Improving the Representation of Whitecap Fraction and Sea Salt Aerosol Emissions in the ECMWF IFS-AER

The European Centre for Medium-Range Weather Forecasts (ECMWF) operates the Integrated Forecasting System aerosol module (IFS-AER) to provide daily global analysis and forecast of aerosols for the Copernicus Atmosphere Monitoring Service (CAMS). New estimates of sea salt aerosol emissions have been implemented in the IFS-AER using a new parameterization of whitecap fraction as a function of wind speed and sea surface temperature. The effect of whitecap fraction simulated by old and new parameterizations has been evaluated by comparing the IFS-AER new sea salt aerosol characteristics to those of aerosol retrievals. The new parameterization brought a significant improvement as compared to the two parameterizations of sea salt aerosol emissions previously implemented in the IFS-AER. Likewise, the simulated sea salt aerosol optical depth and surface concentration are significantly improved, as compared against ground and remote sensing products.

A New Instrument for Determining the Coarse-Mode Sea Salt Aerosol Size Distribution

Sea salt aerosol(s) (SSA) play a significant role in the atmosphere through aerosol direct and indirect effects, and in atmospheric chemistry as a source of tropospheric bromine. In-situ measurements of coarse-mode SSA particles are limited because of their low concentration and relatively large sizes (dry radius, rd > 0.5 μm). With this in mind, a new, low-cost, easily usable method for sampling coarse-mode SSA particles in the marine boundary layer was developed. A SSA particle sampler that uses an impaction method was designed and built using 3D printing and Arduino microcontrollers and sensors. It exposes polycarbonate slides to ambient airflow remotely on a kite-based platform to capture coarse-mode SSA particles. Because it is a smaller version of the Giant Nucleus Impactor (GNI), designed for use on aircraft, it is named the miniature-Giant Nucleus Impactor, or “mini-GNI”. After sample collection, the same optical microscope methodology utilized by the GNI was used to analyze the wetted salt particles that impacted onto the slides. In this proof-of-concept study, multiple mini-GNIs were attached serially to a kite string, allowing for sampling at multiple altitudes simultaneously. The robustness of the results from this new instrument and methodology for sampling at ambient RH (~ 75 %) the SSA particle size distribution with rd > 3.3 μ m are compared with a similar study. We find that the SSA particle number concentration decreases weakly with altitude and shows no correlation to instantaneous U10 wind speed along the windward coastline of O‘ ahu in the Hawaiian Islands.

Southern Ocean latitudinal gradients of cloud condensation nuclei

The Southern Ocean region is one of the most pristine in the world and serves as an important proxy for the pre-industrial atmosphere. Improving our understanding of the natural processes in this region is likely to result in the largest reductions in the uncertainty of climate and earth system models. While remoteness from anthropogenic and continental sources is responsible for its clean atmosphere, this also results in the dearth of atmospheric observations in the region. Here we present a statistical summary of the latitudinal gradient of aerosol (condensation nuclei larger than 10 nm, CN10) and cloud condensation nuclei (CCN at various supersaturations) concentrations obtained from five voyages spanning the Southern Ocean between Australia and Antarctica from late spring to early autumn (October to March) of the 2017/18 austral seasons. Three main regions of influence were identified: the northern sector (40–45∘ S), where continental and anthropogenic sources coexisted with background marine aerosol populations; the mid-latitude sector (45–65∘ S), where the aerosol populations reflected a mixture of biogenic and sea-salt aerosol; and the southern sector (65–70∘ S), south of the atmospheric polar front, where sea-salt aerosol concentrations were greatly reduced and aerosol populations were primarily biologically derived sulfur species with a significant history in the Antarctic free troposphere. The northern sector showed the highest number concentrations with median (25th to 75th percentiles) CN10 and CCN0.5 concentrations of 681 (388–839) cm−3 and 322 (105–443) cm−3, respectively. Concentrations in the mid-latitudes were typically around 350 cm−3 and 160 cm−3 for CN10 and CCN0.5, respectively. In the southern sector, concentrations rose markedly, reaching 447 (298–446) cm−3 and 232 (186–271) cm−3 for CN10 and CCN0.5, respectively. The aerosol composition in this sector was marked by a distinct drop in sea salt and increase in both sulfate fraction and absolute concentrations, resulting in a substantially higher CCN0.5/CN10 activation ratio of 0.8 compared to around 0.4 for mid-latitudes. Long-term measurements at land-based research stations surrounding the Southern Ocean were found to be good representations at their respective latitudes; however this study highlighted the need for more long-term measurements in the region. CCN observations at Cape Grim (40∘39′ S) corresponded with CCN measurements from northern and mid-latitude sectors, while CN10 observations only corresponded with observations from the northern sector. Measurements from a simultaneous 2-year campaign at Macquarie Island (54∘30′ S) were found to represent all aerosol species well. The southernmost latitudes differed significantly from both of these stations, and previous work suggests that Antarctic stations on the East Antarctic coastline do not represent the East Antarctic sea-ice latitudes well. Further measurements are needed to capture the long-term, seasonal and longitudinal variability in aerosol processes across the Southern Ocean.

Field evidence of autocatalytic iodine release from atmospheric aerosol

<p>Reactive iodine plays a key role in determining the oxidation capacity of the atmosphere in addition to being implicated in the formation of new particles in the marine environment. Recycling of reactive iodine from heterogeneous processes on sea-salt aerosol was hypothesized over two decades ago but the understanding of this mechanism has been limited to laboratory studies and has not been confirmed in the atmosphere until now. Here, we report the first direct ambient observations of hypoiodous acid (HOI) and heterogeneous recycling of iodine monochloride (ICl) and iodine monobromide (IBr) at Mace Head Observatory in Ireland (53°19’ N, 9°54’ W) during the summer of 2018. A newly developed bromide based chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (Br-CI-APi-TOF) was deployed to measure I<sub>2</sub>, HOI, ICl, and IBr. Significant levels of ICl and IBr, with mean daily maxima of 4.3 and 3.0 pptv (1 min-average), respectively, have been observed throughout the campaign. We show that the heterogeneous reaction of HOI on marine aerosol and subsequent production of iodine interhalogens (ICl and IBr) are much faster than previously thought. These results indicate that the fast formation of iodine interhalogens, together with their rapid photolysis, results in more efficient recycling of atomic iodine than currently estimated by the models. The photolysis of the observed ICl and IBr leads to 32% increase in the daytime average of atomic iodine production rate, thereby enhancing the average daytime iodine-catalyzed ozone loss rate by 10-20%. Our findings provide the first direct field evidence that the autocatalytic mechanism of iodine release from marine aerosol is important in the atmosphere and can have significant impacts on atmospheric oxidation capacity and new particle formation in the troposphere.</p>

Assessing Sea-State Effects on Sea-Salt Aerosol Modeling in the Lower Atmosphere Using Lidar and In-Situ Measurements

Atmospheric-chemical coupled models usually parameterize sea-salt aerosol (SSA) emissions using whitecap fraction estimated considering only wind speed and ignoring sea state. This approach may introduce inaccuracies in SSA simulation. This study aims to assess the impact of sea state on SSA modeling, applying a new parameterization for whitecap fraction estimation based on wave age, calculated by the ratio between wave phase velocity and wind speed. To this end, the new parameterization was incorporated in the coupled Chemical Hydrological Atmospheric Ocean wave modeling System (CHAOS). CHAOS encompasses the wave model (WAM) two-way coupled through the OASIS3-MCT coupler with the Advanced Weather Research and Forecasting model coupled with Chemistry (WRF-ARW-Chem) and, thus, enabling the concurrent simulation of SSAs, wind speed and wave phase velocity. The simulation results were evaluated against in-situ and lidar measurements at 2 stations in Greece (Finokalia on 4 and 15 July 2014 and Antikythera-PANGEA on 15 September 2018). The results reveal significant differences between the parameterizations with the new one offering a more realistic representation of SSA levels in some layers of the lower atmosphere. This is attributed to the enhancement of the bubble-bursting mechanism representation with air-sea processes controlling whitecap fraction. Our findings also highlight the contribution of fresh wind-generated waves to SSA modeling.

Southern Ocean latitudinal gradients of Cloud Condensation Nuclei

The Southern Ocean region is one of the most pristine in the world, and serves as an important proxy for the pre-industrial atmosphere. Improving our understanding of the natural processes in this region are likely to result in the largest reductions in the uncertainty of climate and earth system models. While remoteness from anthropogenic and continental sources is responsible for its clean atmosphere, this also results in the dearth of atmospheric observations in the region. Here we present a statistical summary of the latitudinal gradient of aerosol and cloud condensation nuclei concentrations obtained from five voyages spanning the Southern Ocean between Australia and Antarctica from late-spring to early autumn (October to March) of the 2017/18 austral seasons. Three main regions of influence were identified: the northern sector (40–45° S) where continental and anthropogenic sources added to the background marine aerosol populations; the mid-latitude sector (45–65° S), where the aerosol populations reflected a mixture of biogenic and sea-salt aerosol; and the southern sector (65–70° S), south of the atmospheric Polar Front, where sea-salt aerosol concentrations were greatly reduced and aerosol populations were primarily biologically-derived sulfur species with a significant history in the Antarctic free-troposphere. The northern sector showed the highest number concentrations with median (25th to 75th percentiles) CN10 and CCN0:5 concentrations of (388–839) cm−3 and 322 (105–443) cm−3, respectively. Concentrations in the mid-latitudes were typically around 350 cm−3 and 160 cm−3 for CN10 and CCN0:5, respectively. In the southern sector, concentrations rose markedly, reaching 447 (298–446) cm−3 and 232 (186–271) cm−3 for CN10 and CCN0:5, respectively. The aerosol composition in this sector was marked by a distinct drop in sea-salt and increase in both sulfate fraction and absolute concentrations, resulting in a substantially higher CCN0:5 / CN10 activation ratio of 0.8 compared to around 0.4 for mid-latitudes. Long-term measurements at land-based research stations surrounding the Southern Ocean were found to be good representations at their respective latitudes i.e. CCN observations at Cape Grim (40°39'S) corresponded with CCN measurements from northern and mid-latitude sectors, while CN10 observations only corresponded with observations from the northern sector. Measurements from a simultaneous two year campaign at Macquarie Island (54°30'S) were found to represent all aerosol species well. The southern-most latitudes differed significantly from either of these stations and previous work suggests that Antarctic stations on the East Antarctic coastline do not represent the East Antarctic sea-ice latitudes well. Further measurements are needed to capture the long-term, seasonal and longitudinal variability in aerosol processes across the Southern Ocean.

Atmospheric Ageing of Inorganic Sea Spray Aerosol: Implications for Hygroscopicity and Cloud Activation Potential

Sea spray aerosol (SSA) contributes significantly to natural aerosol particle concentrations globally, in marine areas even dominantly. The potential changes of the omnipresent inorganic fraction of SSA due to atmospheric ageing is largely unexplored. We demonstrate that ageing of liquid NaCl and artificial sea salt aerosol by exposure to ozone and UV light leads to a substantial decrease in hygroscopicity and cloud activation potential. The results point towards surface reactions that are more crucial for small particles and the formation of salt structures with water bound within the aerosols, termed hydrates. Our findings suggest an increased formation of hydrate forming salts during ageing and the presence of hydrates in dried SSA. Field observations indicate a reduced hygroscopic growth of sub-micrometre SSA in the marine atmosphere compared to pure NaCl which is typically attributed to organic matter or sulphates. Aged inorganic sea salt offers an additional explanation for reduced hygroscopicity and cloud activation potential.

Seasonal Evolution of Size-Segregated Particulate Mercury in the Atmospheric Aerosol Over Terra Nova Bay, Antarctica

Size-fractionated particulate mercury (PHg) measurements were performed from November 2017 to January 2018 at Terra Nova Bay (Antarctica) for the first time. Samples were collected every 10 days by a six-stage high-volume cascade impactor with size classes between 10 μm and 0.49 μm. Total PHg concentrations were maxima (87 ± 8 pg m−3) in November, then decreased to values ~40% lower and remained almost constant until the end of the sampling period (~30 pg m−3). The trimodal aerosol mass distribution reveals that from 30% to 90% of the total PHg came in the size > 1.0 μm. Hg in the two coarse fractions was probably produced by the adsorption of oxidized Hg species transported by air masses from the Antarctic plateau or produced locally by sea ice edges. PHg in accumulation mode seemed to be related to gas–particle partitioning with sea salt aerosol. Finally, average dry deposition fluxes of PHg were calculated to be 0.36 ± 0.21 ng m−2 d−1 in the accumulation mode, 47 ± 44 ng m−2 d−1 in the first coarse mode, and 37 ± 31 ng m−2 d−1 in the second coarse mode. The present work contributed to the comprehension of the Hg biogeochemical cycle, but further research studies are needed.

Evaluating the impact of blowing-snow sea salt aerosol on springtime BrO and O₃ in the Arctic

We use the GEOS-Chem chemical transport model to examine the influence of bromine release from blowing-snow sea salt aerosol (SSA) on springtime bromine activation and O3 depletion events (ODEs) in the Arctic lower troposphere. We evaluate our simulation against observations of tropospheric BrO vertical column densities (VCDtropo) from the GOME-2 (second Global Ozone Monitoring Experiment) and Ozone Monitoring Instrument (OMI) spaceborne instruments for 3 years (2007–2009), as well as against surface observations of O3. We conduct a simulation with blowing-snow SSA emissions from first-year sea ice (FYI; with a surface snow salinity of 0.1 psu) and multi-year sea ice (MYI; with a surface snow salinity of 0.05 psu), assuming a factor of 5 bromide enrichment of surface snow relative to seawater. This simulation captures the magnitude of observed March–April GOME-2 and OMI VCDtropo to within 17 %, as well as their spatiotemporal variability (r=0.76–0.85). Many of the large-scale bromine explosions are successfully reproduced, with the exception of events in May, which are absent or systematically underpredicted in the model. If we assume a lower salinity on MYI (0.01 psu), some of the bromine explosions events observed over MYI are not captured, suggesting that blowing snow over MYI is an important source of bromine activation. We find that the modeled atmospheric deposition onto snow-covered sea ice becomes highly enriched in bromide, increasing from enrichment factors of ∼5 in September–February to 10–60 in May, consistent with composition observations of freshly fallen snow. We propose that this progressive enrichment in deposition could enable blowing-snow-induced halogen activation to propagate into May and might explain our late-spring underestimate in VCDtropo. We estimate that the atmospheric deposition of SSA could increase snow salinity by up to 0.04 psu between February and April, which could be an important source of salinity for surface snow on MYI as well as FYI covered by deep snowpack. Inclusion of halogen release from blowing-snow SSA in our simulations decreases monthly mean Arctic surface O3 by 4–8 ppbv (15 %–30 %) in March and 8–14 ppbv (30 %–40 %) in April. We reproduce a transport event of depleted O3 Arctic air down to 40∘ N observed at many sub-Arctic surface sites in early April 2007. While our simulation captures 25 %–40 % of the ODEs observed at coastal Arctic surface sites, it underestimates the magnitude of many of these events and entirely misses 60 %–75 % of ODEs. This difficulty in reproducing observed surface ODEs could be related to the coarse horizontal resolution of the model, the known biases in simulating Arctic boundary layer exchange processes, the lack of detailed chlorine chemistry, and/or the fact that we did not include direct halogen activation by snowpack chemistry.