Role of Iodine Recycling on Sea-Salt Aerosols in the Global Marine Boundary Layer.

Heterogeneous uptake of hypoiodous acid (HOI), the dominant inorganic iodine species in the marine boundary layer (MBL), on sea-salt aerosol (SSA) to form iodine monobromide and iodine monochloride has been adopted in models with assumed efficiency. Recently, field measurements have reported a much faster rate of this recycling process than previously assumed in models. Here, we conduct global model simulations to quantify the range of effects of iodine recycling within the MBL, using Conventional, Updated, and Upper-limit coefficients. When considering the Updated coefficient, iodine recycling significantly enhances gaseous inorganic iodine abundance (∼40%), increases halogen atom production rates (∼40% in I, >100% in Br, and ∼60% in Cl), and reduces oxidant levels (-7% in O3, -2% in OH, and -4% in HO2) compared to the simulation without the process. We appeal for further direct measurements of iodine species, laboratory experiments on the controlling factors, and multiscale simulations of iodine heterogeneous recycling.

Impact of sea ice on the physicochemical characteristics of marine aerosols in the Arctic Ocean.

Marine aerosols (MA) can be influenced by sea ice concentration, potentially playing a pivotal role in the formation of cloud condensation nuclei and exerting an impact on regional climate. In this study, a high-resolution aerosol observation system was employed to measure the concentration and size of aerosols in the floating ice region and seawater region of the Arctic Ocean during the 8th and 9th Chinese Arctic Expedition Research Cruise. The identification of aerosol sources was conducted using a modified positive definite matrix factorization method and a backward air mass trajectory model. Two types of MA including the sea-salt aerosol (SSA) and the marine biogenic aerosol (BA) were identified and their concentrations were calculated. Then the physical-chemical characteristics of MA in the floating ice region and seawater region were compared under normalized conditions (-2.5 °C < T < -0.1 °C; 5.80 m/s < WS < 10.95 m/s) to discern the impact of sea ice. A unimodal distribution was observed for MA number concentration with a dominant peak ranging from 0.5 µm to 1.0 µm in size range. The findings revealed that the presence of sea ice cover led to a significant reduction of 52.2 % in the number concentration of SSA, while exerting minimal influence on its composition. BA number concentration in the floating ice region was 33.3 % higher than that in the seawater region. Strong winds (wind speed >6.5 m/s) transported organic matter and nutrients entrapped in sea ice into the atmosphere, leading to an increase in BA concentration. However, the presence of sea ice cover hampered the exchange of biogenic gases between the ocean and air, resulting in a reduction of secondary BA formation. Our study elucidates the correlation between MA release and sea ice coverage in the Arctic Ocean, thereby establishing a theoretical foundation for climate prediction models.

Study of an Arctic blowing snow-induced bromine explosion event in Ny-Ålesund, Svalbard.

Bromine explosion events (BEEs) are important processes that influence the atmospheric oxidation capacity, especially in the polar troposphere during spring. Although sea ice surface is thought to be a significant bromine source, bromine release mechanisms remain unclear. High-resolution ground-based observations of reactive bromine, such as BrO, are important for assessing the potential impacts on tropospheric ozone and evaluating chemical models. However, previous model studies paid little attention to Svalbard, which is surrounded by both open ocean and sea ice. In this paper, we present continuous BrO slant column densities and vertical column densities derived by Multi-Axis Differential Optical Absorption Spectroscopy deployed at Ny-Ålesund (78.92°N, 11.93°E) in March 2017. We focused on one BEE in mid-March, during which the vertical column densities of BrO surged from 4.26 × 1013 molecular cm-2 to the peak at 1.23 × 1014 molecular cm-2 on March 17, surface ozone depleted from a background level of 46.25 parts per billion by volume (ppbv) to 13.9 ppbv. This case study indicates that the BEE was strongly associated with blowing snow induced by the cyclone systems that approached Svalbard from March 14 to 18. By considering meteorological conditions, sea ice coverage, and airmass trajectory history, we demonstrate that sea salt aerosols (SSAs) from blowing snow on sea ice, rather than from open ocean, are attributed to the occurrence of this BEE. Model results from a parallelized-tropospheric offline model of chemistry and transport (p-TOMCAT) indicate that this BEE was mainly triggered by a blowing snow event associated with a low-pressure cyclone system. The concentration of blowing-snow-sourced SSAs surged to peak when the airmass pass across the sea-ice-covered area under high wind speed, which is a critical factor in the process of bromine explosion observed in Ny-Ålesund. Due to the coarse resolution, the possible delayed timing of bromine release from SSA and the model-data discrepancies still exist.

Relative role of black carbon and sea-salt aerosols as cloud condensation nuclei over a high altitude urban atmosphere in eastern Himalaya.

The present study is an attempt to investigate the relative role of black carbon (BC) and sea-salt aerosols on the CCN activation over a high altitude station, Darjeeling (27.1° N and 88.15° E, 2200 m asl) at eastern Himalaya. Aerosols (CN, CCN, BC and PM2.5) were measured during premonsoon and monsoon in 2017 and 2018. A unique sampling strategy and a novel methodology were adopted that enabled us to quantitatively and separately determine the contributions of local emissions (LE), valley wind transport (VWT) and long-range transport (LRT) to BC aerosols and their role in CCN activation. On the other hand, the contributions of transported sea-salt (NaCl) aerosols to CCN activation were also determined when they interact with the local anthropogenic soluble species and when they do not. CCN (0.5% super-saturation) concentrations were found to be increased when BC aerosols were more aged (~ 80 cm-3 and 218 cm-3 increase in CCN for 1 µg m-3 increase in BCLE and BCLRT with activation ratios of 0.17 and 0.55 respectively). Local anthropogenic acidic species (SO42-/H2SO4 (g) and NO3-/HNO3 (g)) interact with NaCl resulting to Cl- depletion. Cl- depletion was increased with the increase in NO3- + SO42-(45% for1 µg m-3increase in NO3- + SO42-) that in turn sharply decreased the AR of NaCl (0.04 for 1% increase in Cl- depletion). On the other hand, higher the NO3- + SO42-, higher were the CCN activation of transported BC which could be due to the soluble coating on BC. The important and interesting fact is that when transported and interacted with anthropogenic soluble species, BC aerosols (though hydrophobic) act as much better CCN than NaCl (though hydrophilic).

Size resolved aerosol respiratory doses in a Mediterranean urban area: From PM10 to ultrafine particles.

In the framework of the 2017 "carbonaceous aerosol in Rome and Environs" (CARE) experiment, particle number size distributions have been continuously measured on February 2017 in downtown Rome. These data have been used to estimate, through MPPD model, size and time resolved particle mass, surface area and number doses deposited into the respiratory system. Dosimetry estimates are presented for PM10, PM2.5, PM1 and Ultrafine Particles (UFPs), in relation to the aerosol sources peculiar to the Mediterranean basin and to the atmospheric conditions. Particular emphasis is focused on UFPs and their fraction deposited on the olfactory bulb, in view of their possible translocation to the brain. The site of PM10 deposition within the respiratory system considerably changes, depending on the aerosol sources and then on its different size distributions. On making associations between health endpoints and aerosol mass concentrations, the relevant coarse and fine fractions would be more properly adopted, because they have different sources, different capability of penetrating deep into the respiratory system and different toxicological implications. The separation between them should be set at 1 µm, rather than at 2.5 µm, because the fine fraction is considerably less affected by the contribution of the natural sources. Mass dose is a suitable metric to describe coarse aerosol events but gives a poor representation of combustion aerosol. This fraction of particles, made of UFPs and of accumulation mode particles (mainly with size below 0.2 µm), is of high health relevance. It elicited the highest oxidative activity in the CARE experiment and is properly described by the particle surface area and by the number metrics. Such metrics are even more relevant for the UFP doses deposited on the olfactory bulb, in consideration of the role recognized to oxidative stress in the progression of neurodegenerative diseases. Such metrics would be more appropriate, rather than PMx mass concentrations, to correlate neurodegenerative pathologies with aerosol pollution.

Measurement-based investigation of ozone deposition to vegetation under the effects of coastal and photochemical air pollution in the Eastern Mediterranean.

Dry deposition of ozone (O3) to vegetation is an important pathway for its removal from the troposphere, and it can lead to adverse effects in plants and changes in climate. However, our mechanistic understanding of O3 dry deposition is insufficient to adequately account for it in global and regional models, primarily because this process is highly complicated by feedback mechanisms and sensitivity to specific characteristics of vegetative environment and atmospheric dynamics and composition. We hypothesized that measuring dry deposition of O3 to vegetation near the Eastern Mediterranean (EM) coast, where large variations in meteorological conditions and photochemical air pollution frequently occur, would enable identifying the mechanisms controlling O3 deposition to vegetation. Moreover, we have only limited knowledge of O3 deposition to vegetation occurring near a coastline, under air pollution, or in the EM. This study investigated O3 deposition to mixed Mediterranean vegetation between the summers of 2015 and 2017, 3.6 km away from the EM coast, using the eddy covariance technique to quantify vertical flux of O3 and its partitioning to stomatal and non-stomatal flux, concurrent with nitrogen oxide (NOx), sulfur dioxide and carbon monoxide. Surprisingly, nighttime O3-deposition velocity (Vd) was smaller than daytime Vd by only ~20-37% on average for all measurement periods, primarily related to moderate nighttime atmospheric stability due to proximity to the seashore. We provide evidence for the role of sea-salt aerosols in enhancing O3 deposition via surface-wetness buildup at low relative humidity near the coast, and for daytime enhancement of O3 deposition by the combined effects of biogenic volatile organic compound emission and surface-wetness buildup. We further show that NOx emitted from elevated emission sources can reduce O3 deposition, and even lead to a positive O3 flux, demonstrating the importance of adequately taking into account the impact of air pollution on O3 deposition to vegetation.

Continental-scale variation in chloride/bromide ratios of wet deposition.

Chlorine and bromine play crucial roles in atmospheric element cycles and are important environmental tracers in catchment investigations, so understanding their distribution at the Earth's near-surface is imperative for deciphering their behaviour. This study presents the first continental-scale analysis of Cl- and Br- concentrations of wet deposition, based on six and half years of weekly samples collected across North America. A recently developed imputation algorithm was applied to estimate the high proportion of censored Br- values, as well as the other eight analytes, based on the multivariate relationships of nine analytes. The results are consistent with previous studies that have found that the concentrations of these two ions in wet deposition, and the Cl-/Br- ratios of wet deposition decrease with distance inland. Close to the coast, Cl-/Br- ratios of wet deposition are similar to the ratio found in seawater (~288 by mass), rapidly decrease to approximately a third of the seawater ratio at ~200km inland, and then decrease at a much lesser rate to reach mass-ratios of 20 to 10 at ~1500km inland, following a logarithmic regression. The Niagara Falls and the Great Salt Lake are identified as localised sources of atmospheric solutes based on elevated Cl-/Br- ratios of wet deposition at proximal sites. Our observations provide further confidence in the findings presented in previous studies that have shown that Cl-/Br- ratios systematically decrease with increasing distance from the coast, despite the potential confounding impact of other processes, such as weather patterns, chemical behaviour and anthropogenic activity. Our results provide improved estimates of Cl-/Br- ratios of wet deposition source water in the absence of site-specific data.

[Physico-chemical Characteristics of Individual Aerosol Particles in Marine Atmosphere on South Hemisphere].

During the 29th Chinese National Antarctic Research Expedition (CHIANRE), individual particle samples were collected from South China to Antarctic during November 2012 to April 2013. A transmission electron microscopy with energy-dispersive X-ray spectrometry (TEM-EDS) was employed to analyze the morphology, mixing state, composition, and relative abundances of individual aerosol particles. Atmospheric particles were classified into four types:sea salt, mineral, S-rich and C-rich. Sea salt aerosols (SSA) were dominant in the marine particles from South China to Antarctic, and they were further divided into three sub-types:fresh SSA, partially aged SSA, and fully aged SSA. Partially and fully aged SSA accounted for 86% of total SSA number. Interestingly, surface of partially aged SSA and fully aged SSA contained abundant rod-like Na2SO4. Mineral dust particles increased in the coastal areas which were influenced by continental air. In addition, we found that S-rich particles were abundant at two sampling sites (the middle eastern of Indian Ocean and Antarctic inland). The back trajectories of air masses indicated that these S-rich particles were mainly formed via the oxidation of dimethyl sulfide (DMS) emitted from the marine phytoplanktons. Our study suggests that the SSA aging process in the South Hemisphere atmosphere was controlled by the DMS which is different from the SSA aging under the influence of anthropogenic pollutants in the North Hemisphere.