scholarly journals Overview of the 2007 and 2008 campaigns conducted as part of the Greenland Summit Halogen-HO<sub>x</sub> Experiment (GSHOX)

2012 ◽  
Vol 12 (7) ◽  
pp. 17135-17150
Author(s):  
J. L. Thomas ◽  
J. E. Dibb ◽  
J. Stutz ◽  
R. von Glasow ◽  
S. Brooks ◽  
...  
Keyword(s):  
Marine Boundary Layer ◽  
Vertical Mixing ◽  
Greenland Ice Sheet ◽  
Elemental Mercury ◽  
Near Surface ◽  
Gaseous Elemental Mercury ◽  
Mixing Ratios ◽  
The North ◽  
Polar Snow ◽  
Active Bromine

Abstract. From 10 May through 17 June, 2007 and 6 June through 9 July, 2008 intensive sampling campaigns at Summit, Greenland confirmed that active bromine chemistry is occurring in and above the snow pack at the highest part of the Greenland ice sheet (72°36' N, 38° 25' W and 3.2 km a.s.l.). Direct measurements found BrO and soluble gas phase Br− mixing ratios in the low pptv range on many days (maxima <10 pptv). Conversion of up to 200 pg m−3 of gaseous elemental mercury (GEM) to reactive gaseous mercury (RGM) and enhanced OH relative to HO2 plus RO2 confirm that active bromine chemistry is impacting chemical cycles even at such low abundances of reactive bromine species. However, it does not appear that Bry chemistry can fully account for observed perturbations to HOx partitioning, suggesting unknown additional chemical processes may be important in this unique environment, or that our understanding of coupled NOx-HOx−Bry chemistry above sunlit polar snow is incomplete. Rapid transport from the North Atlantic marine boundary layer occasionally caused enhanced BrO at Summit (just two such events observed during the 12 weeks of sampling over the two seasons). In general observed reactive bromine was linked to activation of bromide (Br−) in, and release of reactive bromine from, the snowpack. A coupled snow-atmosphere one-dimensional model that assumed snow photochemistry as the only source successfully simulated observed NO and BrO at Summit during a three day interval when winds were weak (transport not a factor). The source of Br− in surface and near surface snow at Summit is not entirely clear, but concentrations were observed to increase when stronger vertical mixing brought free tropospheric air to the surface. Reactive Bry mixing ratios above the snow often increased in the day or two following increases in snow concentration, but this response was not consistent. On seasonal time scales concentrations of Br− in snow and reactive bromine in the air were directly related.

scholarly journals Overview of the 2007 and 2008 campaigns conducted as part of the Greenland Summit Halogen-HO<sub>x</sub> Experiment (GSHOX)

2012 ◽  
Vol 12 (22) ◽  
pp. 10833-10839 ◽  
Author(s):  
J. L. Thomas ◽  
J. E. Dibb ◽  
J. Stutz ◽  
R. von Glasow ◽  
S. Brooks ◽  
...  
Keyword(s):  
Marine Boundary Layer ◽  
Vertical Mixing ◽  
Greenland Ice Sheet ◽  
Elemental Mercury ◽  
Near Surface ◽  
Gaseous Elemental Mercury ◽  
Mixing Ratios ◽  
The North ◽  
Polar Snow ◽  
Active Bromine

Abstract. From 10 May through 17 June 2007 and 6 June through 9 July 2008 intensive sampling campaigns at Summit, Greenland confirmed that active bromine chemistry is occurring in and above the snow pack at the highest part of the Greenland ice sheet (72°36´ N, 38°25´ W and 3.2 km above sea level). Direct measurements found BrO and soluble gas phase Br− mixing ratios in the low pptv range on many days (maxima < 10 pptv). Conversion of up to 200 pg m−3 of gaseous elemental mercury (GEM) to reactive gaseous mercury (RGM) and enhanced OH relative to HO2 plus RO2 confirm that active bromine chemistry is impacting chemical cycles even at such low abundances of reactive bromine species. However, it does not appear that Bry chemistry can fully account for observed perturbations to HOx partitioning, suggesting unknown additional chemical processes may be important in this unique environment, or that our understanding of coupled NOx-HOx-Bry chemistry above sunlit polar snow is incomplete. Rapid transport from the north Atlantic marine boundary layer occasionally caused enhanced BrO at Summit (just two such events observed during the 12 weeks of sampling over the two seasons). In general observed reactive bromine was linked to activation of bromide (Br−) in, and release of reactive bromine from, the snowpack. A coupled snow-atmosphere model simulated observed NO and BrO at Summit during a three day interval when winds were weak. The source of Br− in surface and near surface snow at Summit is not entirely clear, but concentrations were observed to increase when stronger vertical mixing brought free tropospheric air to the surface. Reactive Bry mixing ratios above the snow often increased in the day or two following increases in snow concentration, but this response was not consistent. On seasonal time scales concentrations of Br− in snow and reactive bromine in the air were directly related.

scholarly journals Investigation of processes controlling GEM oxidation at mid-latitudinal marine, coastal, and inland sites

2016 ◽  
Author(s):  
Z. Ye ◽  
H. Mao ◽  
C.-J. Lin ◽  
S. Y. Kim
Keyword(s):  
Marine Boundary Layer ◽  
State Of The Art ◽  
Elemental Mercury ◽  
Atmospheric Mercury ◽  
Chemical Mechanism ◽  
Atmospheric Conditions ◽  
Gaseous Elemental Mercury ◽  
Mixing Ratios ◽  
Marine Site ◽  
Study Sites

Abstract. A box model incorporating a state-of-the-art chemical mechanism for atmospheric mercury (Hg) cycling was developed to investigate oxidation of gaseous elemental mercury (GEM) at three locations in the northeastern United States: Appledore Island (marine), Thompson Farm (coastal, rural), and Pack Monadnock (inland, rural, elevated). The chemical mechanism improved model's ability to simulate the formation of gaseous oxidized mercury (GOM) at the study sites. At the coastal and inland sites, GEM oxidation was predominated by O3 and OH, contributing 80–99 % of total GOM production during daytime. H2O2 initiated GEM oxidation was significant (~ 33 % of the total GOM) at the inland site during nighttime. In the marine boundary layer (MBL), Br and BrO were dominant GEM oxidants contributing ~ 70 % of the total GOM production during mid-day, while O3 dominated GEM oxidation (50–90 % of GOM production) over the remaining day. Following the production of HgBr from GEM + Br, HgBr was oxidized by BrO, HO2, OH, ClO, and IO to form Hg(II) brominated GOM species. However, under atmospheric conditions, the prevalent GEM oxidants in the MBL could be Br / BrO or O3 / OH depending on Br and BrO mixing ratios. Relative humidity and products of the CH3O2 + BrO reaction possibly affected significantly the mixing ratios of Br or BrO radicals and subsequently GOM formation. Gas-particle partitioning could be potentially important in the production of GOM as well as Br and BrO at the marine site.

scholarly journals Speciated mercury at marine, coastal, and inland sites in New England – Part 1: Temporal variability

2012 ◽  
Vol 12 (11) ◽  
pp. 5099-5112 ◽  
Author(s):  
H. Mao ◽  
R. Talbot
Keyword(s):  
New England ◽  
Marine Boundary Layer ◽  
Limit Of Detection ◽  
Inversion Layer ◽  
Warm Season ◽  
Elemental Mercury ◽  
Positive Trend ◽  
Gaseous Elemental Mercury ◽  
Mixing Ratios ◽  
Nocturnal Inversion

Abstract. A comprehensive analysis was conducted using long-term continuous measurements of gaseous elemental mercury (Hg0), reactive gaseous mercury (RGM), and particulate phase mercury (HgP) at coastal (Thompson Farm, denoted as TF), marine (Appledore Island, denoted as AI), and elevated inland (Pac Monadnock, denoted as PM) sites from the AIRMAP Observatories in southern New Hampshire, USA. Decreasing trends in background Hg0 were identified in the 7.5- and 5.5-yr records at TF and PM with decline rates of 3.3 parts per quadrillion by volume (ppqv) yr−1 and 6.3 ppqv yr−1, respectively. Common characteristics at these sites were the reproducible annual cycle of Hg0 with its maximum in winter-spring and minimum in fall, comprised of a positive trend in the warm season (spring – early fall) and a negative one in the cool season (late fall – winter). Year-to-year variability was observed in the warm season decline in Hg0 at TF varying from a minimum total (complete) seasonal loss of 43 ppqv in 2009 to a maximum of 92 ppqv in 2005, whereas variability remained small at AI and PM. The coastal site TF differed from the other two sites with its exceptionally low levels (as low as below 50 ppqv) in the nocturnal inversion layer possibly due to dissolution in dew water. Measurements of Hg0 at PM exhibited the smallest diurnal to annual variability among the three environments, where peak levels rarely exceeded 250 ppqv and the minimum was typically 100 ppqv. It should be noted that summertime diurnal patterns at TF and AI were opposite in phase indicating strong sink(s) for Hg0 during the day in the marine boundary layer, which was consistent with the hypothesis of Hg0 oxidation by halogen radicals there. Mixing ratios of RGM in the coastal and marine boundary layers reached annual maxima in spring and minima in fall, whereas at PM levels were generally below the limit of detection (LOD) except in spring. RGM levels at AI were higher than at TF and PM indicating a stronger source strength in the marine environment. Mixing ratios of HgP at AI and TF were close in magnitude to RGM levels and were mostly below 1 ppqv. Diurnal variation in HgP was barely discernible at TF and AI in spring and summer. Higher levels of HgP were observed during the day, while values that were smaller, but above the LOD, occurred at night.

scholarly journals Investigation of processes controlling summertime gaseous elemental mercury oxidation at midlatitudinal marine, coastal, and inland sites

2016 ◽  
Vol 16 (13) ◽  
pp. 8461-8478 ◽  
Author(s):  
Zhuyun Ye ◽  
Huiting Mao ◽  
Che-Jen Lin ◽  
Su Youn Kim
Keyword(s):  
Marine Boundary Layer ◽  
Elemental Mercury ◽  
Atmospheric Mercury ◽  
Box Model ◽  
Chemical Mechanism ◽  
Gaseous Elemental Mercury ◽  
Diurnal Cycles ◽  
Mixing Ratios ◽  
Halogen Chemistry ◽  
Marine Site

Abstract. A box model incorporating a state-of-the-art chemical mechanism for atmospheric mercury (Hg) cycling was developed to investigate the oxidation of gaseous elemental mercury (GEM) at three locations in the northeastern United States: Appledore Island (AI; marine), Thompson Farm (TF; coastal, rural), and Pack Monadnock (PM; inland, rural, elevated). The chemical mechanism in this box model included the most up-to-date Hg and halogen chemistry. As a result, the box model was able to simulate reasonably the observed diurnal cycles of gaseous oxidized mercury (GOM) and chemical speciation bearing distinct differences between the three sites. In agreement with observations, simulated GOM diurnal cycles at AI and TF showed significant daytime peaks in the afternoon and nighttime minimums compared to flat GOM diurnal cycles at PM. Moreover, significant differences in the magnitude of GOM diurnal amplitude (AI > TF > PM) were captured in modeled results. At the coastal and inland sites, GEM oxidation was predominated by O3 and OH, contributing 80–99 % of total GOM production during daytime. H2O2-initiated GEM oxidation was significant (∼ 33 % of the total GOM) at the inland site during nighttime. In the marine boundary layer (MBL) atmosphere, Br and BrO became dominant GEM oxidants, with mixing ratios reaching 0.1 and 1 pptv, respectively, and contributing ∼ 70 % of the total GOM production during midday, while O3 dominated GEM oxidation (50–90 % of GOM production) over the remaining day when Br and BrO mixing ratios were diminished. The majority of HgBr produced from GEM+Br was oxidized by NO2 and HO2 to form brominated GOM species. Relative humidity and products of the CH3O2+BrO reaction possibly significantly affected the mixing ratios of Br or BrO radicals and subsequently GOM formation. Gas–particle partitioning could potentially be important in the production of GOM as well as Br and BrO at the marine site.

scholarly journals Temperature and sunlight controls of mercury oxidation and deposition atop the Greenland ice sheet

2011 ◽  
Vol 11 (16) ◽  
pp. 8295-8306 ◽  
Author(s):  
S. Brooks ◽  
C. Moore ◽  
D. Lew ◽  
B. Lefer ◽  
G. Huey ◽  
...  
Keyword(s):  
Thermal Dissociation ◽  
Elevation Angle ◽  
Ice Sheet ◽  
Greenland Ice Sheet ◽  
Elemental Mercury ◽  
Near Surface ◽  
Gaseous Elemental Mercury ◽  
Halogen Chemistry ◽  
Marine Source ◽  
Remote Environment

Abstract. We conducted the first ever mercury speciation measurements atop the Greenland ice sheet at Summit Station (Latitude 72.6° N, Longitude 38.5° W, Altitude 3200 m) in the Spring and Summer of 2007 and 2008. These measurements were part of the collaborative Greenland Summit Halogen-HOx experiment (GSHOX) campaigns investigating the importance of halogen chemistry in this remote environment. Significant levels of BrO (1–5 pptv) in the near surface air were often accompanied by diurnal dips in gaseous elemental mercury (GEM), and in-situ production of reactive gaseous mercury (RGM). While halogen (i.e. Br) chemistry is normally associated with marine boundary layers, at Summit, Greenland, far from any marine source, we have conclusively detected bromine and mercury chemistry in the near surface air. The likely fate of the formed mercury-bromine radical (HgBr) is further oxidation to stable RGM (HgBr2, HgBrOH, HgBrCl...), or thermal decomposition. These fates appear to be controlled by the availability of Br, OH, Cl, etc. to produce RGM (Hg(II)), versus the lifetime of HgBr by thermal dissociation. At Summit, the production of RGM appears to require a sun elevation angle of >5 degrees, and an air temperature of 5 degrees, while the formation of RGM from HgBr requires a temperature

scholarly journals Temperature and sunlight controls of mercury oxidation and deposition atop the Greenland ice sheet

2011 ◽  
Vol 11 (2) ◽  
pp. 3663-3691 ◽  
Author(s):  
S. Brooks ◽  
C. Moore ◽  
D. Lew ◽  
B. Lefer ◽  
G. Huey ◽  
...  
Keyword(s):  
Thermal Dissociation ◽  
Ice Sheet ◽  
Greenland Ice Sheet ◽  
Elemental Mercury ◽  
Near Surface ◽  
Gaseous Elemental Mercury ◽  
Halogen Chemistry ◽  
Marine Source ◽  
Remote Environment ◽  
Marine Boundary Layers

Abstract. We conducted the first ever mercury speciation measurements atop the Greenland ice sheet at Summit Station (Latitude 72.6° N, Altitude 3200 m) in the Spring and Summer of 2007 and 2008. These measurements were part of the GSHOX campaigns investigating the importance of halogen chemistry in this remote environment. Significant levels of BrO (1–5 pptv) in the near surface air were often accompanied by depletions of gaseous elemental mercury (GEM) below background levels, and in-situ production of reactive gaseous mercury (RGM). While halogen (i.e. Br) chemistry is normally associated with marine boundary layers, at Summit, Greenland, far from any marine source, we have conclusively detected bromine and mercury chemistry in the near surface air. We suggest that the fate of the formed mercury-bromine radical (HgBr) is further oxidation to stable RGM (HgBr2, HgBrOH, HgBrCl, etc.), or thermal decomposition. These fates appear to be controlled by the availability of Br, OH, Cl, etc. to produce RGM (Hg(II)), verses the lifetime of HgBr by thermal dissociation. At Summit, the availability of Br appears to be controlled by J(Br2), requiring a sun angle of > 5 degrees, while the formation of RGM from HgBr requires a temperature < −15 °C. The majority of the deposited RGM is readily photoreduced and re-emitted to the air as GEM. However, a very small fraction becomes buried at depth. Extrapolating to the entire Greenland ice sheet, we calculate an estimated net annual sequestration of ~ 13 metric tons Hg per year, buried long-term under the sunlit photoreduction zone.

scholarly journals Speciated mercury at marine, coastal, and inland sites in New England – Part 1: Temporal variability

2011 ◽  
Vol 11 (12) ◽  
pp. 32301-32336 ◽  
Author(s):  
H. Mao ◽  
R. Talbot
Keyword(s):  
New England ◽  
Marine Boundary Layer ◽  
Limit Of Detection ◽  
Inversion Layer ◽  
Warm Season ◽  
Elemental Mercury ◽  
Rural Site ◽  
Gaseous Elemental Mercury ◽  
Mixing Ratios ◽  
Nocturnal Inversion

Abstract. A comprehensive analysis was conducted using long-term continuous measurements of gaseous elemental mercury (Hgo), reactive mercury (RGM), and particulate phase mercury (HgP) at coastal (Thompson Farm, denoted as TF), marine (Appledore Island, denoted as AI), and elevated inland (Pac Monadnock, denoted as PM) sites from the AIRMAP Observatories. Decreasing trends in background Hgo were identified in the 7- and 5-yr records at TF and PM with decline rates of 3.3 parts per quadrillion by volume (ppqv) yr−1 and 6.3 ppqv yr−1, respectively. Common characteristics at these sites were the reproducible annual cycle of Hgo with its maximum in winter-spring and minimum in fall as well as a decline/increase trend in the warm/cool season. The coastal site TF differed from the other two sites with its exceptionally low levels (as low as below 50 ppqv) in the nocturnal inversion layer probably due to dissolution in dew water. Year-to-year variability was observed in the warm season decline in Hgo at TF varying from a minimum total seasonal loss of 20 ppqv in 2010 to a maximum of 92 ppqv in 2005, whereas variability remained small at AI and PM. Measurements of Hgo at PM, an elevated inland rural site, exhibited the smallest diurnal to annual variability among the three environments, where peak levels rarely exceeded 250 ppqv and the minimum was typically 100 ppqv. It should be noted that summertime diurnal patterns at TF and AI are opposite in phase indicating strong sink(s) for Hgo during the day in the marine boundary layer, which is consistent with the hypothesis of Hgo oxidation by halogen radicals there. Mixing ratios of RGM in the coastal and marine boundary layers reached annual maximum in spring and minimum in fall, whereas at PM levels were generally below the limit of detection (LOD) except in spring. RGM levels at AI were higher than at TF and PM indicating a stronger source strength(s) in the marine environment. Mixing ratios of HgP at AI and TF were close in magnitude to RGM levels and were mostly below 1 ppqv. Diurnal variation in HgP was barely discernible at TF and AI in spring and summer with higher levels during the day and smaller but above the LOD at night.

scholarly journals Atmospheric bromoform at Mace Head, Ireland: seasonality and evidence for a peatland source

2005 ◽  
Vol 5 (11) ◽  
pp. 2927-2934 ◽  
Author(s):  
L. J. Carpenter ◽  
D. J. Wevill ◽  
S. O'Doherty ◽  
G. Spain ◽  
P. G. Simmonds
Keyword(s):  
Boundary Layer ◽  
Wind Direction ◽  
Marine Boundary Layer ◽  
Land Breeze ◽  
Peat Bogs ◽  
Mixing Ratios ◽  
The North ◽  
Prevailing Wind Direction ◽  
Atmospheric Observations ◽  
Summer Minimum

Abstract. In situ atmospheric observations of bromoform (CHBr3) made over a 2.5 year period at Mace Head, Ireland from May 2001- Dec 2003, including during the NAMBLEX (North Atlantic Marine Boundary Layer Experiment) campaign, show broad maxima from spring until autumn and winter minima, with mixing ratios of 5.3+1.0 pptv (mid March - mid October) and 1.8+0.8 pptv (December-February). This indicates that, unlike CHCl3, which has a summer minimum and winter maximum at Mace Head, local biological sources of CHBr3 have a greater influence on the atmospheric data than photochemical decay during long-range transport. The emission sources are predominantly macroalgal, but we find evidence for a small terrestrial flux from peatland ecosystems, which so far has not been accounted for in the CHBr3 budget. Sharp increases in CHCl3 and CHBr3 concentrations and decreases in O3 concentrations occurred at night when the wind direction switched from an ocean- to a land-based sector (land breeze) and the wind speed dropped to below 5 ms-1. These observations infer a shallow atmospheric boundary layer with increased O3 deposition and concentration of local emissions of both CHCl3 and CHBr3. The ratio of ΔCHCl3/ΔCHBr3 varied strongly according to the prevailing wind direction; from 0.60+0.15 in south-easterly (100-170° and northerly (340-20°) air to 2.5+0.4 in north-easterly (40-70°) air. Of these land-sectors, the south-easterly air masses are likely to be strongly influenced by macroalgal beds along the coast and the emission ratios probably reflect those from seaweeds in addition to land sources. The north-easterly airmasses however had an immediate fetch inland, which locally is comprised of coastal peatland ecosystems (peat bogs and coastal conifer plantations), previously identified as being strong sources of atmospheric CHCl3 under these conditions. Although we cannot entirely rule out other local land or coastal sources, our observations also suggest peatland ecosystem emissions of CHBr3. We use correlations between CHCl3 and CHBr3 during the north-easterly land breeze events in conjunction with previous estimates of local wetland CHCl3 release to tentatively deduce a global wetland CHBr3 source of 20.4(0.4-948) Gg yr-1, which is approximately 7% of the total global source.

scholarly journals Impacts of Large-Scale Circulation on Urban Ambient Concentrations of Gaseous Elemental Mercury in New York, USA

2017 ◽  
Author(s):  
Huiting Mao ◽  
Dolly Hall ◽  
Zhuyun Ye ◽  
Ying Zhou ◽  
Dirk Felton ◽  
...  
Keyword(s):  
New York ◽  
North American ◽  
Large Scale ◽  
Measurement Data ◽  
Elemental Mercury ◽  
Urban Site ◽  
Large Scale Circulation ◽  
Gaseous Elemental Mercury ◽  
The North ◽  
The Impact

Abstract. The impact of large-scale circulation on urban gaseous elemental mercury (GEM) was investigated through analysis of 2008–2015 measurement data from an urban site in New York City (NYC), New York, USA. Distinct annual cycles were observed in 2009–2010 with mixing ratios in warm seasons (i.e. spring–summer) 10–20 ppqv (~ 10 %–25 %) higher than in cool seasons (i.e. fall–winter). This annual cycle was disrupted in 2011 by an anomalously strong influence of the North American trough in that warm season and was reproduced in 2014 with annual amplitude enhanced up to ~ 70 ppqv associated with a particularly strong Bermuda High. North American trough axis index (TAI) and intensity index (TII) were used to characterize the effect of the North American trough on NYC GEM especially in winter and summer. The intensity and position of the Bermuda High had a significant impact on GEM in warm seasons supported by a strong correlation (r reaching 0.96, p 

Gaseous mercury in coastal urban areas

2010 ◽  
Vol 7 (6) ◽  
pp. 537 ◽  
Author(s):  
Anne L. Soerensen ◽  
Henrik Skov ◽  
Matthew S. Johnson ◽  
Marianne Glasius
Keyword(s):  
Urban Areas ◽  
Marine Boundary Layer ◽  
Elemental Mercury ◽  
Atmospheric Mercury ◽  
Mercury Deposition ◽  
Mercury Emissions ◽  
Gaseous Elemental Mercury ◽  
Gaseous Mercury ◽  
Range Transport ◽  
Aquatic Food

Environmental context Mercury is a neurotoxin that bioaccumulates in the aquatic food web. Atmospheric emissions from urban areas close to the coast could cause increased local mercury deposition to the ocean. Our study adds important new data to the current limited knowledge on atmospheric mercury emissions and dynamics in coastal urban areas. Abstract Approximately 50% of primary atmospheric mercury emissions are anthropogenic, resulting from e.g. emission hotspots in urban areas. Emissions from urban areas close to the coast are of interest because they could increase deposition loads to nearby coastal waters as well as contribute to long range transport of mercury. We present results from measurements of gaseous elemental mercury (GEM) and reactive gaseous mercury (RGM) in 15 coastal cities and their surrounding marine boundary layer (MBL). An increase of 15–90% in GEM concentration in coastal urban areas was observed compared with the remote MBL. Strong RGM enhancements were only found in two cities. In urban areas with statistically significant GEM/CO enhancement ratios, slopes between 0.0020 and 0.0087 ng m–3 ppb–1 were observed, which is consistent with other observations of anthropogenic enhancement. The emission ratios were used to estimate GEM emissions from the areas. A closer examination of data from Sydney (Australia), the coast of Chile, and Valparaiso region (Chile) in the southern hemisphere, is presented.

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