scholarly journals Two-years of NO<sub>3</sub> radical observations in the boundary layer over the Eastern Mediterranean

2007 ◽  
Vol 7 (2) ◽  
pp. 315-327 ◽  
Author(s):  
M. Vrekoussis ◽  
N. Mihalopoulos ◽  
E. Gerasopoulos ◽  
M. Kanakidou ◽  
P. J. Crutzen ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Heterogeneous Reaction ◽  
Eastern Mediterranean ◽  
North Coast ◽  
Data Set ◽  
East Europe ◽  
Dinitrogen Pentoxide ◽  
Mixing Ratios ◽  
The North

Abstract. This is the first study that investigates the seasonal variability of nitrate (NO3) radicals in the marine boundary layer over the East Mediterranean Sea. An extensive data set of NO3 radical observations on the north coast of Crete for more than two years (June 2001–September 2003) is presented here. NO3 radicals follow a distinct seasonal dependency with the highest seasonally average mixing ratios in summer (5.6±1.2 pptv) and the lowest in winter (1.2±1.2 pptv). Episodes with high NO3 mixing ratios have been encountered mainly in polluted air masses originating from mainland Greece, Central and East Europe, and Turkey. Ancillary measurements of ozone, nitrogen dioxide (NO2) and meteorological parameters have been conducted and used to reveal possible relationship with the observed NO3 variability. The acquired NO2 nighttime observations provide the up-to-date most complete overview of NO2 temporal variability in the area. The data show correlations of the NO3 nighttime mixing ratios with temperature (positive), relative humidity (negative) and to a lesser extend with O3 (positive). As inferred from these observations, on average the major sink of NO3 radicals in the area is the heterogeneous reaction of dinitrogen pentoxide (N2O5) on aqueous particles whereas the homogeneous gas phase reactions of NO3 are most important during spring and summer. These observations support a significant contribution of NO3 nighttime chemistry to the oxidizing capacity of the troposphere.

scholarly journals Two-years of NO<sub>3</sub> radical observations in the boundary layer over the Eastern Mediterranean

2006 ◽  
Vol 6 (5) ◽  
pp. 9517-9544
Author(s):  
M. Vrekoussis ◽  
N. Mihalopoulos ◽  
E. Gerasopoulos ◽  
M. Kanakidou ◽  
P. Crutzen ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Heterogeneous Reaction ◽  
Eastern Mediterranean ◽  
North Coast ◽  
Peroxy Radicals ◽  
Data Set ◽  
Positive Correlation ◽  
Mixing Ratios ◽  
The North

Abstract. This is the first study that investigates the seasonal variability of nitrate (NO3) radicals in the marine boundary layer over the East Mediterranean Sea. An extensive data set of NO3 radical observations on the north coast of Crete for more than two years (June 2001–September 2003) is presented here. NO3 radicals follow a distinct seasonal dependency with maximum mixing ratios in summer (5.6±1.2 pptv) and minimum in winter (1.2±1.2 pptv). Episodes with high NO3 mixing ratios have been encountered mainly in polluted air masses originating from mainland Greece, Central and East Europe, and Turkey. Ancillary measurements of ozone, nitrogen dioxide (NO2 and meteorological parameters have been conducted and used to explain the observed NO3 variability. The acquired NO2 nighttime observations provide the up-to-date most complete overview of NO2 temporal variability in the area. The data show that the NO3 nighttime mixing ratios are primarily dependent on NO2 (positive correlation) and relative humidity (negative correlation) and to a lesser extend on temperature (positive correlation). As inferred from these observations, on average the major sink of NO3 radicals in the area is the heterogeneous reaction of dinitrogen pentoxide (N2O5) on aqueous particles whereas the homogeneous gas phase reactions of NO3 are most important during spring and summer. NO 3 chemistry in the area significantly contributes to VOC oxidation and to the nighttime formation of peroxy radicals, nitric acid and particulate nitrate.

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 Role of the NO<sub>3</sub> radicals in oxidation processes in the eastern Mediterranean troposphere during the MINOS campaign

2004 ◽  
Vol 4 (1) ◽  
pp. 169-182 ◽  
Author(s):  
M. Vrekoussis ◽  
M. Kanakidou ◽  
N. Mihalopoulos ◽  
P. J. Crutzen ◽  
J. Lelieveld ◽  
...  
Keyword(s):  
Eastern Mediterranean ◽  
Meteorological Data ◽  
Optical Absorption Spectroscopy ◽  
North Coast ◽  
Ionization Mass ◽  
Oh Radical ◽  
Mixing Ratios ◽  
The North ◽  
South East Europe ◽  
No3 Radical

Abstract. During the MINOS campaign (28 July-18 August 2001) the nitrate (NO3) radical was measured at Finokalia station, on the north coast of Crete in South-East Europe using a long path (10.4 km) Differential Optical Absorption Spectroscopy instrument (DOAS). Hydroxyl (OH) radical was also measured by a Chemical Ionization Mass-Spectrometer (Berresheim et al., 2003). These datasets represent the first simultaneous measurements of OH and NO3 radicals in the area. NO3 radical concentrations ranged from less than 3x107 up to 9x108 radicals· cm-3 with an average nighttime value of 1.1x108 radicals· cm-3. The observed NO3 mixing ratios are analyzed on the basis of the corresponding meteorological data and the volatile organic compound (VOC) observations which were measured simultaneously at Finokalia station. The importance of the NO3 radical chemistry relatively to that of OH in the dimethylsulfide (DMS) and nitrate cycles is also investigated. The observed NO3 levels regulate the nighttime variation of DMS. The loss of DMS by NO3 during night is about 75% of that by OH radical during day. NO3 and nitrogen pentoxide (N2O5) reactions account for about 21% of the total nitrate (HNO3(g)+NO-3(g)) production.

scholarly journals Airborne DOAS measurements in Arctic: vertical distributions of aerosol extinction coefficient and NO<sub>2</sub> concentration

2011 ◽  
Vol 11 (5) ◽  
pp. 13525-13574
Author(s):  
A. Merlaud ◽  
M. Van Roozendael ◽  
N. Theys ◽  
C. Fayt ◽  
C. Hermans ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Scattered Light ◽  
Optical Absorption Spectroscopy ◽  
North Coast ◽  
Aerosol Extinction ◽  
Back Trajectories ◽  
The North ◽  
Source Regions ◽  
Vertical Distributions

Abstract. We report airborne differential optical absorption spectroscopy (DOAS) measurements of aerosol extinction and NO2 tropospheric profiles performed off the North coast of Norway in April 2008. The DOAS instrument was installed on the Safire ATR-42 aircraft during the POLARCAT-France spring campaign and recorded scattered light spectra in near-limb geometry using a scanning telescope. We use O4 slant column measurements to derive the aerosol extinction at 360 nm. Regularization is based on the maximum a posteriori solution, for which we compare a linear and a logarithmic approach. The latter inherently constrains the solution to positive values and yields aerosol extinction profiles more consistent with independently measured size distributions. Two soundings are presented, performed on 8 April 2008 above 71° N, 22° E and on 9 April 2008 above 70° N, 17.8° E. The first profile shows aerosol extinction and NO2 in the marine boundary layer with respective values of 0.04±0.005 km−1 and 1.9±0.3 × 109 molec cm−3. A second extinction layer of 0.01±0.003 km−1 is found at 4 km altitude. During the second sounding, clouds prevented us to retrieve profile parts under 3 km altitude but a layer with enhanced extinction (0.025±0.005 km−1) and NO2 (1.95±0.2 × 109 molec cm−3) is clearly detected at 4 km altitude. From CO and ozone in-situ measurements complemented by back-trajectories, we interpret the measurements in the free troposphere as, for the first sounding, a mix between stratospheric and polluted air from Northern Europe and for the second sounding, polluted air from Central Europe containing NO2. Considering the boundary layer measurements of the first flight, modeled source regions indicate closer sources, especially the Kola Peninsula smelters, which can explain the NO2 enhancement not correlated with a CO increase at the same altitude.

scholarly journals Iodine oxide in the global marine boundary layer

2015 ◽  
Vol 15 (2) ◽  
pp. 583-593 ◽  
Author(s):  
C. Prados-Roman ◽  
C. A. Cuevas ◽  
T. Hay ◽  
R. P. Fernandez ◽  
A. S. Mahajan ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Atmospheric Chemistry ◽  
Ozone Depletion ◽  
Marine Boundary Layer ◽  
Data Set ◽  
Mixing Ratios ◽  
Field Campaigns ◽  
Ozone Depletion Potential ◽  
Ubiquitous Presence ◽  
Inorganic Precursors

Abstract. Emitted mainly by the oceans, iodine is a halogen compound important for atmospheric chemistry due to its high ozone depletion potential and effect on the oxidizing capacity of the atmosphere. Here we present a comprehensive data set of iodine oxide (IO) measurements in the open marine boundary layer (MBL) made during the Malaspina 2010 circumnavigation. Results show IO mixing ratios ranging from 0.4 to 1 pmol mol−1 (30% uncertainty) and, complemented with additional field campaigns, this data set confirms through observations the ubiquitous presence of reactive iodine chemistry in the global marine environment. We use a global model with organic (CH3I, CH2ICl, CH2I2 and CH2IBr) and inorganic (HOI and I2) iodine ocean emissions to investigate the contribution of the different iodine source gases to the budget of IO in the global MBL. In agreement with previous estimates, our results indicate that, globally averaged, the abiotic precursors contribute about 75 % to the IO budget. However, this work reveals a strong geographical pattern in the contribution of organic vs. inorganic precursors to reactive iodine in the global MBL.

scholarly journals Increasing ozone in marine boundary layer inflow at the west coasts of North America and Europe

2009 ◽  
Vol 9 (4) ◽  
pp. 1303-1323 ◽  
Author(s):  
D. D. Parrish ◽  
D. B. Millet ◽  
A. H. Goldstein
Keyword(s):  
Boundary Layer ◽  
North America ◽  
North American ◽  
West Coast ◽  
American West ◽  
Marine Boundary Layer ◽  
North American West ◽  
Mixing Ratios ◽  
The North ◽  
Marine Air

Abstract. An effective method is presented for determining the ozone (O3) mixing ratio in the onshore flow of marine air at the North American west coast. By combining the data available from all marine boundary layer (MBL) sites with simultaneous wind data, decadal temporal trends of MBL O3 in all seasons are established with high precision. The average springtime temporal trend over the past two decades is 0.46 ppbv/yr with a 95% confidence limit of 0.13 ppbv/yr, and statistically significant trends are found for all seasons except autumn, which does have a significantly smaller trend than other seasons. The average trend in mean annual ozone is 0.34±0.09 ppbv/yr. These decadal trends at the North American west coast present a striking comparison and contrast with the trends reported for the European west coast at Mace Head, Ireland. The trends in the winter, spring and summer seasons compare well at the two locations, while the Mace Head trend is significantly greater in autumn. Even though the trends are similar, the absolute O3 mixing ratios differ markedly, with the marine air arriving at Europe in all seasons containing 7±2 ppbv higher ozone than marine air arriving at North America. Further, the ozone mixing ratios at the North American west coast show no indication of stabilizing as has been reported for Mace Head. In a larger historical context the background boundary layer O3 mixing ratios over the 130 years covered by available data have increased substantially (by a factor of two to three), and this increase continues at present, at least in the MBL of the Pacific coast region of North America. The reproduction of the increasing trends in MBL O3 over the past two decades, as well as the difference in the O3 mixing ratios between the two coastal regions will present a significant challenge for global chemical transport models. Further, the ability of the models to at least semi-quantitatively reproduce the longer-term, historical trends may an even greater challenge.

scholarly journals Atmospheric bromoform at Mace Head, Ireland: Evidence for a peatland source

2005 ◽  
Vol 5 (4) ◽  
pp. 5935-5955 ◽  
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–December 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 0.6+0.1 in south-easterly (100–170°) air to 1.9+0.8 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 have a fetch predominantly over land, 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 land breeze events in conjunction with previous estimates of local wetland CHCl3 release to tentatively deduce a global wetland CHBr3 source of 26.9 (0.5–1247) Gg yr−1, which is approximately 10% of the total global source.

scholarly journals Role of NO<sub>3</sub> radical in oxidation processes in the eastern Mediterranean troposphere during the MINOS campaign

2003 ◽  
Vol 3 (3) ◽  
pp. 3135-3169 ◽  
Author(s):  
M. Vrekoussis ◽  
M. Kanakidou ◽  
N. Mihalopoulos ◽  
P. J. Crutzen ◽  
J. Lelieveld ◽  
...  
Keyword(s):  
Eastern Mediterranean ◽  
Meteorological Data ◽  
Optical Absorption Spectroscopy ◽  
North Coast ◽  
Ionization Mass ◽  
Average Value ◽  
Mixing Ratios ◽  
The North ◽  
South East Europe ◽  
No3 Radical

Abstract. During the MINOS campaign (28 July–18 August 2001) nitrate (NO3) radical was measured at Finokalia, on the north coast of Crete in South-East Europe using a long path (10.4 km) Differential Optical Absorption Spectroscopy instrument (DOAS). Hydroxyl (OH) radical was also measured by a Chemical Ionization Mass-Spectrometer (Berresheim et al., this issue). These datasets represent the first simultaneous measurements of OH and NO3 radicals in the area. NO3 radical concentrations ranged from less than 3·107 up to 9·108 radical·cm-3 with an average value of 1.1·108 radical·cm−3.  The observed NO3 mixing ratios are analyzed on the basis of the corresponding meteorological data and the volatile organic compound (VOC) observations simultaneously obtained at Finokalia station. The importance of the NO3 radical relatively to that of OH in the dimethylsulfide (DMS) and nitrate cycles is also investigated. The observed NO3 levels clearly regulate the diurnal variation of DMS. NO3 and N2O5 reactions account for about 21% of the total nitrate (HNO3(g) + NO−3(part)) production.

scholarly journals Airborne DOAS measurements in Arctic: vertical distributions of aerosol extinction coefficient and NO<sub>2</sub> concentration

2011 ◽  
Vol 11 (17) ◽  
pp. 9219-9236 ◽  
Author(s):  
A. Merlaud ◽  
M. Van Roozendael ◽  
N. Theys ◽  
C. Fayt ◽  
C. Hermans ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Scattered Light ◽  
Optical Absorption Spectroscopy ◽  
North Coast ◽  
Aerosol Extinction ◽  
Back Trajectories ◽  
The North ◽  
Source Regions ◽  
Vertical Distributions

Abstract. We report on airborne Differential Optical Absorption Spectroscopy (DOAS) measurements of aerosol extinction and NO2 tropospheric profiles performed off the North coast of Norway in April 2008. The DOAS instrument was installed on the Safire ATR-42 aircraft during the POLARCAT-France spring campaign and recorded scattered light spectra in near-limb geometry using a scanning telescope. We use O4 slant column measurements to derive the aerosol extinction at 360 nm. Regularization is based on the maximum a posteriori solution, for which we compare a linear and a logarithmic approach. The latter inherently constrains the solution to positive values and yields aerosol extinction profiles more consistent with independently measured size distributions. We present results from two soundings performed on 8 April 2008 above 71° N, 22° E and on 9 April 2008 above 70° N, 17.8° E. The first profile shows aerosol extinction and NO2 in the marine boundary layer with respective values of 0.04 ± 0.005 km−1 and 1.9 ± 0.3 × 109 molec cm−3. A second extinction layer of 0.01 ± 0.003 km−1 is found at 4 km altitude where the NO2 concentration is 0.32 ± 0.2 × 109 molec cm−3. During the second sounding, clouds prevent retrieval of profile parts under 3 km altitude but a layer with enhanced extinction (0.025 ± 0.005 km−1) and NO2 (1.95 ± 0.2 × 109 molec cm−3) is clearly detected at 4 km altitude. From CO and ozone in-situ measurements complemented by back-trajectories, we interpret the measurements in the free troposphere as, for the first sounding, a mix between stratospheric and polluted air from Northern Europe and for the second sounding, polluted air from Central Europe containing NO2. Considering the boundary layer measurements of the first flight, modeled source regions indicate closer sources, especially the Kola Peninsula smelters, which can explain the NO2 enhancement not correlated with a CO increase at the same altitude.

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