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 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 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 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 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 Significant concentrations of nitryl chloride sustained in the morning: Investigations of the causes and impacts on ozone production in a polluted region of northern China

2016 ◽  
Author(s):  
Yee Jun Tham ◽  
Zhe Wang ◽  
Qinyi Li ◽  
Hui Yun ◽  
Weihao Wang ◽  
...  
Keyword(s):  
Inversion Layer ◽  
Northern China ◽  
Residual Layer ◽  
Ozone Production ◽  
Rural Site ◽  
Ionization Mass ◽  
Dinitrogen Pentoxide ◽  
Mixing Ratios ◽  
Nitryl Chloride ◽  
Nocturnal Inversion

Abstract. Nitryl chloride (ClNO2) is a dominant source of chlorine radical in polluted environment and can significantly affect the atmospheric oxidative chemistry. However, the abundance of ClNO2 and its exact role are not fully understood under different environmental conditions. During the summer of 2014, we deployed a chemical ionization mass spectrometer to measure ClNO2 and dinitrogen pentoxide (N2O5) at a rural site in the polluted North China Plain. Elevated mixing ratios of ClNO2 (> 350 pptv) were observed at most of the nights with low levels of N2O5 (< 200 pptv). The highest ClNO2 mixing ratio of 2070 pptv (1-min average) was observed in a plume from megacity (Tianjin) and was characterized with faster N2O5 heterogeneous loss rate and ClNO2 production rate compared to average condition. The abundant ClNO2 concentration kept increasing even after sunrise and reached a peak 4 hours later. Such highly sustained ClNO2 peaks after sunrise are discrepant from the previously observed typical diurnal pattern. Meteorological and chemical analysis show that the sustained ClNO2 morning peaks are caused by significant ClNO2 production in the residual layer at night followed by downward mixing after break-up of the nocturnal inversion layer in the morning. We estimated that ~ 1.7–4.0 ppbv of ClNO2 would exist in the residual layer in order to maintain the observed morning ClNO2 peaks at the surface site. Observation-based box model analysis show that photolysis of ClNO2 produced chlorine radical with a rate up to 1.12 ppbv h−1, accounting for 10–30 % of primary ROx production in the morning hours. The perturbation in total radical production leads to an increase of integrated daytime net ozone production by 3 % (4.3 ppbv) on average, and with a larger increase of 13 % (11 ppbv) in megacity outflow that was characterized with higher ClNO2 and relatively lower OVOC to NMHC ratio.

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 Significant concentrations of nitryl chloride sustained in the morning: investigations of the causes and impacts on ozone production in a polluted region of northern China

2016 ◽  
Vol 16 (23) ◽  
pp. 14959-14977 ◽  
Author(s):  
Yee Jun Tham ◽  
Zhe Wang ◽  
Qinyi Li ◽  
Hui Yun ◽  
Weihao Wang ◽  
...  
Keyword(s):  
Inversion Layer ◽  
Northern China ◽  
Residual Layer ◽  
Ozone Production ◽  
Rural Site ◽  
Ionization Mass ◽  
Dinitrogen Pentoxide ◽  
Mixing Ratios ◽  
Nitryl Chloride ◽  
Nocturnal Inversion

Abstract. Nitryl chloride (ClNO2) is a dominant source of chlorine radical in polluted environment, and can significantly affect the atmospheric oxidative chemistry. However, the abundance of ClNO2 and its exact role are not fully understood under different environmental conditions. During the summer of 2014, we deployed a chemical ionization mass spectrometer to measure ClNO2 and dinitrogen pentoxide (N2O5) at a rural site in the polluted North China Plain. Elevated mixing ratios of ClNO2 (> 350 pptv) were observed at most of the nights with low levels of N2O5 (< 200 pptv). The highest ClNO2 mixing ratio of 2070 pptv (1 min average) was observed in a plume from a megacity (Tianjin), and was characterized with a faster N2O5 heterogeneous loss rate and ClNO2 production rate compared to average conditions. The abundant ClNO2 concentration kept increasing even after sunrise, and reached a peak 4 h later. Such highly sustained ClNO2 peaks after sunrise are discrepant from the previously observed typical diurnal pattern. Meteorological and chemical analysis shows that the sustained ClNO2 morning peaks are caused by significant ClNO2 production in the residual layer at night followed by downward mixing after breakup of the nocturnal inversion layer in the morning. We estimated that  ∼  1.7–4.0 ppbv of ClNO2 would exist in the residual layer in order to maintain the observed morning ClNO2 peaks at the surface site. Observation-based box model analysis show that photolysis of ClNO2 produced chlorine radical with a rate up to 1.12 ppbv h−1, accounting for 10–30 % of primary ROx production in the morning hours. The perturbation in total radical production leads to an increase of integrated daytime net ozone production by 3 % (4.3 ppbv) on average, and with a larger increase of 13 % (11 ppbv) in megacity outflow that was characterized with higher ClNO2 and a relatively lower oxygenated hydrocarbon (OVOC) to non-methane hydrocarbon (NMHC) ratio.

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.

scholarly journals Real-time measurements of ammonia, acidic trace gases and water-soluble inorganic aerosol species at a rural site in the Amazon Basin

2004 ◽  
Vol 4 (4) ◽  
pp. 967-987 ◽  
Author(s):  
I. Trebs ◽  
F. X. Meixner ◽  
J. Slanina ◽  
R. Otjes ◽  
P. Jongejan ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Amazon Basin ◽  
Limit Of Detection ◽  
Trace Gases ◽  
Water Soluble ◽  
Rural Site ◽  
Wet Season ◽  
Inlet System ◽  
Mixing Ratios ◽  
Inorganic Aerosol

Abstract. We measured the mixing ratios of ammonia (NH3), nitric acid (HNO3), nitrous acid (HONO), hydrochloric acid (HCl), sulfur dioxide (SO2 and the corresponding water-soluble inorganic aerosol species, ammonium (NH4+), nitrate (NO3-), nitrite (NO2-), chloride (Cl- and sulfate (SO42-), and their diel and seasonal variations at a pasture site in the Amazon Basin (Rondônia, Brazil). This study was conducted within the framework of LBA-SMOCC (Large Scale Biosphere Atmosphere Experiment in Amazonia - Smoke Aerosols, Clouds, Rainfall and Climate: Aerosols from Biomass Burning Perturb Global and Regional Climate). Sampling was performed from 12 September to 14 November 2002, extending from the dry season (extensive biomass burning activity), through the transition period to the wet season (background conditions). Measurements were made continuously using a wet-annular denuder (WAD) in combination with a Steam-Jet Aerosol Collector (SJAC) followed by suitable on-line analysis. A detailed description and verification of the inlet system for simultaneous sampling of soluble gases and aerosol compounds is presented. Overall measurement uncertainties of the ambient mixing ratios usually remained below 15%. The limit of detection (LOD) was determined for each single data point measured during the field experiment. Median LOD values (3σ-definition) were ≤0.015ppb for acidic trace gases and aerosol anions and ≤0.118ppb for NH3 and aerosol NH4+. Mixing ratios of acidic trace gases remained below 1ppb throughout the measurement period, while NH3 levels were an order of magnitude higher. Accordingly, mixing ratios of NH4+ exceeded those of other inorganic aerosol contributors by a factor of 4 to 10. During the wet season, mixing ratios decreased by nearly a factor of 3 for all compounds compared to those observed when intensive biomass burning took place. Additionally, N-containing gas and aerosol species featured pronounced diel variations. This is attributed to strong relative humidity and temperature variations between day and night as well as to changing photochemistry and stability conditions of the planetary boundary layer. HONO exhibited a characteristic diel cycle with high mixing ratios at nighttime and was not completely depleted by photolysis during daylight hours.

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