Atmospheric Chemistry of Gaseous Oxidized Mercury at a Coastal Site in Atlantic Canada

Abstract A chemistry box model containing a comprehensive suite of mercury (Hg) oxidation mechanisms involving O3, OH, H2O2, Br, BrO, NO2, HO2, and other oxidants was used to simulate the formation of gaseous oxidized mercury (GOM) and understand the chemical processes driving the observed trends in GOM at Kejimkujik, Nova Scotia, Canada. Simulations were conducted using chemical schemes with and without oxidation by O3 and OH. The major oxidants of Hg are O3 and OH (79%), H2O2 (10%), Br with second-stage HgBr oxidation by NO2 (7%), and BrO (3%) in simulations where all GEM oxidation reactions were considered simultaneously. In an alternative chemical scheme without gas-phase oxidation by O3 and OH, the dominant GOM species were HgBrNO2 (58%) and HgBrO (23.5%). Using this chemical scheme, the model reproduced the observed GOM at sub-ppqv Br2 mixing ratios. In the scheme with O3 and OH, the variability in GOM between seasons and between continental and marine air masses was mainly due to the variability in gaseous elemental Hg, O3, OH, and aerosol liquid water content (LWC). LWC governs the partitioning of GOM to the aerosol aqueous phase in the model. In the scheme without O3 and OH, the variability in GOM by season and airmass origin strongly depends on Br and BrO, suggesting that rigorous validation of modeled Br and BrO data are essential for improving the model predictions of GOM in coastal environments.

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Investigation of atmospheric hydrogen cyanide: a modelling perspective

10.5194/egusphere-egu21-8865 ◽

2021 ◽

Author(s):

Antonio G. Bruno ◽

Jeremy J. Harrison ◽

David P. Moore ◽

Martyn P. Chipperfield ◽

Richard J. Pope

Keyword(s):

Biomass Burning ◽

Atmospheric Chemistry ◽

Hydrogen Cyanide ◽

Three Dimensional ◽

Oxidation Reactions ◽

Loss Mechanism ◽

Mixing Ratios ◽

The Individual ◽

Atmospheric Loss ◽

Physical And Chemical

Hydrogen cyanide (HCN) is one of the most abundant cyanides present in the global atmosphere, and is a tracer of biomass burning, especially for peatland fires. The HCN lifetime is 2&#8211;5 months in the troposphere but several years in the stratosphere. Understanding the physical and chemical mechanisms of HCN variability is important due to its non-negligible role in the nitrogen cycle. The main source of tropospheric HCN is biomass burning with minor contributions from industry and transport. The main loss mechanism of atmospheric HCN is the reaction with the hydroxyl radical (OH). Ocean uptake is also important, while in the stratosphere oxidation by reaction with O(1D) needs to be considered.HCN variability can be investigated using chemical model simulations, such as three-dimensional (3-D) chemical transport models (CTMs). Here we use an adapted version of the TOMCAT 3-D CTM at a 1.2&#176;x1.2&#176; spatial resolution from the surface to ~60 km for 12 idealised HCN tracers which quantify the main loss mechanisms of HCN, including ocean uptake, atmospheric oxidation reactions and their combinations. The TOMCAT output of the HCN distribution in the period 2004-2020 has been compared with HCN profiles measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) over an altitude grid from 6 to 42 km. HCN model data have also been compared with ground-based measurements of HCN columns from NDACC FTIR stations and with in-situ volume mixing ratios (VMRs) from NOAA ground-based measurement sites.The model outputs for the HCN tracer with full treatment of the loss processes generally agree well with ACE-FTS measurements, as long as we use recent laboratory values for the atmospheric loss reactions. Diagnosis of the individual loss terms shows that decay of the HCN profile in the upper stratosphere is due mainly to the O(1D) sink. In order to test the magnitude of the tropospheric OH sink and the magnitude of the ocean sink, we also show the comparisons of the model tracers with surface-based observations. The implications of our results for understanding HCN and its variability are then discussed.

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Atmospheric bromoform at Cape Point, South Africa: a first time series on the African continent

10.5194/acp-2017-244 ◽

2017 ◽

Author(s):

Brett Kuyper ◽

Carl J. Palmer ◽

Casper Labuschagne ◽

Chris J. C. Reason

Keyword(s):

South Africa ◽

Austral Spring ◽

Data Set ◽

Air Masses ◽

Mixing Ratios ◽

Front End ◽

Potential Source ◽

High Concentrations ◽

Marine Air ◽

First Time

Abstract. Bromoform mixing ratios in marine air were measured at Cape Point Global Atmospheric Watch Station, South Africa. This represents the first ever bromoform data set recorded at this unique location. Manual daily measurements were made during a month long field campaign (austral spring 2011) using a GC-ECD with a custom built front end thermal desorption trap. The measured concentrations ranged between 2.3 ± 0.4 and 84.7 ± 10.8 ppt with a mean of 24.7 ± 3.1 ppt. Our analysis shows the concentration of bromform varies significantly according to wind direction and the trajectory of the air mass sampled. Air masses which had come into contact with multiple potential source of bromoform showed the highest average mixing ratios. The measurements reported here represent some of the highest recorded coastal bromoform concentrations globally. These high concentrations may be explained by the multiple local sources of bromoform around Cape Point.

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Friagem Event in Central Amazon and its Influence on Micrometeorological Variables and Atmospheric Chemistry

10.5194/acp-2020-564 ◽

2020 ◽

Author(s):

Guilherme F. Camarinha-Neto ◽

Julia C. P. Cohen ◽

Cléo Q. Dias-Júnior ◽

Matthias Sörgel ◽

José Henrique Cattanio ◽

...

Keyword(s):

Atmospheric Chemistry ◽

Temperature Drop ◽

Atmospheric Modeling ◽

Amazon Region ◽

Cold Pool ◽

Large Temperature ◽

Mixing Ratio ◽

Air Masses ◽

Central Amazon ◽

Mixing Ratios

Abstract. In the period between July 9th and 11th, 2014 a Friagem event reached the central Amazon region causing significant changes in microclimate and atmospheric chemistry. On July 11th, the southwest flow related to the Friagem converged with the easterly winds in the central Amazon region. The interaction between these two distinct air masses formed a convection band, which intensified over the Manaus region and the Amazon Tall Tower Observatory (ATTO) site. The satellite images show the evolution of convective activity on July 11th, which lead to 21 mm of precipitation in the ATTO site. Moreover, the arrival of the Friagem caused a sudden drop in temperature and a predominance of southerly winds, which could be seen in Porto Velho between July 7th and 8th and in Manaus and ATTO site from July 9th to 11th. The results of ERA reanalysis and Brazilian developments on the Regional Atmospheric Modeling System (BRAMS) simulations show that this Friagem event coming from the southwest, carries a mass of air with higher O3 and NO2 mixing ratios and lower CO mixing ratio compared to the air masses present at the central Amazon. At lake Balbina the Friagem intensifies the local circulations, such as the breeze phenomena. At the Manaus region and ATTO site, the main effects of the Friagem event are: a decrease in the incoming solar radiation (due to intense cloud formation), a large temperature drop and a distinct change in surface O3 and CO2 mixing ratios. As the cold air of the Friagem was just in the lower 500 m the most probable cause of this change is that a cold pool above the forest prevented vertical mixing causing accumulation of CO2 from respiration and very low O3 mixing ratio due to photochemistry reduction and limited mixing within the boundary layer.

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Temporal variations of black carbon in Guangzhou, China, in summer 2006

Atmospheric Chemistry and Physics ◽

10.5194/acp-10-6471-2010 ◽

2010 ◽

Vol 10 (14) ◽

pp. 6471-6485 ◽

Cited By ~ 48

Author(s):

R. L. Verma ◽

L. K. Sahu ◽

Y. Kondo ◽

N. Takegawa ◽

S. Han ◽

...

Keyword(s):

Black Carbon ◽

Temporal Variations ◽

Back Trajectories ◽

Air Masses ◽

Mixing Ratios ◽

Diurnal Patterns ◽

Air Mass Types ◽

The Pearl River ◽

Carbon Dioxide Co2 ◽

Marine Air

Abstract. In situ measurements of the mass concentration of black carbon (BC) and mixing ratios of carbon monoxide (CO) and carbon dioxide (CO2) were made at Guangzhou, an urban measurement site in the Pearl River Delta (PRD), China, in July 2006. The average ± standard deviation (SD) concentrations of BC, CO, and CO2 were 4.7± 2.3 μgC m−3, 798± 459 ppbv, and 400± 13 ppmv, respectively. The trends of these species were mainly controlled by synoptic-scale changes in meteorology during the campaign. Based on back trajectories, data are analyzed separately for two different air mass types representing northerly and southerly flows. The northerly air masses, which constituted ~25% of the campaign, originated mostly in the PRD and hence represent observations on regional scales. On the other hand, during southerly flow (~75%), the measurements were influenced by dilution due to cleaner marine air. The diurnal patterns of BC, CO, and CO2 exhibited peak concentrations during the morning and evening hours coinciding with rush-hour traffic. The ratios of OC/BC were lower during the morning hour peaks in the concentrations of primary pollutants due to their fresh emissions mainly from vehicular traffic in Guangzhou. The diurnal variations of BC observed in southerly air masses tended to follow the traffic patterns of heavy-duty vehicles (HDV) in Guangzhou, while the roles of other sources need to be investigated. The slopes of ΔBC/ΔCO, ΔBC/ΔCO2, and ΔCO/ΔCO2 observed during northerly flows were 0.0045 μgC m−3/ppbv, 0.13 μgC m−3/ppmv, and 49.4 ppbv/ppmv, respectively, agreeing reasonably with their respective emission ratios derived from regional emission inventories.

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Pollution trace gas distributions and their transport in the Asian monsoon upper troposphere and lowermost stratosphere during the StratoClim campaign 2017

Atmospheric Chemistry and Physics ◽

10.5194/acp-20-14695-2020 ◽

2020 ◽

Vol 20 (23) ◽

pp. 14695-14715

Author(s):

Sören Johansson ◽

Michael Höpfner ◽

Oliver Kirner ◽

Ingo Wohltmann ◽

Silvia Bucci ◽

...

Keyword(s):

Atmospheric Chemistry ◽

Large Scale ◽

Trajectory Analysis ◽

Asian Summer Monsoon ◽

Trace Gas ◽

Ozone Monitoring Instrument ◽

Air Masses ◽

Upper Troposphere ◽

Mixing Ratios ◽

Monitoring Service

Abstract. We present the first high-resolution measurements of pollutant trace gases in the Asian summer monsoon upper troposphere and lowermost stratosphere (UTLS) from the Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) during the StratoClim (Stratospheric and upper tropospheric processes for better climate predictions) campaign based in Kathmandu, Nepal, 2017. Measurements of peroxyacetyl nitrate (PAN), acetylene (C2H2), and formic acid (HCOOH) show strong local enhancements up to altitudes of 16 km. More than 500 pptv of PAN, more than 200 pptv of C2H2, and more than 200 pptv of HCOOH are observed. Air masses with increased volume mixing ratios of PAN and C2H2 at altitudes up to 18 km, reaching to the lowermost stratosphere, were present at these altitudes for more than 10 d, as indicated by trajectory analysis. A local minimum of HCOOH is correlated with a previously reported maximum of ammonia (NH3), which suggests different washout efficiencies of these species in the same air masses. A backward trajectory analysis based on the models Alfred Wegener InsTitute LAgrangian Chemistry/Transport System (ATLAS) and TRACZILLA, using advanced techniques for detection of convective events, and starting at geolocations of GLORIA measurements with enhanced pollution trace gas concentrations, has been performed. The analysis shows that convective events along trajectories leading to GLORIA measurements with enhanced pollutants are located close to regions where satellite measurements by the Ozone Monitoring Instrument (OMI) indicate enhanced tropospheric columns of nitrogen dioxide (NO2) in the days prior to the observation. A comparison to the global atmospheric models Copernicus Atmosphere Monitoring Service (CAMS) and ECHAM/MESSy Atmospheric Chemistry (EMAC) has been performed. It is shown that these models are able to reproduce large-scale structures of the pollution trace gas distributions for one part of the flight, while the other part of the flight reveals large discrepancies between models and measurement. These discrepancies possibly result from convective events that are not resolved or parameterized in the models, uncertainties in the emissions of source gases, and uncertainties in the rate constants of chemical reactions.

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Temporal variation of elemental carbon in Guangzhou, China, in summer 2006

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-9-24629-2009 ◽

2009 ◽

Vol 9 (6) ◽

pp. 24629-24667 ◽

Cited By ~ 2

Author(s):

R. L. Verma ◽

L. K. Sahu ◽

Y. Kondo ◽

N. Takegawa ◽

S. Han ◽

...

Keyword(s):

Elemental Carbon ◽

Back Trajectories ◽

Air Masses ◽

Traffic Pattern ◽

Mixing Ratios ◽

Diurnal Patterns ◽

Air Mass Types ◽

The Pearl River ◽

Carbon Dioxide Co2 ◽

Marine Air

Abstract. In situ measurements of the mass concentration of elemental carbon (EC) and mixing ratios of carbon monoxide (CO) and carbon dioxide (CO2) were made at Guangzhou, an urban measurement site in the Pearl River Delta (PRD), China, in July 2006. The average±standard deviation (SD) concentrations of EC, CO, and CO2 were 4.7±2.3 μg C m−3, 798±459 ppbv and 400±13 ppmv, respectively. The trends of these species were mainly controlled by synoptic-scale changes in meteorology during the campaign. Based on back trajectories, data are analyzed separately for two different air mass types representing northerly and southerly flows. Northerly air masses, constituting about 25% of the campaign, were mainly impacted by stagnant conditions, resulting in elevated levels of pollutants. On the other hand, southerly air masses measured during most of the campaign were mostly influenced by clean marine air. The diurnal patterns of EC, CO, and CO2 exhibited peak concentrations during the morning and evening hours coinciding with rush-hour traffic. The diurnal variations of EC and ΔEC/ΔCO closely followed the traffic pattern of heavy-duty vehicles (HDV) in Guangzhou, similar to that observed in Beijing. The level of EC in this campaign was similar to values reported during previous studies at other sites surrounding Guangzhou. The average slopes of ΔEC/ΔCO, ΔEC/ΔCO2, and ΔCO/ΔCO2 were 0.0054 μg C m−3/ppbv, 0.15 μg C m−3/ppmv, and 46.4 ppbv/ppmv, respectively, agreeing reasonably well with their respective emission ratios derived from regional emission inventories.

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Trace gas composition in the Asian summer monsoon anticyclone: A case study based on aircraft observations and model simulations

10.5194/acp-2016-997 ◽

2016 ◽

Author(s):

Klaus-D. Gottschaldt ◽

Hans Schlager ◽

Robert Baumann ◽

Heiko Bozem ◽

Veronika Eyring ◽

...

Keyword(s):

Summer Monsoon ◽

Atmospheric Chemistry ◽

Asian Summer Monsoon ◽

Trace Gas ◽

Gas Composition ◽

Back Trajectories ◽

Air Masses ◽

Mixing Ratios ◽

Asian Summer

Abstract. We present in-situ measurements of the trace gas composition of the upper tropospheric (UT) Asian summer monsoon anticyclone (ASMA) performed with the High Altitude and LOng range (HALO) research aircraft in the frame of the Earth System Model Validation (ESMVal) campaign. Air masses with enhanced O3 mixing ratios were encountered after entering the ASMA at its southern edge at about 150 hPa on 18 September 2012. This is in contrast to previous studies, reporting that the anticyclone's interior is dominated by recently uplifted air with low O3 in the monsoon season. We also observed enhanced CO and HCl in the ASMA, tracers for boundary layer pollution and tropopause layer (TL) air or stratospheric inmixing, respectively. In addition, reactive nitrogen was enhanced in the ASMA. Along the HALO flight track across the ASMA boundary, strong gradients of these tracers separate anticyclonic from outside air. Lagrangian trajectory calculations using HYSPLIT show that HALO sampled three times a filament of UT air, which included air masses uplifted from the lower or mid troposphere north of the Bay of Bengal. The trace gas gradients between UT and uplifted air masses were preserved during transport within a belt of streamlines fringing the central part of the anticyclone (fringe), but are smaller than the gradients across the ASMA boundary. Our data represent the first in-situ observations across the southern and downstream the eastern ASMA flank, respectively. Back-trajectories starting at the flight track furthermore indicate that HALO transected the ASMA where it was just splitting into a Tibetan and an Iranian part. The O3-rich filament is diverted from the fringe towards the interior of the original anticyclone, and at least partially bound to become part of the new Iranian eddy. A simulation with the ECHAM/MESSy Atmospheric Chemistry (EMAC) model is found to reproduce the observations reasonably well. It shows that O3-rich air is entrained by the outer streamlines of the anticyclone at its eastern flank. Back-trajectories and increased HCl mixing ratios indicate that the entrained air originates in the stratospherically influenced TL. Photochemical ageing of air masses in the ASMA additionally increases O3 in originally O3-poor, but CO-rich air. Simulated monthly mean trace gas distributions show decreased O3 in the ASMA centre not in general, but only at the 100 hPa level in July and August, as also reported by previous studies. However, at lower altitudes and in September the ASMA is dominated by increased O3, indicating that the above processes are more important for the ASMA trace gas budgets than previously thought.

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The friagem event in the central Amazon and its influence on micrometeorological variables and atmospheric chemistry

Atmospheric Chemistry and Physics ◽

10.5194/acp-21-339-2021 ◽

2021 ◽

Vol 21 (1) ◽

pp. 339-356

Author(s):

Guilherme F. Camarinha-Neto ◽

Julia C. P. Cohen ◽

Cléo Q. Dias-Júnior ◽

Matthias Sörgel ◽

José Henrique Cattanio ◽

...

Keyword(s):

Atmospheric Chemistry ◽

Temperature Drop ◽

Atmospheric Modeling ◽

Cloud Formation ◽

Cold Pool ◽

Large Temperature ◽

Mixing Ratio ◽

Air Masses ◽

Central Amazon ◽

Mixing Ratios

Abstract. In the period between 9 and 11 July 2014, a friagem event reached the Amazon region. On 11 July, the southwest flow related to the friagem converged with the easterly winds in the central Amazon. The interaction between these two distinct air masses formed a convection band, which intensified over the Manaus region and the Amazon Tall Tower Observatory (ATTO) site. The satellite images show the evolution of convective activity on 11 July, which led to 21 mm of precipitation at the ATTO site. Moreover, the arrival of the friagem caused a sudden drop in temperature and a predominance of southerly winds, which could be seen in Porto Velho between 7 and 8 July and in Manaus and the ATTO site from 9 to 11 July. The results of ERA-Interim reanalysis and Brazilian developments on the Regional Atmospheric Modeling System (BRAMS) simulations show that this friagem event coming from the southwest, carries a mass of air with higher O3 and NO2 mixing ratios and lower CO mixing ratio compared to the air masses present in the central Amazon. At Lake Balbina, the friagem intensifies the local circulations, such as the breeze phenomena. In the Manaus region and at the ATTO site, the main effects of the friagem event are a decrease in the incoming solar radiation (due to intense cloud formation), a large temperature drop and a distinct change in surface O3 and CO2 mixing ratios. As the cold air of the friagem was just in the lower 500 m the most probable cause of this change is that a cold pool above the forest prevented vertical mixing causing accumulation of CO2 from respiration and very low O3 mixing ratio due to photochemistry reduction and limited mixing within the boundary layer.

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The role of chlorine in global tropospheric chemistry

Atmospheric Chemistry and Physics ◽

10.5194/acp-19-3981-2019 ◽

2019 ◽

Vol 19 (6) ◽

pp. 3981-4003 ◽

Cited By ~ 47

Author(s):

Xuan Wang ◽

Daniel J. Jacob ◽

Sebastian D. Eastham ◽

Melissa P. Sulprizio ◽

Lei Zhu ◽

...

Keyword(s):

Boundary Layer ◽

Atmospheric Chemistry ◽

Sea Salt ◽

Tropospheric Chemistry ◽

Mixing Ratios ◽

Sea Salt Aerosol ◽

Oxidation Of Methane ◽

Heterogeneous Processes ◽

Marine Air ◽

Global Mean

Abstract. We present a comprehensive simulation of tropospheric chlorine within the GEOS-Chem global 3-D model of oxidant–aerosol–halogen atmospheric chemistry. The simulation includes explicit accounting of chloride mobilization from sea salt aerosol by acid displacement of HCl and by other heterogeneous processes. Additional small sources of tropospheric chlorine (combustion, organochlorines, transport from stratosphere) are also included. Reactive gas-phase chlorine Cl*, including Cl, ClO, Cl2, BrCl, ICl, HOCl, ClNO3, ClNO2, and minor species, is produced by the HCl+OH reaction and by heterogeneous conversion of sea salt aerosol chloride to BrCl, ClNO2, Cl2, and ICl. The model successfully simulates the observed mixing ratios of HCl in marine air (highest at northern midlatitudes) and the associated HNO3 decrease from acid displacement. It captures the high ClNO2 mixing ratios observed in continental surface air at night and attributes the chlorine to HCl volatilized from sea salt aerosol and transported inland following uptake by fine aerosol. The model successfully simulates the vertical profiles of HCl measured from aircraft, where enhancements in the continental boundary layer can again be largely explained by transport inland of the marine source. It does not reproduce the boundary layer Cl2 mixing ratios measured in the WINTER aircraft campaign (1–5 ppt in the daytime, low at night); the model is too high at night, which could be due to uncertainty in the rate of the ClNO2+Cl- reaction, but we have no explanation for the high observed Cl2 in daytime. The global mean tropospheric concentration of Cl atoms in the model is 620 cm−3 and contributes 1.0 % of the global oxidation of methane, 20 % of ethane, 14 % of propane, and 4 % of methanol. Chlorine chemistry increases global mean tropospheric BrO by 85 %, mainly through the HOBr+Cl- reaction, and decreases global burdens of tropospheric ozone by 7 % and OH by 3 % through the associated bromine radical chemistry. ClNO2 chemistry drives increases in ozone of up to 8 ppb over polluted continents in winter.

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The role of chlorine in tropospheric chemistry

10.5194/acp-2018-1088 ◽

2018 ◽

Cited By ~ 1

Author(s):

Xuan Wang ◽

Daniel J. Jacob ◽

Sebastian D. Eastham ◽

Melissa P. Sulprizio ◽

Lei Zhu ◽

...

Keyword(s):

Boundary Layer ◽

Atmospheric Chemistry ◽

Sea Salt ◽

Tropospheric Chemistry ◽

Mixing Ratios ◽

Sea Salt Aerosol ◽

Oxidation Of Methane ◽

Heterogeneous Processes ◽

Marine Air ◽

Global Mean

Abstract. We present a comprehensive simulation of tropospheric chlorine within the GEOS-Chem global 3-D model of oxidant-aerosol-halogen atmospheric chemistry. The simulation includes explicit accounting of chloride mobilization from sea-salt aerosol by acid displacement of HCl and by other heterogeneous processes. Additional sources of tropospheric chlorine (combustion, organochlorines, transport from stratosphere) are small in comparison. Reactive gas-phase chlorine Cl*, including Cl, ClO, Cl2, BrCl, ICl, HOCl, ClNO3, ClNO2, and minor species, is produced by the HCl + OH reaction and by heterogeneous conversion of sea-salt aerosol chloride to BrCl, ClNO2, Cl2, and ICl. The model simulates successfully the observed mixing ratios of HCl in marine air (highest at northern mid-latitudes) and the associated HNO3 decrease from acid displacement. It captures the high ClNO2 mixing ratios observed in continental surface air at night with chlorine of sea salt origin transported inland as HCl and fine aerosol. It simulates successfully the vertical profiles of HCl measured from aircraft, where enhancements in the continental boundary layer can again be explained by transport inland of the marine source. It does not reproduce the boundary layer Cl2 mixing ratios measured in the WINTER aircraft campaign (1–5 ppt in the daytime, low at night); the model is too high at night compared to WINTER observations, which could be due to uncertainty in the rate of the ClNO2 + Cl− reaction, but we have no explanation for the daytime observations. The global mean tropospheric concentration of Cl atoms in the model is 620 cm−3 and contributes 1.0 % of the global oxidation of methane, 20 % of ethane, 14 % of propane, and 4 % of methanol. Chlorine chemistry increases global mean tropospheric BrO by 85 %, mainly through the HOBr + Cl− reaction, and decreases global burdens of tropospheric ozone by 7 % and OH by 3 % through the associated bromine radical chemistry. ClNO2 chemistry drives increases in ozone of up to 8 ppb over polluted continents in winter.

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