Atmospheric Bases-Enhanced Iodic Acid Nucleation: Altitude-Dependent Characteristics and Molecular Mechanisms.

Iodic acid (IA), the key driver of marine aerosols, is widely detected within the gas and particle phases in the marine boundary layer (MBL) and even the free troposphere (FT). Although atmospheric bases like dimethylamine (DMA) and ammonia (NH3) can enhance IA particles formation, their different efficiencies and spatial distributions make the dominant base-stabilization mechanisms of forming IA particles unclear. Herein, we investigated the IA-DMA-NH3 nucleation system through quantum chemical calculations at the DLPNO-CCSD(T)/aug-cc-pVTZ(-PP)//ωB97X-D/6-311++G(3df,3pd) + aug-cc-pVTZ-PP level of theory and cluster dynamics simulations. We provide molecular-level evidence that DMA and NH3 can jointly stabilize the IA clusters. The formation rates of IA clusters initially decline before rising from the MBL to the FT, owing to variations in mechanism. In the MBL, IA-DMA nucleation predominates, while the contribution of IA-DMA-NH3 synergistic nucleation cannot be overlooked in polar and NH3-polluted regions. In the lower FT, IA-DMA-NH3 nucleation prevails, whereas in the upper FT, IA-NH3 nucleation dominates. The efficiency of IA-DMA-NH3 nucleation is comparable to that of IA-iodous acid nucleation in the MBL and sulfuric acid-NH3 nucleation in the FT. Hence, the IA-DMA-NH3 mechanism holds promise for revealing the missing sources of tropospheric IA particles.

Description of a Dimethylmercury Automatic Analyzer for the High-Resolution Measurement of Dissolved Gaseous Mercury Species in Surface Ocean Waters.

Our understanding of the significance of dimethylmercury (DMHg) to the mercury (Hg) global ocean biogeochemical cycle is unclear because of the lack of detailed DMHg measurements in the water column. To our knowledge, 30 years of published studies have generated no more than 200 DMHg data points in the ocean surface waters and marine boundary layer (MBL). To improve the precision and reduce the uncertainty in determining DMHg in surface seawater, we developed a simple and robust DMHg automatic analyzer (DAA). This DAA system couples the main sampling and analytic steps, including a continuous flow chamber, with dual Carbotrap preconcentration, a gas chromatographic column, a cold vapor atomic fluorescence spectrometry, and a data logger for signal integration. We compared the operation, performance, and reproducibility between our DAA and the traditional manual analytic method. Its advantages include the ease of operation, the high time resolution and precision (30 min sampling and <5% relative variation), and long-term stability (2 weeks). The DAA can determine DMHg in both the MBL and surface seawater. The estimated detection limits for DMHg with the DAA in the atmosphere and in surface seawater are 10 pg/m3 and 0.2 fM, respectively. The successful DAA field measurement in coastal waters indicates that it can help detect the low DMHg concentration in surface seawater, and the time series DMHg data helped our understanding of the DMHg behavior (sources and sinks) and its flux into the MBL. The comparison of DMHg concentration in various oceans also suggests that the coastal region had the lowest averaged DMHg, up to an order of magnitude lower than other ecosystems.

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.

MAX-DOAS observation in the midlatitude marine boundary layer: Influences of typhoon forced air mass.

As a passive remote sensing technique, MAX-DOAS method was widely used to investigate the vertical profiles of aerosol and trace gases in the lower troposphere. However, the measurements for midlatitude marine boundary layer are rarely reported, especially during the storm weather system. In this study, the MAX-DOAS was used to retrieve the aerosol, HCHO and NO2 vertical distribution at Huaniao Island of East China Sea in summer 2018, during which a strong tropical cyclone developed and passed through the measurement site. The observed aerosol optical depth (AOD), HCHO- and NO2-VCDs (Vertical Column Density) were in the range of 0.19-0.97, (2.57-12.27) × 1015 molec/cm2, (1.24-4.71) × 1015 molec/cm2, which is much higher than remote ocean area due to the short distance to continent. The vertically resolved aerosol extinction coefficient (AEC), HCHO and NO2 presented the decline trend with the increase of height. After the typhoon passing through, the distribution of high levels of aerosol and HCHO stretched to about 1 km and the abundances of the bottom layer were found as double higher than before, reaching 0.51 km-1 and 2.44 ppbv, while NO2 was still constrained within about 300 m with 2.59 ppbv in the bottom layer. The impacts of typhoon process forced air mass were also observed at the suburban site in Shanghai in view of both the aerosol extinction and chemical components. The different changes on air quality associated with typhoon and its mechanism in two different environments: coastal island and coastal city are worthy of further investigation as it frequent occurred in East Asia during summer and fall.

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer.

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Marine Boundary Layer Height Obtained by New Numerical Regularization Method Based on GPS Radio Occultation Data.

The boundary layer height (BLH) determines the interface between the lower and the free atmosphere, and it is a key variable in numerical simulations and aerosol and environmental pollution studies. This article proposes a novel method in conjunction with numerical regularization to analyze the climate characteristics of the marine boundary layer height (MBLH) using 2007-2011 GPS-RO data from the COSMIC mission. The MBLH corresponds to the smallest gradient, which is calculated using the numerical regulation method where the regulation parameters are determined by the double-parameter model function method. The results reveal the relationship between the MBLH and ocean currents for the first time. A low MBLH is associated with cold seasons and seas where cold ocean currents prevail whereas a high MBLH is related to warm seasons and seas where warm currents prevail. This correlation was validated by comparing the obtained results with different occultation data including atmprf and echprf, which also showed that atmprf is more sensitive to convective cloud top capture. To test the credibility of the results, the standard deviation was used to express the MBLH confidence level. The results show that the standard deviation of the MBLH was highest in low latitudes and lowest in the middle and high latitudes. Furthermore, we analyzed the trends in interannual MBLH variations, which display significant seasonal variations and spatial distributions that correspond with the current and subsolar point. Finally, we conducted a case study in the South China Sea, and identified a distinctive seasonal change and interannual decline in MBLH.

The Marine Boundary Layer Height over the Western North Pacific Based on GPS Radio Occultation, Island Soundings, and Numerical Models.

This paper estimates marine boundary layer height (MBLH) over the western North Pacific (WNP) based on Global Positioning System Radio Occultation (GPS-RO) profiles from the Formosa Satellite Mission 3 (FORMOSAT-3)/Constellation Observing System for Meteorology, Ionosphere, and Climate (COSMIC) satellites, island soundings, and numerical models. The seasonally-averaged MBLHs computed from nine years (2007⁻2015) of GPS-RO data are inter-compared with those obtained from sounding observations at 15 island stations and from the European Centre for Medium-Range Weather Forecasts (ECMWF) Reanalysis (ERA-Interim) and National Centers for Environmental Prediction Global Forecast System (NCEP GFS) data over the WNP from 2012 to 2015. It is found that the MBLH using nine years of GPS-RO data is smoother and more consistent with that obtained from sounding observations than is the MBLH using four years of GPS-RO data in a previous study. In winter, higher MBLHs are found around the subtropical latitudes and over oceans east of Japan, which are approximately located within the paths of the North Equatorial Current and the Kuroshio Current. The MBLH is also significantly higher in winter than in summer over the WNP. The above MBLH pattern is generally similar to those obtained from the analysis data of the ERA-Interim and NCEP GFS, but the heights are about 200 m higher. The verification with soundings suggests that the ERA-Interim has a better MBLH estimation than the NCEP GFS. Thus, the MBLH distributions obtained from both the nine-year GPS-RO and the ERA-Interim data can represent well the climatological MBLH over the WNP, but the heights should be adjusted about 30 m lower for the former and ~200 m higher for the latter. A positive correlation between the MBLH and the instability of the lower atmosphere exists over large near-shore areas of the WNP, where cold air can move over warm oceans from the land in winter, resulting in an increase in lower-atmospheric instability and providing favorable conditions for convection to yield a higher MBLH. During summer, the lower-atmospheric instability becomes smaller and the MBLH is thus lower over near-shore oceans.

Typhoon- and pollution-driven enhancement of reactive bromine in the mid-latitude marine boundary layer.

Tropospheric reactive bromine is important for atmospheric chemistry, regional air pollution, and global climate. Previous studies have reported measurements of atmospheric reactive bromine species in different environments, and proposed their main sources, e.g. sea-salt aerosol (SSA), oceanic biogenic activity, polar snow/ice, and volcanoes. Typhoons and other strong cyclonic activities (e.g. hurricanes) induce abrupt changes in different earth system processes, causing widespread destructive effects. However, the role of typhoons in regulating reactive bromine abundance and sources remains unexplored. Here, we report field observations of bromine oxide (BrO), a critical indicator of reactive bromine, on the Huaniao Island (HNI) in the East China Sea in July 2018. We observed high levels of BrO below 500 m with a daytime average of 9.7 ± 4.2 pptv and a peak value of ∼26 pptv under the influence of a typhoon. Our field measurements, supported by model simulations, suggest that the typhoon-induced drastic increase in wind speed amplifies the emission of SSA, significantly enhancing the activation of reactive bromine from SSA debromination. We also detected enhanced BrO mixing ratios under high NOx conditions (ppbv level) suggesting a potential pollution-induced mechanism of bromine release from SSA. Such elevated levels of atmospheric bromine noticeably increase ozone destruction by as much as ∼40% across the East China Sea. Considering the high frequency of cyclonic activity in the northern hemisphere, reactive bromine chemistry is expected to play a more important role than previously thought in affecting coastal air quality and atmospheric oxidation capacity. We suggest that models need to consider the hitherto overlooked typhoon- and pollution-mediated increase in reactive bromine levels when assessing the synergic effects of cyclonic activities on the earth system.

Methane emissions from oil and gas platforms in the Bohai Sea, China.

Although oil and gas explorations contribute to atmospheric methane (CH4) emissions, their impact and influence along the shelf seas of China remain poorly understood. From 2012 to 2017, we conducted four ship-based surveys of CH4 in the seawater column and boundary layer of the Bohai Sea, China, and further measured CO2 and several meteorological parameters. The average observed CH4 mixing ratios in the boundary layer and its concentrations in seawater column were 1950 ± 46 ppb in November 2012 (dissolved CH4 was not observed in this survey), 2222 ± 109 ppb and 13.0 ± 5.9 nmol/L in August 2014, 2014 ± 20 ppb and 5.4 ± 1.4 nmol/L in February 2017, and 1958 ± 25 ppb and 5.3 ± 3.8 nmol/L in May 2017, respectively. The results demonstrated that the CH4 emissions from the oil and gas platforms accounted for approximately 72.5 ± 27.0% of the increase in the background atmospheric CH4 in the local area. The remaining emissions were attributed to land-sea air mass transportation. Conversely, the influence of the air-sea exchange was negligible, measuring within the 10-3 ppb range. For carbon balance calibration, the mean flaring efficiency of the oil-associated gas based on the enhancement of CO2 (ΔCO2) and enhancement sum of CO2 and CH4 (ΔCO2 + ΔCH4) was 98.5 ± 0.5%. Furthermore, the CH4 emission rate from the oil and gas platforms was 0.026 ± 0.017 Tg/year, which was approximately 7.2 times greater than the sea-to-air CH4 flux over the entire Bohai Sea area. Thus, oil and gas platforms must be recognized as important artificial hotspot sources of atmospheric CH4 in the Bohai Sea.

Impact of air-sea exchange on the spatial distribution of atmospheric methane in the Dalian Bay and adjacent coastal area, China.

To date, the impact of air-sea exchange on spatial distribution of atmospheric methane (CH4 hereafter) remains less understood in the coastal areas of China. Here we measured the dissolved and atmospheric CH4 in the Dalian Bay and adjacent area in July and August 2014, respectively. Results showed that the study area was a net significant source of atmospheric CH4, with a mean sea-to-air CH4 flux of 170.6 ± 149.5 µmol/(m2·day). We optimized a method to accurately quantify the elevated atmospheric CH4 mole fraction (△CH4 hereafter) caused by air-sea exchange. The calculated △CH4 in the study area ranged from 15.4 to 102.1 nmol/mol, 1.5-10.2 nmol/mol, and 0.03-0.22 nmol/mol at the mixing height of 1, 10, and 471 m, respectively. The △CH4 mole fractions caused by air-sea exchange were positive with sea-to-air CH4 flux and in situ observed atmospheric CH4 mole fraction, while negative with altitude. Under the standard conditions, we defined 50.8 µmol/(m2·day) as the criteria value of sea-to-air CH4 flux which could result in a detectable elevation atmospheric CH4 mole fraction at a height of 10 m.

Chemical and isotopic characteristics of PM10 over the Bay of Bengal: Effects of continental outflow on a marine environment.

Pollutants transport from South and Southeast Asia can profoundly affect the marine atmospheric boundary layer (MABL) over the Bay of Bengal (BoB). This study presents chemical and stable isotopic composition of PM10 collected at Port Blair Island (11.6°N, 92.7°E) located in the middle of the BoB during the late northeast monsoon (February-April), a period when the BoB receives considerable continental outflow. These samples (n = 50) were analysed for major ions, carbonaceous species, trace metals, and isotopic composition of total C, N, and S components. Mass concentration of PM10 ranged from 24 to 65 µg m-3 during the study period. The dominance of continental inputs over a marine realm was evident by a significant amount of non-sea-salt (nss)-SO42- (range: 1.8 to 16.9 µg m-3), which accounts for ~65% of the total water-soluble inorganic constituents. The impact of anthropogenic emissions was further evident from the widespread depletion of chloride (range: 57-100%, avg.: 98 ± 7%) from sea-salt aerosols. Carbonaceous species (elemental carbon and organic matter) contributed nearly 35% to PM10. Further, average δ13C (-25.6‰ ± 0.5) and δ34S (4.5‰ ± 1.3) values observed over the marine study region were similar to those found in typical urban environments. δ15N values (13.7‰ ± 5.1) show the significant presence of combustion sources along with the effect of atmospheric processing. Aerosol δ13C values correlate positively with the ratio of water-soluble organic carbon to total organic carbon, indicating the aging of organic aerosols during the transport. Chemical and isotopic data suggest that both biomass burning (BB) and fossil fuel burning (FFB) contributed to ambient PM10 with relatively more contribution of BB during February to early March and that of FFB during late March to middle of April. In aggregate, this study provides newer insights into sources of carbonaceous species and their chemical processing in MABL of BoB.

Nitrous acid in marine boundary layer over eastern Bohai Sea, China: Characteristics, sources, and implications.

Nitrous acid (HONO) serves as a key source of hydroxyl radicals and plays important roles in atmospheric photochemistry. In this study, gaseous HONO and related species and parameters were measured in autumn of 2016 at a marine background site on Tuoji Island in eastern Bohai Sea, China. The HONO concentration in marine boundary layer (MBL) was on average 0.20 ±â€¯0.20 ppbv (average ±â€¯standard deviation) with a maximum hourly value of 1.38 ppbv. It exhibited distinct diurnal variations featuring with elevated concentrations in the late night and frequent concentration peaks in the early afternoon. During nighttime, the HONO was produced at a fast rate with the NO2-HONO conversion rate ranging from 0.006 to 0.036 h-1. The fast HONO production and the strong dependence of temperature implied the enhancement of nocturnal HONO formation caused by air-sea interactions at high temperature. At daytime, HONO concentration peaks were frequently observed between 13:00-15:00. The observed daytime HONO concentrations were substantially higher than those predicted in the photostationary state in conditions of intensive solar radiation and high temperature. Strong or good correlations between the missing HONO production rate and temperature or photolysis frequency suggest a potential source of HONO from the photochemical conversions of nitrogen-containing compounds in sea microlayer. The source intensity strengthened quickly when the temperature was high. The abnormally high concentrations of daytime HONO contributed a considerable fraction to the primary OH radicals in the MBL.

Atmospheric transport of 131I and 137Cs from Fukushima by the East Asian northeast monsoon.

The Lagrangian particle dispersion model FLEXPART was used to simulate atmospheric dispersion of radionuclides from the Fukushima nuclear power plant (FNPP) towards the Tropical Western Pacific (TWP) and Southeast Asia (SEA). The simulation model distinguished between hemispherical transport via the jet stream and regional transport within the marine boundary layer by the East Asian northeast monsoon. This regional transport was driven by anticyclonic circulation over southern Japan and the western Pacific resulting from a recurrent eastward extension of the Siberian High to the Pacific Ocean. Activity concentrations of 131I and 137Cs measured at ten monitoring stations in TWP and SEA were used to validate the particle dispersion model. Good agreement between the FLEXPART model and observations yields confidence regarding its application to assess radiation impacts and support emergency planning in response to a possible future nuclear accident in the region.

Simulation of urban boundary and canopy layer flows in port areas induced by different marine boundary layer inflow conditions.

Computational fluid dynamics (CFD) simulations and wind-tunnel (WT) tests can be considered as boundary-value problems, where the inlet boundary condition, which is usually obtained inferring inlet mean wind profiles from on-site measurements or other type of experimental data, represents the large-scale atmospheric forcing exerted at the outer limit of the urban model. It is not clear, however, to which extent the choice of different inflow wind speed profiles may affect WT and CFD results in the urban environment. In the present study, this aspect is investigated through the comparison of the wind flow fields simulated numerically and tested experimentally in an atmospheric boundary layer wind tunnel (ABLWT) within a district of Livorno city, Italy, called "Quartiere La Venezia". Three different shapes of inflow profiles were tested using the CFD technique and the results were compared with each other: one is based on the approach-flow profiles measured upstream of the urban model in the WT test section (WT profile) and two are based on anemometric data corresponding to the approach-flow profile measured by means of a LiDAR wind profiler (LiDAR profile 1 and 2). The analysis showed that using different wind speed profiles does not affect significantly the results in the urban canopy layer (UCL), where correlations of 95% and 98% were found between the LiDAR profile 1 and 2 data and the WT profile data (at z = 0.02 m above the bottom), respectively. Conversely, the different inflow profiles strongly affected the results above the UCL. This means that the local-scale effects induced on the wind field in the UCL by the urban texture are dominated mainly by the larger-scale forcing, as within the canopy the flow remains topologically invariant despite the different inflow conditions.

Air pollution survey across the western Mediterranean Sea: overview on oxygenated volatile hydrocarbons (OVOCs) and other gaseous pollutants.

Despite the Mediterranean Sea basin is among the most sensitive areas over the world for climate change and air quality issues, it still remains less studied than the oceanic regions. The domain investigated by the research ship Minerva Uno cruise in Summer 2015 was the Tyrrhenian Sea. An overview on the marine boundary layer (MBL) concentration levels of carbonyl compounds, ozone (O3), and sulfur dioxide (SO2) is reported. The north-western Tyrrhenian Sea samples showed a statistically significant difference in acetone and SO2 concentrations when compared to the south-eastern ones. Acetone and SO2 values were higher in the southern part of the basin; presumably, a blend of natural (including volcanism) and anthropogenic (shipping) sources caused this difference. The mean acetone concentration reached 5.4 µg/m3; formaldehyde and acetaldehyde means were equal to 1.1 µg/m3 and 0.38 µg/m3, respectively. Maximums of 3.0 µg/m3 for formaldehyde and 1.0 µg/m3 for acetaldehyde were detected along the route from Civitavecchia to Fiumicino. These two compounds were also present at levels above the average in proximity of petrol-refining plants on the coast; in fact, formaldehyde reached 1.56 µg/m3 and 1.60 µg/m3, respectively, near Milazzo and Augusta harbors; meanwhile, acetaldehyde was as high as 0.75 µg/m3 at both sites. The levels of formaldehyde agreed with previously reported measurements over Mediterranean Sea and elsewhere; besides, a day/night trend was observed, confirming the importance of photochemical formation for this pollutant. According to this study, Mediterranean Sea basin, which is a closed sea, was confirmed to suffer a high anthropic pressure impacting with diffuse emissions, while natural contribution to pollution could come from volcanic activity, particularly in the south-eastern Tyrrhenian Sea region.

The sea-air exchange of mercury (Hg) in the marine boundary layer of the Augusta basin (southern Italy): concentrations and evasion flux.

The first attempt to systematically investigate the atmospheric mercury (Hg) in the MBL of the Augusta basin (SE Sicily, Italy) has been undertaken. In the past the basin was the receptor for Hg from an intense industrial activity which contaminated the bottom sediments of the Bay, making this area a potential source of pollution for the surrounding Mediterranean. Three oceanographic cruises have been thus performed in the basin during the winter and summer 2011/2012, where we estimated averaged Hgatm concentrations of about 1.5±0.4 (range 0.9-3.1) and 2.1±0.98 (range 1.1-3.1) ng m(-3) for the two seasons, respectively. These data are somewhat higher than the background Hg atm value measured over the land (range 1.1±0.3 ng m(-3)) at downtown Augusta, while are similar to those detected in other polluted regions elsewhere. Hg evasion fluxes estimated at the sea/air interface over the Bay range from 3.6±0.3 (unpolluted site) to 72±0.1 (polluted site of the basin) ng m(-2) h(-1). By extending these measurements to the entire area of the Augusta basin (~23.5 km(2)), we calculated a total sea-air Hg evasion flux of about 9.7±0.1 g d(-1) (~0.004 tyr(-1)), accounting for ~0.0002% of the global Hg oceanic evasion (2000 tyr(-1)). The new proposed data set offers a unique and original study on the potential outflow of Hg from the sea-air interface at the basin, and it represents an important step for a better comprehension of the processes occurring in the marine biogeochemical cycle of this element.