Marine Atmospheric Aerosols Research Articles

Molecular composition of organic aerosols in urban and marine atmosphere: A comparison study using FIGAERO-I-CIMS, ESI-FT-ICR MS, and GC × GC-EI-ToF-MS

Molecular composition of organic aerosols in urban and marine atmosphere: A comparison study using FIGAERO-I-CIMS, ESI-FT-ICR MS, and GC × GC-EI-ToF-MS

Optical properties of chain-like atmospheric aerosol particles

Using the generalized multiparticle Mie-solution method, this study examines the optical properties of chain-like particles under different atmospheric conditions and various arrangements. The structural composition of aerosols exhibits a more pronounced impact on their extinction and absorption cross sections when the incident wavelength is below 600 nm, whereas significant changes are observed in backscattering cross sections for incident wavelengths above 600 nm. As the orientation angle between the incident wave and particle chain increases, the extinction cross sections and absorption cross sections exhibit varying degrees of decline. Furthermore, marine atmospheric aerosol chains demonstrate similar extinction cross sections to those of polluted atmospheric aerosols, and their absorption cross sections closely resemble those of clean atmospheric aerosols. In addition, for a particle chain of fixed length, the greater the disparity in particle sizes within the chain, the larger the difference between the backscattering cross section and that of the chains with equal particle sizes. This research provides theoretical support for assessing the climate effects of aerosols and inverting aerosol properties by LiDAR data.

Cruise observation of the marine atmosphere and ship emissions in South China Sea: Aerosol composition, sources, and the aging process

Marine atmospheric aerosols impact the global climate and biogeochemical cycles. However, how the composition, sources, and aging of these aerosols affect the above processes has not been thoroughly studied. Here, we conducted ship-based measurements in the northern South China Sea to investigate the chemical composition and aging of aerosols from various sources during the summer of 2019. Separate measurements were conducted at the bow (marine environment) and stern (cooking, smoking, and engine exhaust) of the ship. Source apportionment of organic aerosols (OAs) was conducted using positive matrix factorization (PMF) and trajectory models. The results showed that ship exhaust and coastal submicron particles were composed of comparable sulfate and organic fractions (both approximately 43%), distinct from the sulfate-dominated particles in the marine atmosphere (52–77%). PMF using the multilinear engine-2 solver identified five factors for the stern sampling period: hydrocarbon-like OA (HOA-I, 9%), slightly oxidized HOA (HOA-II, 25%), cooking OA (COA, 13%), cigarette smoke OA (CSOA, 4%), and low-volatility oxygenated OA (LV-OOA, 49%). The primary OAs (HOA-I/II + COA + CSOA), derived mostly from direct ship-related emissions, contributed to approximately half of the OAs, whereas the contribution from the highly aged marine atmosphere was only 20%. Notably, certain living-related emissions (i.e., COA and CSOA), which were often neglected in previous studies, might represent a considerable contribution to OA emissions from the ship. Four factors were identified for the bow sampling periods: HOA (13%), biomass burning OA (BBOA, 9%), semi-volatile OOA (7%), and LV-OOA (71%). The BBOAs from the Indo-China and Malay peninsulas were aged, converted to secondary organic aerosols (SOAs) during transport, and influenced by the combined photo-oxidation and liquid-phase reactions, indicating a substantial impact of BB on SOA formation. Our study highlights the influence of ship and inland emissions and their aging during transport on marine atmospheric aerosols.

Source apportionment of marine atmospheric aerosols in northern South China Sea during summertime 2018

Marine atmospheric aerosols play important roles in the global radiation balance and climate change. Hence, measuring physiochemical aerosol properties is essential to better understand their formation, aging processes, and source origins. However, high temporal resolution measurements of submicron particles are currently scarce in the northern South China Sea (SCS). In this study, we conducted a ship-based cruise campaign with a scanning mobility particle sizer and an online time of flight aerosol chemical speciation monitor to measure the particle number size distribution (PNSD) and the chemical composition of submicron particles over the northern SCS during summer 2018. The mean concentration of non-refractory submicron particulate matter (NR-PM1) was generally 9.11 ± 4.86 μg m−3; sulfate was the most abundant component, followed by organics, ammonium, nitrate, and chloride. Positive matrix factorization (PMF) analysis was applied to the PNSD (size PMF) and organic aerosols (OA PMF) and further investigated the source apportionment of the submicron particles. The size PMF identified four factors, including ship exhaust, ship influencing marine primary, continent affected marine secondary, and mixed accumulation aerosols. The most abundant particles in the number concentration were associated with ship emissions, which accounted for approximately 44 %. The submicron organic aerosols were highly oxidized and composed of low-volatility oxygenated OA (LV-OOA, 68 %), semi-volatile OOA (SV-OOA, 21 %), and hydrocarbon-like OA (HOA, 11 %). The backward trajectory of air masses showed that the northern SCS was most frequently (64.7 %) influenced by air masses from the Indo-Chinese Peninsula (ICP) during the campaign, implying that pollutants from ICP have a significant impact on the atmosphere of the northern SCS during summer. Thus, in situ ship-based cruise measurements can provide valuable data on the physiochemical characteristics of marine atmospheric aerosols to better understand their source origins.

Contribution of Volcanic and Fumarolic Emission to the Aerosol in Marine Atmosphere in the Central Mediterranean Sea: Results from Med-Oceanor 2017 Cruise Campaign

This work studied the contribution of the geogenic sources volcanoes and fumaroles to the aerosol in marine atmosphere in the central Mediterranean basin. For this purpose, in the framework of the Med-Oceanor measurement program, we carried out a cruise campaign in the summer of 2017 to investigate the impact to the aerosol of the most important Mediterranean volcanoes (Mount Etna, Stromboli Island, and Marsili Seamount) and solfatara areas (Phlegraean Fields complex, Volcano Islands, Ischia Island, and Panarea submarine fumarole). We collected PM10 and PM2.5 samples in 12 sites and performed chemical characterization to gather information about the concentration of major and trace elements, elemental carbon (EC), organic carbon (OC), and ionic species. The use of triangular plots and the calculation of enrichment factors confirmed the interception of volcanic plume. We integrated the outcomes from chemical characterization with the use of factor analysis and SEM/EDX analysis for the source apportionment. Anthropogenic and natural sources including shipping emissions, volcanic and fumarolic load, as well as sea spray were identified as the main factors affecting aerosol levels in the study area. Furthermore, we performed pattern recognition analysis by stepwise linear discriminant analysis to seek differences in the composition of PM10 and PM2.5 samples according to their volcanic or solfatara origin.

Effect of air masses motion on the rapid change of aerosols in marine atmosphere

The impact of air masses motion on marine aerosol properties was investigated using an on-board single particle mass spectrometer (SPAMS) deployed for the determination of single particle size resolved chemical composition over Southeast China Sea. Two aerosol blooms (E1 and E2) were observed during the cruise. High average particle number count occurred in E1 (7320), followed by E2 (5850), which was more than 100–150 times of the average particle number count during normal periods. Particles were classified as four major sources, including continental source, shipping source, marine source, and transport source based on the mass spectral similarity. Transport source was identified as those particles with high particle number count occurred only during aerosol bloom period. Three sub-types of EC-Ca, OC-Ca, and Al-rich were classified as transport source. EC-Ca was the dominant particles of the transport source, accounting for more than 70% of the total particles in aerosol bloom events. A uni-modal size distribution in the size range of 0.1–2.0 μm was observed during normal period, while a bimodal distribution with a tiny mode (<0.3 μm) and a coarse mode between 0.4 and 0.6 μm was present during aerosol bloom. The variation of aerosol source is consistent with air masses back trajectories, for the reason that most of the long-range air trajectories are from the ocean, while short air trajectories originate in the continental regions, which means that air masses have a significant impact on the aerosol physical–chemical properties along their tracks.

Chemical transfer of dissolved organic matter from surface seawater to sea spray water-soluble organic aerosol in the marine atmosphere

It is critical to understand how variations in chemical composition in surface seawater (SSW) affect the chemistry of marine atmospheric aerosols. We investigated the sea-to-air transfer of dissolved organic carbon (DOC) via cruise measurements of both ambient aerosols and SSW in the Oyashio and its coastal regions, the western subarctic Pacific during early spring. Sea spray aerosols (SSAs) were selected based on the stable carbon isotope ratio of water-soluble organic carbon (WSOC) (δ13CWSOC) and concentrations of glucose as a molecular tracer in marine aerosols together with local surface wind speed data. For both SSA and SSW samples, excitation-emission matrices were obtained to examine the transfer of fluorescent organic material. We found that the ratios of fluorescence intensity of humic-like and protein-like substances in the submicrometer SSAs were significantly larger than those in the bulk SSW (~63%). This ratio was also larger for the supermicrometer SSAs than for the SSW. The results suggest significant decomposition of protein-like DOC on a timescale of <12–24 h and/or preferential production of humic-like substances in the atmospheric aerosols regardless of the particle size. This study provides unique insights into the complex transfer of DOC from the ocean surface to the atmosphere.

Effects of continental anthropogenic sources on organic aerosols in the coastal atmosphere of East China

Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM2.5 samples from the marine and Changdao Island atmospheres were 5.5 ± 3.1 μgC/m3 and 6.9 ± 2.4 μgC/m3, respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM2.5 samples was 17.0 ± 20.2 ng/m3, indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the “North China” marine atmospheric samples. The “Northeast China” marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM2.5 without considering high spatial resolution source data and meteorological parameters.

海洋大气气溶胶粒子谱分布及其消光特征分析

海洋大气气溶胶粒子谱分布及其消光特征分析

Surface Electric Fields of Aqueous Solutions of NH4NO3, Mg(NO3)2, NaNO3, and LiNO3: Implications for Atmospheric Aerosol Chemistry

Ammonium (NH4+), magnesium (Mg2+), sodium (Na+), and nitrate (NO3–) ions are common constituents of ocean waters and found in abundance in marine atmospheric aerosols. Revealing the surface propensity (surface activity) of relevant ions provides insight into heterogeneous aerosol processes and potential impact on atmospheric chemistry. However, there is sparse surface data on NH4+, Mg2+, and little consensus for nitrate’s surface activity. Phase-resolved vibrational sum frequency generation (VSFG) experiments are highly well-suited for this task; yet, only aqueous NaNO3 salt has been studied by this technique to date. Here we investigate NH4+, Mg2+, and Na+, in addition to lithium (Li+), to fully understand the effect of countercations on nitrate but also to elucidate the surface propensity of the countercations themselves as this is the first phase-resolved heterodyne-detected (HD-)VSFG study to address nitrate with countercations beyond sodium. We show the presence of an interfacial electric field generated by surface-active NO3– and its counterions, including NH4+, a cation that is commonly identified with nitrate in tropospheric aerosol generated in urban regions. We find that NH4+, Li+, Na+, and Mg2+ are less surface-active relative to NO3–, with Mg2+ being the least so. The cation identity and the ion concentration determine the magnitude of this electric field, which decreases in the order of Mg2+ > Na+ > Li+ > NH4+ at the ∼2 M NO3– concentration (highly relevant to low water content aerosol). Important to note is that the surface charge density does not completely dictate the trend observed as one might expect.

Low-molecular-weight hydroxyacids in marine atmospheric aerosol: evidence of a marine microbial origin

Abstract. Lactic acid (LA) and glycolic acid (GA), which are low-molecular-weight hydroxyacids, were identified in the particle and gas phases within the marine atmospheric boundary layer over the western subarctic North Pacific. A major portion of LA (81%) and GA (57%) was present in the particulate phase, which is consistent with the presence of a hydroxyl group in these molecules leading to the low volatility of the compounds. The average concentration (±SD) of LA in more biologically influenced marine aerosols (33 ± 58 ng m−3) was substantially higher than that in less biologically influenced aerosols (11 ± 12 ng m−3). Over the oceanic region of phytoplankton blooms, the concentration of aerosol LA was comparable to that of oxalic acid, which was the most abundant diacid during the study period. A positive correlation was found between the LA concentrations in more biologically influenced aerosols and chlorophyll a in seawater (r2 = 0.56), suggesting an important production of aerosol LA possibly associated with microbial (e.g., lactobacillus) activity in seawater and/or aerosols. Our finding provides a new insight into the poorly quantified microbial sources of marine organic aerosols (OAs) because such low-molecular-weight hydroxyacids are key intermediates for OA formation.

Thermokarst lake waters across the permafrost zones of western Siberia

Abstract. This work describes the hydrochemical composition of thermokarst lake and pond ecosystems, which are observed in various sizes with different degrees of permafrost influence and are located in the northern part of western Siberia within the continuous and discontinuous permafrost zones. We analysed the elemental chemical composition of the lake waters relative to their surface areas (from 10 to 106 m2) and described the elemental composition of the thermokarst water body ecosystems in detail. We revealed significant correlations between the Fe, Al, dissolved organic carbon (DOC) and various chemical elements across a latitude gradient covering approximately 900 km. Several groups of chemical elements that reflect the evolution of the studied water bodies were distinguished. Combining the data for the studied latitude profile with the information available in the current literature demonstrated that the average dissolved elemental concentrations in lakes with different areas depend specifically on the latitudinal position, which is presumably linked to (1) the elements leached from frozen peat, which is the main source of the solutes in thermokarst lakes, (2) marine atmospheric aerosol depositions, particularly near the sea border and (3) short-range industrial pollution by certain metals from the largest Russian Arctic smelter. We discuss the evolution of the chemical compositions observed in thermokarst lakes during their formation and drainage and predict the effect that changing the permafrost regime in western Siberia has on the hydrochemistry of the lakes.

Molecular dynamics simulations reveal the assembly mechanism of polysaccharides in marine aerosols.

The high Arctic marine environment has recently detected polymer gels in atmospheric aerosol particles and cloud water originating from the surface microlayer of the open leads within the pack ice area. These polysaccharide molecules are water insoluble but water solvated, highly surface-active and highly hydrated (99% water). In order to add to the understanding and to complement missing laboratory characterization of marine polymer gels we have in this work performed an atomistic study of the assembly process and interfacial properties of polysaccharides. Our study reveals a number of salient features of the microscopic process behind polysaccharide assembly into nanogels. With three- and four-repeating units the polysaccharides assemble into a cluster in 50 ns. The aggregates grow quicker by absorbing one or two polymers each time, depending on the unit length and the type of inter-bridging cation. Although both the hydrophobic and hydrophilic domains are contracted, the latter dominates distinctly upon the contraction of solvent accessible surface areas. The establishment of inter-chain hydrogen-bonds is the key to the assembly while ionic bridges can further promote aggregation. During the assembly of the more bent four-unit polymers, intra-chain hydrogen bonds are significantly diminished by Ca(2+). Meanwhile, the percentage of Ca(2+) acting as an ionic bridge is more eminent, highlighting the significance of Ca(2+) ions for longer-chain polysaccharides. The aggregates are able to enhance surface tension more in the presence of Ca(2+) than in the presence of Na(+) owing to their more compact structure. These conclusions all demonstrate that studies of the present kind provide insight into the self-assembly process and interfacial properties of marine gels. We hope this understanding will keep up the interest in the complex and the fascinating relationship between marine microbiology, atmospheric aerosols, clouds and climate.

Cloud droplet activation mechanisms of amino acid aerosol particles: insight from molecular dynamics simulations

Atmospheric amino acids constitute a large fraction of water-soluble organic nitrogen compounds in aerosol particles, and have been confirmed as effective cloud condensation nuclei (CCN) materials in laboratory experiments. We present a molecular dynamics (MD) study of six amino acids with different structures and chemical properties that are relevant to the remote marine atmospheric aerosol–cloud system, with the aim of investigating the detailed mechanism of their induced changes in surface activity and surface tension, which are important properties for cloud drop activation. Distributions and orientations of the amino acid molecules are studied; these l-amino acids are serine (SER), glycine (GLY), alanine (ALA), valine (VAL), methionine (MET) and phenylalanine (PHE) and are categorised as hydrophilic and amphiphilic according to their affinities to water. The results suggest that the presence of surface-concentrated amphiphilic amino acid molecules give rise to enhanced Lennard–Jones repulsion, which in turn results in decreased surface tension of a planar interface and an increased surface tension of the spherical interface of droplets with diameters below 10 nm. The observed surface tension perturbation for the different amino acids under study not only serves as benchmark for future studies of more complex systems, but also shows that amphiphilic amino acids are surface active. The MD simulations used in this study reproduce experimental results of surface tension measurements for planar interfaces and the method is therefore applicable for spherical interfaces of nano-size for which experimental measurements are not possible to conduct.

Influence of seawater and its aerosols on copper patina composition

X-ray diffraction analysis was used to monitor patina composition on copper samples exposed during one-year period to different seawater zones (splash, tidal and full immersion) and marine atmospheric aerosols. Two phases contributed most to patina formation: cuprite (copper oxide) and atacamite (copper chloride compound). Their relative XRD spectra intensities were very similar in patina formed in the tidal sea zone, but atacamite became the sole majority phase in the full immersion zone. The cuprite phase decreased over time, and two minority copper sulfates phases appeared: posnjakite and chalcanthite (CuSO4). The results revealed that copper patina composition is strongly influenced by chloride pollution and specific zone conditions. Additional factors, such as wind-blown sand, continuous dredging in coastal areas and vessel docking, influenced degree of pollutant compound adherence to patinas and consequently their structure (porous or compact).

An Aerosol Model of the Marine and Coastal Atmospheric Surface Layer

We present a microphysical model for the surface layer marine and coastal atmospheric aerosols that is based on long-term observations of size distributions for 0.01–100 µm particles. The fundamental feature of the model is a parameterization of amplitudes and widths for aerosol modes of the aerosol size distribution function (ASDF) as functions of fetch and wind speed. The shape of ASDF and its dependence on meteorological parameters, height above sea level (H), fetch (X), wind speed (U) and relative humidity (RH), are investigated. At present, the model covers the ranges H = 0–25 m, U = 3–18 km s−1, X ≤ 120 km and RH = 40–98%. The latest version of the Marine Aerosol Extinction Profiles model (MaexPro) is described and applied to the computation and analysis of the spectral profiles of aerosol extinction coefficients α(λ) in the wavelength band λ = 0.2–12 µm. MaexPro is based on the aforementioned aerosol model assuming spherically shaped aerosol particles and the well-known Mie theory. The spectral profiles of α(λ) calculated by MaexPro are in good agreement with observational data and the numerical results obtained from the Navy Aerosol Model (NAM) and the Advanced Navy Aerosol Model (ANAM). Moreover, MaexPro was found to be an accurate and reliable tool for investigating the optical properties of atmospheric aerosols.

Visible and infrared extinction of atmospheric aerosol in the marine and coastal environment

The microphysical model Marine Aerosol Extinction Profiles (MaexPro) for surface layer marine and coastal atmospheric aerosols, which is based on long-term observations of size distributions for 0.01-100 μm particles, is presented. The fundamental feature of the model is a parameterization of amplitudes and widths for aerosol modes of the aerosol size distribution function (ASDF) as functions of fetch and wind speed. The shape of the ASDF and its dependence on meteorological parameters, altitudes above the sea level (H), fetch (X), wind speed (U), and relative humidity is investigated. The model is primarily to characterize aerosols for the near-surface layer (within 25 m). The model is also applicable to higher altitudes within the atmospheric boundary layer, where the change in the vertical profile of aerosol is not very large. In this case, it is only valid for "clean" marine environments, in the absence of air pollution or any other major sources of continental aerosols, such desert dust or smoke from biomass burning. The spectral profiles of the aerosol extinction coefficients calculated by MaexPro are in good agreement with observational data and the numerical results obtained by the well-known Navy Aerosol Model and Advanced Navy Aerosol Model codes. Moreover, MaexPro was found to be an accurate and reliable instrument for investigation of the optical properties of atmospheric aerosols.

Free and combined amino acids in marine background atmospheric aerosols over the Eastern Mediterranean

During a six-week intensive field campaign at a background marine site of the Eastern Mediterranean, consecutive 24-h air samples were collected and analyzed for combined (CAA) and free amino acids (FAA), as well as for key chemical characteristics of aerosols. The total concentration of CAA (719 ± 326 pmol m−3) was on average four times higher than that of FAA (172 ± 147 pmol m−3), while glycine was the most abundant compound detected in both FAA and CAA. Back-trajectory analysis demonstrated that the geographical origin of the air masses did not have a significant influence on the atmospheric levels of amino acids. Wind speed was found to be the most important meteorological factor and it exhibited a negative correlation with both FAA and CAA. Moreover, FAA and CAA concentrations showed a more pronounced correlation with water-soluble organic carbon (WSOC) than elemental carbon. On average, FAA and CAA accounted for 0.3 ± 0.2% and 1.8 ± 0.8% of WSOC, respectively. The levels of anionic surfactants determined as methylene blue active substances did not show any positive correlation with CAA, while the corresponding correlation with FAA was only of marginal significance. The total protein concentration measured by NanoOrange assay was six times higher compared to that measured through CAA. It is suggested that the results from the application of commercially available protein quantitation kits should always be considered with caution, as these are more prone to matrix-related interferences.

Research on characters of the marine atmospheric boundary layer structure and aerosol profiles by high spectral resolution lidar

We briefly discuss the characters of aerosol profiles in the marine atmospheric boundary layer (MABL) detected by a high spectral resolution lidar (HSRL) system developed by Ocean University of China. In this 532-nm lidar system, an iodine filter is used to reject the Mie scattering signal and extract the Rayleigh signal. We deduce the aerosol scattering ratio (Rb) by the HSRL and analyze the correlation index of Rb and relative humidity (RH) under different weather conditions. The height of MABL is derived from the Rb profiles using a wavelet method.

Photochemistry of Iron in Simulated Crustal Aerosols with Dimethyl Sulfide Oxidation Products

Iron contained in dust-derived aerosol particles deposited into remote oceans is essential for phytoplankton productivity, which controls photosynthesis rate and the uptake and release of climate forcing gases. Understanding chemical mechanisms that control iron bioavailability, that is, its speciation, is therefore crucial for global climate predictions. In the present study, the photoredox chemistry of iron in marine atmospheric aerosol particles was investigated by using ferrihydrite as a surrogate iron phase in the presence of dimethyl sulfide (DMS) derived oxidation products: dimethyl sulfoxide (DMSO), dimethyl sulfone (DMS02), methane sulfinic acid (MSIA), and methane sulfonic acid (MSA). Reactants and products were analyzed with UV-vis absorption spectroscopy, ion chromatography, and a hydrogen peroxide sensitive electrode. Results show that MSIA enhances the photoreductive dissolution of iron in a ligand-to-metal charge transfer reaction producing Fe(II), MSA, and H2O2. The rate law for Fe(II) is close to first order (0.79) with regard to adsorbed MSIA and has an empirical rate constant of 1.4 x 10(-4) s(-1). This mechanism may represent a significant pathway through which iron becomes more bioavailable, and it contributes to models of iron and sulfur chemistries in the marine atmosphere.