scholarly journals Free troposphere as the dominant source of CCN in the Equatorial Pacific boundary layer: long-range transport and teleconnections

2013 ◽  
Vol 13 (1) ◽  
pp. 1279-1326 ◽  
Author(s):  
A. D. Clarke ◽  
S. Freitag ◽  
R. M. C. Simpson ◽  
J. G. Hudson ◽  
S. G. Howell ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Cloud Condensation Nuclei ◽  
Large Fraction ◽  
Deep Convection ◽  
Equatorial Pacific ◽  
Quasi Equilibrium ◽  
Free Troposphere ◽  
Low Carbon ◽  
Mixing Ratios

Abstract. Airborne aerosol measurements in the central equatorial Pacific during PASE (Pacific Atmospheric Sulfur Experiment) revealed that cloud condensation nuclei (CCN) activated in marine boundary layer (MBL) clouds were dominated by entrainment from the free troposphere (FT). About 65% entered at sizes effective as CCN in MBL clouds, while 25% entered the MBL too small to activate but subsequently grew via gas to particle conversion. The remaining 10% were inferred to be sea-salt aerosol; there was no discernable nucleation in the MBL. FT aerosols at low carbon monoxide (CO) mixing ratios (< 63 ppbv) were small and relatively volatile with a number mode around 30–40 nm dry diameter and tended to be associated with cloud outflow from distant deep convection (3000 km or more). Higher CO concentrations were commonly associated with trajectories from South America and the Amazon region (ca. 10 000 km away) and occurred in layers indicative of combustion sources partially scavenged by precipitation. These had number mode near 60–80 nm diameter with a large fraction already CCN.2 (those activated at 0.2% supersaturation and representative of MBL clouds) before entrainment into the MBL. Flight averaged concentrations of CCN.2 were similar for measurements near the surface, below the inversion and above the inversion, confirming that subsidence of FT aerosol dominated MBL CCN.2. Concurrent flight-to-flight variations of CCN.2 at all altitudes below 3 km imply MBL CCN.2 concentrations were in quasi-equilibrium with the FT over a 2–3 day time scale. This extended FT transport over thousands of kilometers indicates teleconnections between MBL CCN and cloud-scavenged sources of both natural and/or residual combustion origin. The low aerosol scattering and mass in such layers results in poor detection by satellite and this source of CCN is not represented in most current models. The measurements confirm nucleation in the MBL was not evident during PASE and argue against the CLAW hypothesis being effective in this region during PASE.

scholarly journals Free troposphere as a major source of CCN for the equatorial pacific boundary layer: long-range transport and teleconnections

2013 ◽  
Vol 13 (15) ◽  
pp. 7511-7529 ◽  
Author(s):  
A. D. Clarke ◽  
S. Freitag ◽  
R. M. C. Simpson ◽  
J. G. Hudson ◽  
S. G. Howell ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Long Range ◽  
Dimethyl Sulfide ◽  
Large Fraction ◽  
Equatorial Pacific ◽  
Long Range Transport ◽  
Quasi Equilibrium ◽  
Free Troposphere ◽  
Inter Tropical Convergence Zone ◽  
Range Transport

Abstract. Airborne aerosol measurements in the central equatorial Pacific during PASE (Pacific Atmospheric Sulfur Experiment) revealed that cloud condensation nuclei (CCN) activated in marine boundary layer (MBL) clouds were strongly influenced by entrainment from the free troposphere (FT). About 65% entered at sizes effective as CCN in MBL clouds, while ~25% entered the MBL too small to activate but subsequently grew via gas to particle conversion. The remaining ~10% were inferred to be sea salt aerosol. FT aerosols at low carbon monoxide (CO) mixing ratios (< 63 ppbv) were mostly volatile at 360 °C with a number mode peak of around 30–40 nm dry diameter and tended to be associated with cloud outflow from distant (3000 km or more) deep convection. Higher CO concentrations were commonly associated with trajectories from South America and the Amazon region (ca. ~10 000 km away) and occurred in layers indicative of combustion sources (biomass burning season) partially scavenged by precipitation. These had number modes near 60–80 nm dry diameter with a large fraction of CCN.2 (those activated at 0.2% supersaturation and representative of MBL clouds) prior to entrainment into the MBL. Flight averaged concentrations of CCN.2 were similar for measurements near the surface, below the inversion and in the FT just above the inversion, confirming that subsidence and entrainment of FT aerosol strongly influenced MBL CCN.2. Concurrent flight-to-flight variations of CCN.2 at all altitudes below 3 km also imply MBL CCN.2 concentrations were in quasi-equilibrium with the FT over a 2–3 day timescale. The observed FT transport over thousands of kilometers indicates teleconnections between MBL CCN and cloud-scavenged sources of both natural and/or residual combustion origin. Nonetheless, in spite of its importance, this source of CCN number is not well represented in most current models and is generally not detectable by satellite because of the low aerosol scattering in such layers as a result of cloud scavenging. In addition, our measurements confirm nucleation in the MBL was not evident during PASE and argue against a localized linear relation in the MBL between dimethyl sulfide (DMS) and CCN suggested by the CLAW hypothesis. However, when the FT is not impacted by long-range transport, sulfate aerosol derived from DMS pumped aloft in the ITCZ (Inter-Tropical Convergence Zone) can provide a source of CCN to the boundary layer via FT teleconnections involving more complex non-linear processes.

Regional modelling of aerosol interaction with deep convection and the effect on new particle formation over Amazonia

2020 ◽  
Author(s):  
Xuemei Wang ◽  
Daniel Grosvenor ◽  
Hamish Gordon ◽  
Meinrat O. Andreae ◽  
Ken Carslaw
Keyword(s):  
Boundary Layer ◽  
Cloud Condensation Nuclei ◽  
Deep Convection ◽  
Particle Formation ◽  
Nucleation Mechanism ◽  
Transport Processes ◽  
Radiative Properties ◽  
Free Troposphere ◽  
New Particle Formation ◽  
New Particles

&lt;p&gt;It has been estimated that over 50% of the present-day global low-level cloud condensation nuclei (CCN) are formed from new particle formation (NPF), and that this process has a substantial effect on the radiative properties of shallow clouds (Gordon et al. 2017). In contrast, we have a very limited understanding of how NPF affects deep convective clouds. Deep clouds could interact strongly with NPF because they extend into the high free troposphere where most new particles are formed, and they are responsible for most of the vertical transport of the nucleating vapours. Andreae et al. (2018) hypothesised from ACRIDICON-CHUVA campaign that organic gas molecules are transported by deep convection to the upper troposphere where they are oxidised and produce new particles, which are then be entrained into the boundary layer and grow to CCN-relevent sizes.&lt;/p&gt;&lt;p&gt;Here we study the interaction of deep convection and NPF using the United Kingdom Chemistry and Aerosols (UKCA) model coupled with the Cloud-AeroSol Interacting Microphyics (CASIM) embedded in the regional configuration of UK Met Office Hadley Centre Global Environment Model (HadGEM3). We simulate several days over a 1000 km region of the Amazon at 4 km resolution. We then compare the regional model, which resolves cloud up- and downdrafts, with the global model with parameterised convection and low resolution.&lt;/p&gt;&lt;p&gt;Our simulations highlight three findings. Firstly, solely using a binary H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;-H&lt;sub&gt;2&lt;/sub&gt;O nucleation mechanism strongly underestimates total aerosol concentrations compared to observations by a factor of 1.5-8 below 3 km over the Amazon. This points to the potential role of an additional nucleation mechanism, most likely involving biogenic compounds that occurs throughout more of the free troposphere. Secondly, deep convection transports insoluble gases such as DMS and monoterpenes vertically but not SO&lt;sub&gt;2&lt;/sub&gt;&amp;#160;or H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;. The time scale for DMS oxidation (~ 1 day) is much longer than for monoterpene (1-2 hours), which points to the importance of simulating biogenic nucleation over the Amazon in a cloud-resolving model, while lower-resolution global models may adequately capture DMS effects on H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; nucleation. Finally, we also examine the Andreae et al (2018) hypothesis of aerosol supply to the boundary layer by quantifying cloud-free and cloudy up- and downdraft transport. The transport of newly formed aerosols into the boundary layer is 8 times greater in cloud-free regions than in the clouds, but these transport processes are of similar magnitude for large aerosols.&lt;/p&gt;

scholarly journals Impact of nucleation on global CCN

2009 ◽  
Vol 9 (3) ◽  
pp. 12999-13037 ◽  
Author(s):  
J. Merikanto ◽  
D. V. Spracklen ◽  
G. W. Mann ◽  
S. J. Pickering ◽  
K. S. Carslaw
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Environmental Changes ◽  
Control Strategies ◽  
Cloud Condensation Nuclei ◽  
Free Troposphere ◽  
Carbonaceous Particles ◽  
Upper Troposphere ◽  
Low Level ◽  
Primary Emissions

Abstract. Cloud condensation nuclei (CCN) are derived from particles emitted directly into the atmosphere (primary emissions) or from the growth of nanometer-sized particles nucleated in the atmosphere. It is important to separate these two sources because they respond in different ways to gas and particle emission control strategies and environmental changes. Here, we use a global aerosol microphysics model to quantify the contribution of primary and nucleated particles to global CCN. The model considers primary emissions of sea spray, sulfate and carbonaceous particles, and nucleation processes appropriate for the free troposphere and boundary layer. We estimate that 45% of global low-level cloud CCN at 0.2% supersaturation are secondary aerosol derived from nucleation (ranging between 31–49% taking into account uncertainties primary emissions and nucleation rates), the remainder being directly emitted as primary aerosol. The model suggests that 35% of CCN (0.2%) in low-level clouds were created in the free and upper troposphere. In the marine boundary layer 55% of CCN (0.2%) are from nucleation, 45% being entrained from the free troposphere. Both in global and marine boundary layer 10% of CCN (0.2%) is nucleated in the boundary layer. Combinations of model runs show that primary and nucleated CCN are non-linearly coupled. In particular, boundary layer nucleated CCN are strongly suppressed by both primary emissions and entrainment of particles nucleated in the free troposphere. Elimination of all primary emissions reduces global CCN (0.2%) by only 20% and elimination of upper tropospheric nucleation reduces CCN (0.2%) by only 12% because of increased impact of boundary layer nucleation on CCN.

scholarly journals Influence of corona discharge on the ozone budget in the tropical free troposphere: a case study of deep convection during GABRIEL

2014 ◽  
Vol 14 (17) ◽  
pp. 8917-8931 ◽  
Author(s):  
H. Bozem ◽  
H. Fischer ◽  
C. Gurk ◽  
C. L. Schiller ◽  
U. Parchatka ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Corona Discharge ◽  
Deep Convection ◽  
Convective Transport ◽  
Free Troposphere ◽  
Direct Production ◽  
Model Calculations ◽  
Mixing Ratios ◽  
Outflow Region

Abstract. Convective redistribution of ozone and its precursors between the boundary layer (BL) and the free troposphere (FT) influences photochemistry, in particular in the middle and upper troposphere (UT). We present a case study of convective transport during the GABRIEL campaign over the tropical rain forest in Suriname in October 2005. During one measurement flight the inflow and outflow regions of a cumulonimbus cloud (Cb) have been characterized. We identified a distinct layer between 9 and 11 km altitude with enhanced mixing ratios of CO, O3, HOx, acetone and acetonitrile. The elevated O3 contradicts the expectation that convective transport brings low-ozone air from the boundary layer to the outflow region. Entrainment of ozone-rich air is estimated to account for 62% (range: 33–91%) of the observed O3. Ozone is enhanced by only 5–6% by photochemical production in the outflow due to enhanced NO from lightning, based on model calculations using observations including the first reported HOx measurements over the tropical rainforest. The "excess" ozone in the outflow is most probably due to direct production by corona discharge associated with lightning. We deduce a production rate of 5.12 × 1028 molecules O3 flash−1 (range: 9.89 × 1026–9.82 × 1028 molecules O3 flash−1), which is at the upper limit of the range reported previously.

scholarly journals Global and regional modeling of clouds and aerosols in the marine boundary layer during VOCALS: the VOCA intercomparison

2015 ◽  
Vol 15 (1) ◽  
pp. 153-172 ◽  
Author(s):  
M. C. Wyant ◽  
C. S. Bretherton ◽  
R. Wood ◽  
G. R. Carmichael ◽  
A. Clarke ◽  
...  
Keyword(s):  
Boundary Layer ◽  
General Circulation ◽  
Marine Boundary Layer ◽  
Quantitative Estimation ◽  
Cloud Condensation Nuclei ◽  
Cloud Droplet ◽  
General Circulation Models ◽  
Free Troposphere ◽  
Aerosol Cloud ◽  
Aerosol Cloud Interactions

Abstract. A diverse collection of models are used to simulate the marine boundary layer in the southeast Pacific region during the period of the October–November 2008 VOCALS REx (VAMOS Ocean Cloud Atmosphere Land Study Regional Experiment) field campaign. Regional models simulate the period continuously in boundary-forced free-running mode, while global forecast models and GCMs (general circulation models) are run in forecast mode. The models are compared to extensive observations along a line at 20° S extending westward from the South American coast. Most of the models simulate cloud and aerosol characteristics and gradients across the region that are recognizably similar to observations, despite the complex interaction of processes involved in the problem, many of which are parameterized or poorly resolved. Some models simulate the regional low cloud cover well, though many models underestimate MBL (marine boundary layer) depth near the coast. Most models qualitatively simulate the observed offshore gradients of SO2, sulfate aerosol, CCN (cloud condensation nuclei) concentration in the MBL as well as differences in concentration between the MBL and the free troposphere. Most models also qualitatively capture the decrease in cloud droplet number away from the coast. However, there are large quantitative intermodel differences in both means and gradients of these quantities. Many models are able to represent episodic offshore increases in cloud droplet number and aerosol concentrations associated with periods of offshore flow. Most models underestimate CCN (at 0.1% supersaturation) in the MBL and free troposphere. The GCMs also have difficulty simulating coastal gradients in CCN and cloud droplet number concentration near the coast. The overall performance of the models demonstrates their potential utility in simulating aerosol–cloud interactions in the MBL, though quantitative estimation of aerosol–cloud interactions and aerosol indirect effects of MBL clouds with these models remains uncertain.

scholarly journals Influence of corona discharge on the ozone budget in the tropical free troposphere: a case study of deep convection during GABRIEL

2014 ◽  
Vol 14 (4) ◽  
pp. 5233-5270 ◽  
Author(s):  
H. Bozem ◽  
H. Fischer ◽  
C. Gurk ◽  
C. L. Schiller ◽  
U. Parchatka ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Corona Discharge ◽  
Deep Convection ◽  
Convective Transport ◽  
Free Troposphere ◽  
Direct Production ◽  
Model Calculations ◽  
Mixing Ratios ◽  
Steady State Model

Abstract. Convective redistribution of ozone and its precursors between the boundary layer (BL) and the free troposphere (FT) influences photochemistry, in particular that of the middle and upper troposphere (UT). We present a case study of convective transport during the GABRIEL campaign over the tropical rain forest in Suriname in October 2005. During a measurement flight on 12 October the inflow and outflow regions of a cumulonimbus cloud (Cb) have been characterized, providing evidence of convective transport. We identified a distinct layer between 9 and 11 km altitude with enhanced mixing ratios of CO, O3, HOx, acetone and acetonitrile. The elevated O3 contradicts the expectation that convective transport brings low ozone air from the boundary layer to the outflow region. The enhanced mixing ratio of ozone in the outflow was mainly of dynamical origin. Entrainment of ozone rich air at the outflow level into the convective outflow accounts for 62% (range: 33–91%) of the observed O3. Ozone is enhanced by only 5–6% by photochemical production in the outflow due to enhanced NO from lightning, based on steady state model calculations, using in-situ observations including the first reported HOx measurements over the tropical rainforest. The "excess" ozone in the outflow is most probably due to direct production by corona discharge associated with lightning. We deduce a production rate of 5.12 × 1028 molecules O3 flash−1 (range: 9.89 × 1026–9.82 × 1028 molecules O3 flash−1), which is at the upper limit of the range of the values reported previously.

scholarly journals Chemical and aerosol processes in the transition from closed to open cells during VOCALS-REx

2011 ◽  
Vol 11 (2) ◽  
pp. 4687-4748 ◽  
Author(s):  
J. Kazil ◽  
H. Wang ◽  
G. Feingold ◽  
A. D. Clarke ◽  
J. R. Snider ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Dimethyl Sulfide ◽  
Marine Boundary Layer ◽  
Cloud Condensation Nuclei ◽  
Ocean Surface ◽  
Sea Salt ◽  
Free Troposphere ◽  
Near Surface ◽  
Open Cell ◽  
Cell State

Abstract. Chemical and aerosol processes in the transition from closed- to open-cell circulation in the remote, cloudy marine boundary layer are explored. It has previously been shown that precipitation can initiate a transition from the closed- to the open-cellular state, but that the boundary layer cannot maintain this open-cell state without a resupply of cloud condensation nuclei (CCN). Potential sources include wind-driven production of sea salt particles from the ocean, nucleation from the gas phase, and entrainment from the free troposphere. In order to investigate aerosol sources in the marine boundary layer and their role in supplying new particles, we have coupled in detail chemical, aerosol, and cloud processes in the WRF/Chem model, and added state-of-the-art representations of sea salt emissions and aerosol nucleation. We introduce the new features of the model and conduct simulations of the marine boundary layer in the transition from a closed- to an open-cell state. Results are compared with observations in the Southeast Pacific boundary layer during the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx). The transition from the closed- to the open-cell state generates conditions that are conducive to nucleation by forming a cloud-scavenged, ultra-clean layer below the inversion base. Open cell wall updrafts loft dimethyl sulfide from the ocean surface into the ultra-clean layer, where it is oxidized during daytime to SO2 and subsequently to H2SO4. Low H2SO4 condensation sink values in the ultra-clean layer allow H2SO4 to rise to concentrations at which aerosol nucleation proceeds efficiently. The existence of the ultra-clean layer is confirmed by observations. We find that the observed DMS flux from the ocean in the VOCALS-REx region can support a nucleation source of aerosol in open cells that exceeds sea salt emissions in terms of the number of particles produced. The freshly nucleated, nanometer-sized aerosol particles need, however, time grow to sizes large enough to act as CCN. In contrast, mechanical production of particles from the ocean surface by near-surface winds provides a steady source of larger particles that are effective CCN at a rate exceeding a threshold for maintenance of open-cell circulation. Entrainment of aerosol from the free troposphere contributes significantly to boundary layer aerosol for the considered VOCALS-REx case, but less than sea salt aerosol emissions.

scholarly journals Impact of nucleation on global CCN

2009 ◽  
Vol 9 (21) ◽  
pp. 8601-8616 ◽  
Author(s):  
J. Merikanto ◽  
D. V. Spracklen ◽  
G. W. Mann ◽  
S. J. Pickering ◽  
K. S. Carslaw
Keyword(s):  
Boundary Layer ◽  
Marine Boundary Layer ◽  
Environmental Changes ◽  
Control Strategies ◽  
Cloud Condensation Nuclei ◽  
Free Troposphere ◽  
Carbonaceous Particles ◽  
Upper Troposphere ◽  
Low Level ◽  
Primary Emissions

Abstract. Cloud condensation nuclei (CCN) are derived from particles emitted directly into the atmosphere (primary emissions) or from the growth of nanometer-sized particles nucleated in the atmosphere. It is important to separate these two sources because they respond in different ways to gas and particle emission control strategies and environmental changes. Here, we use a global aerosol microphysics model to quantify the contribution of primary and nucleated particles to global CCN. The model considers primary emissions of sea spray, sulfate and carbonaceous particles, and nucleation processes appropriate for the free troposphere and boundary layer. We estimate that 45% of global low-level cloud CCN at 0.2% supersaturation are secondary aerosol derived from nucleation (ranging between 31–49% taking into account uncertainties in primary emissions and nucleation rates), with the remainder from primary emissions. The model suggests that 35% of CCN (0.2%) in global low-level clouds were created in the free and upper troposphere. In the marine boundary layer 55% of CCN (0.2%) are from nucleation, with 45% entrained from the free troposphere and 10% nucleated directly in the boundary layer. Combinations of model runs show that primary and nucleated CCN are non-linearly coupled. In particular, boundary layer nucleated CCN are strongly suppressed by both primary emissions and entrainment of particles nucleated in the free troposphere. Elimination of all primary emissions reduces global CCN (0.2%) by only 20% and elimination of upper tropospheric nucleation reduces CCN (0.2%) by only 12% because of the increased contribution from boundary layer nucleation.

scholarly journals Modeling chemical and aerosol processes in the transition from closed to open cells during VOCALS-REx

2011 ◽  
Vol 11 (15) ◽  
pp. 7491-7514 ◽  
Author(s):  
J. Kazil ◽  
H. Wang ◽  
G. Feingold ◽  
A. D. Clarke ◽  
J. R. Snider ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Dimethyl Sulfide ◽  
Marine Boundary Layer ◽  
Cloud Condensation Nuclei ◽  
Ocean Surface ◽  
Sea Salt ◽  
Free Troposphere ◽  
Near Surface ◽  
Open Cell ◽  
Cell State

Abstract. Chemical and aerosol processes in the transition from closed- to open-cell circulation in the remote, cloudy marine boundary layer are explored. It has previously been shown that precipitation can initiate a transition from the closed- to the open-cellular state, but that the boundary layer cannot maintain this open-cell state without a resupply of cloud condensation nuclei (CCN). Potential sources of CCN include wind-driven production of sea salt from the ocean, nucleation from the gas phase, and entrainment from the free troposphere. In order to investigate CCN sources in the marine boundary layer and their role in supplying new particles, we have coupled in detail chemical, aerosol, and cloud processes in the WRF/Chem model, and added state-of-the-art representations of sea salt emissions and aerosol nucleation. We conduct numerical simulations of the marine boundary layer in the transition from a closed- to an open-cell state. Results are compared with observations in the Southeast Pacific boundary layer during the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx). The transition from the closed- to the open-cell state generates conditions that are conducive to nucleation by forming a cloud-scavenged, ultra-clean layer below the inversion base. Open cell updrafts loft dimethyl sulfide from the ocean surface into the ultra-clean layer, where it is oxidized during daytime to SO2 and subsequently to H2SO4. Low H2SO4 condensation sink values in the ultra-clean layer allow H2SO4 to rise to concentrations at which aerosol nucleation produces new aerosol in significant numbers. The existence of the ultra-clean layer is confirmed by observations. We find that the observed DMS flux from the ocean in the VOCALS-REx region can support a nucleation source of aerosol in open cells that exceeds sea salt emissions in terms of the number of particles produced. The freshly nucleated, nanometer-sized aerosol particles need, however, time to grow to sizes large enough to act as CCN. In contrast, mechanical production of particles from the ocean surface by near-surface winds provides a steady source of larger particles that are effective CCN at a rate exceeding a threshold for maintenance of open-cell circulation. Entrainment of aerosol from the free troposphere contributes significantly to boundary layer aerosol for the considered VOCALS-REx case, but less than sea salt aerosol emissions.

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.

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