moss Point, Mississippi. For the data that were collected between 2007 and 2018, the average concentrations and standard deviations are 1.39 ± 0.22 ng m−3 for GEM, 5.1 ± 10.2 pg m−3 for GOM, 5.9 ± 13.0 pg m−3 for PBM, and 309 ± 407 ng m−2 wk−1 for mercury wet deposition, with interannual trends of −0.009 ng m−3 yr−1 for GEM, −0.36 pg m−3 yr−1 for GOM, 0.18 pg m−3 yr−1 for PBM, and 2.8 ng m−2 wk−1 yr−1 for mercury wet deposition. The diurnal variation of GEM shows lower concentrations in the early morning due to GEM depletion, likely due to plant uptake in high humidity events and slight elevation during the day, likely due to downward mixing to the surface of higher concentrations of GEM in the air aloft. The seasonal variation of GEM shows higher levels in winter and spring and lower levels in summer and fall. Diurnal variations of both GOM and PBM show broad peaks in the afternoon likely due to the photochemical oxidation of GEM. Seasonally, PBM measurements exhibit higher levels in winter and early spring and lower levels in summer with rising levels in fall, while GOM measurements show high levels in late spring/early summer and late fall and low levels in winter. The seasonal variation of mercury wet deposition shows higher values in summer and lower values in winter, due to larger rainfall amounts in summer than in winter. As expected, anticorrelation between mercury wet deposition and the sum of GOM and PBM, but positive correlation between mercury wet deposition and rainfall were observed. Correlation among GOM, ozone, and SO2 suggests possible different GOM sources: direct emissions and photochemical oxidation of GEM, with the possible influence of boundary layer dynamics and seasonal variability. This study indicates that the monitoring site experiences are impacted from local and regional mercury sources as well as large scale mercury cycling phenomena.

Passive air samplers (PASs) for gaseous mercury (Hg) were deployed for time periods between 1 month and 1 year at 20 sites across the globe with continuous atmospheric Hg monitoring using active Tekran instruments. The purpose was to evaluate the accuracy of the PAS vis-a-vis the industry standard active instruments and to determine a sampling rate (SR; the volume of air stripped of gaseous Hg per unit of time) that is applicable across a wide range of conditions. The sites spanned a wide range of latitudes, altitudes, meteorological conditions, and gaseous Hg concentrations. Precision, based on 378 replicated deployments performed by numerous personnel at multiple sites, is 3.(6) +/- 3.(0) %(1), confirming the PAS's excellent reproducibility and ease of use. Using a SR previously determined at a single site, gaseous Hg concentrations derived from the globally distributed PASs deviate from Tekran-based concentrations by 14.(2) +/- 10 %. A recalibration using the entire new data set yields a slightly higher SR of 0.135(4) +/- 0.016 m(3) day(-1). When concentrations are derived from the PAS using this revised SR the difference between concentrations from active and passive sampling is reduced to 8.(8) +/- 7.(5) %. At the mean gaseous Hg concentration across the study sites of 1.54 ng m(-3), this represents an ability to resolve concentrations to within 0.13 ng m(-3). Adjusting the sampling rate to deployment specific temperatures and wind speeds does not decrease the difference in activepassive concentration further (8.(7) +/- 5.(7) %), but reduces its variability by leading to better agreement in Hg concentrations measured at sites with very high and very low temperatures and very high wind speeds. This value (8.(7) +/- 5.(7) %) represents a conservative assessment of the overall uncertainty of the PAS due to inherent uncertainties of the Tekran instruments. Going forward, the recalibrated SR adjusted for temperature and wind speed should be used, especially if conditions are highly variable or deviate considerably from the average of the deployments in this study (9.8(9) degrees C, 3.4(1) m s(-1)). Overall, the study demonstrates that the sampler is capable of recording background gaseous Hg concentrations across a wide range of environmental conditions with accuracy similar to that of industry standard active sampling instruments. Results at sites with active speciation units were inconclusive on whether the PASs take up total gaseous Hg or solely gaseous elemental Hg primarily because gaseous oxidized Hg concentrations were in a similar range as the uncertainty of the PAS.

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.

The Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) airborne instrument is a test bed for upcoming air quality satellite instruments that will measure backscattered ultraviolet, visible and near-infrared light from geostationary orbit. GeoTASO flew on the NASA Falcon aircraft in its first intensive field measurement campaign during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) Earth Venture Mission over Houston, Texas, in September 2013. Measurements of backscattered solar radiation between 420 and 465 nm collected on 4 days during the campaign are used to determine slant column amounts of NO2 at 250 m × 250 m spatial resolution with a fitting precision of 2.2 × 1015 moleculescm−2. These slant columns are converted to tropospheric NO2 vertical columns using a radiative transfer model and trace gas profiles from the Community Multiscale Air Quality (CMAQ) model. Total column NO2 from GeoTASO is well correlated with ground-based Pandora observations (r = 0.90 on the most polluted and cloud-free day of measurements and r = 0.74 overall), with GeoTASO NO2 slightly higher for the most polluted observations. Surface NO2 mixing ratios inferred from GeoTASO using the CMAQ model show good correlation with NO2 measured in situ at the surface during the campaign (r = 0.85). NO2 slant columns from GeoTASO also agree well with preliminary retrievals from the GEO-CAPE Airborne Simulator (GCAS) which flew on the NASA King Air B200 (r = 0.81, slope = 0.91). Enhanced NO2 is resolvable over areas of traffic NOx emissions and near individual petrochemical facilities.

The atmosphere is an important reservoir for mercury pollution, and understanding of oxidation processes is essential to elucidating the fate of atmospheric mercury. Several recent studies have shown that a low bias exists in a widely applied method for atmospheric oxidized mercury measurements. We developed an automated, permeation tube-based calibrator for elemental and oxidized mercury, and we integrated this calibrator with atmospheric mercury instrumentation (Tekran 2537/1130/1135 speciation systems) in Reno, Nevada and at Mauna Loa Observatory, Hawaii, U.S.A. While the calibrator has limitations, it was able to routinely inject stable amounts of HgCl2 and HgBr2 into atmospheric mercury measurement systems over periods of several months. In Reno, recovery of injected mercury compounds as gaseous oxidized mercury (as opposed to elemental mercury) decreased with increasing specific humidity, as has been shown in other studies, although this trend was not observed at Mauna Loa, likely due to differences in atmospheric chemistry at the two locations. Recovery of injected mercury compounds as oxidized mercury was greater in Mauna Loa than in Reno, and greater still for a cation-exchange membrane-based measurement system. These results show that routine calibration of atmospheric oxidized mercury measurements is both feasible and necessary.

Abstract. 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 inter-comparison 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 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 inter-continental flights. The investigated models proved to be able to reproduce the distribution of total and elemental mercury concentrations in the troposphere including inter-hemispheric 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 (RM) patterns depending on altitude. High RM concentrations 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 parametrizations in the chemistry transport models also proved to have a substantial impact on model results.

Different atmospheric mercury forms have been measured at a suburban site in Beltsville, Maryland in the Mid-Atlantic United States since 2007 to investigate their inter-annual, seasonal and diurnal variabilities. Average concentrations and standard deviations of hourly measurements from 2007 to 2015 were 1.41 ± 0.23 ng m−3 for gaseous elemental mercury (GEM), 4.6 ± 33.7 pg m−3 for gaseous oxidized mercury (GOM), and 8.6 ± 56.8 pg m−3 for particulate-bound mercury (PBM). Observations show that on average, the rates of decrease were 0.020 ± 0.007 ng m−3 yr−1 (or 1.3 ± 0.5% yr−1, statistically significant, p-value < 0.01) for GEM, 0.54 ± 0.19 pg m−3 yr−1 (or 7.3 ± 2.6% yr−1, statistically significant, p-value < 0.01) for GOM, and 0.15 ± 0.35 pg m−3 yr−1 (or 1.6 ± 3.8% yr−1, statistically insignificant, p-value > 0.01) for PBM over this nine-year period. In addition, the collocated annual mercury wet deposition decreased at a rate of 0.51 ± 0.24 μg m−2 yr−2 (or 4.2 ± 1.9% yr−1, statistically insignificant, p-value > 0.01). Diurnal variation of GEM shows a slight peak in the morning, likely due to the shallow boundary layer. Seasonal variation of GEM shows lower levels in fall. Both diurnal variations of GOM and PBM show peaks in the afternoon likely due to the photochemical production of reactive mercury from the oxidation of GEM and the influence of boundary layer processes. Seasonally, GOM measurements show high levels in spring and constant low levels in the other three seasons, while PBM measurements exhibit higher levels from late fall to early spring and lower levels from late spring to fall. These measurement data were analyzed using the HYSPLIT back trajectory model in order to examine possible source-receptor relationships at this suburban site. Trajectory frequency analysis shows that high GEM/GOM/PBM events were generally associated with high frequencies of the trajectories passing through areas with high mercury emissions, while low GEM/GOM/PBM levels were largely associated the trajectories passing through relatively clean areas. This study indicates that local and regional sources appear to have a significant impact on the site and these impacts appear to have changed over time, as the local/regional emissions have been reduced.

Abstract Mercury contamination in the Great Lakes continues to have important public health and wildlife ecotoxicology impacts, and atmospheric deposition is a significant ongoing loading pathway. The objective of this study was to estimate the amount and source-attribution for atmospheric mercury deposition to each lake, information needed to prioritize amelioration efforts. A new global, Eulerian version of the HYSPLIT-Hg model was used to simulate the 2005 global atmospheric transport and deposition of mercury to the Great Lakes. In addition to the base case, 10 alternative model configurations were used to examine sensitivity to uncertainties in atmospheric mercury chemistry and surface exchange. A novel atmospheric lifetime analysis was used to characterize fate and transport processes within the model. Model-estimated wet deposition and atmospheric concentrations of gaseous elemental mercury (Hg(0)) were generally within ∼10% of measurements in the Great Lakes region. The model overestimated non-Hg(0) concentrations by a factor of 2–3, similar to other modeling studies. Potential reasons for this disagreement include model inaccuracies, differences in atmospheric Hg fractions being compared, and the measurements being biased low. Lake Erie, downwind of significant local/regional emissions sources, was estimated by the model to be the most impacted by direct anthropogenic emissions (58% of the base case total deposition), while Lake Superior, with the fewest upwind local/regional sources, was the least impacted (27%). The U.S. was the largest national contributor, followed by China, contributing 25% and 6%, respectively, on average, for the Great Lakes. The contribution of U.S. direct anthropogenic emissions to total mercury deposition varied between 46% for the base case (with a range of 24–51% over all model configurations) for Lake Erie and 11% (range 6–13%) for Lake Superior. These results illustrate the importance of atmospheric chemistry, as well as emissions strength, speciation, and proximity, to the amount and source-attribution of mercury deposition.