Characterization of seawater and aerosol particle surfactants using solid phase extraction and mass spectrometry

Surface-active organic molecules (surfactants) may influence the ability of an aerosol particle to act as a cloud condensation nuclei by reducing its surface tension. One source of organic mass in aerosol particles, which may also contain surfactants, is bubble bursting on the sea surface. In order to directly compare these molecules in the ocean and aerosol particles, we developed a method using multiple solid phase extractions and high resolution mass spectrometry to characterize surface active organic molecules in both. This method has extraction efficiencies greater than 85%, 75%, and 60% for anionic, cationic, and nonionic surfactant standards, respectively. In this study, we demonstrate the presence of three ionic classes of surface active organics in atmospheric aerosol particles and estuarine water from Skidaway Island, GA. With this extraction method, organic molecules from both estuarine water and atmospheric aerosol particles significantly reduced surface tension of pure water (surface tension depression of ~ 18 mN/m) and had high ratios of hydrogen to carbon (H/C) and low ratios of oxygen to carbon (O/C), indicative of surfactants. While previous work has observed a larger fraction of anionic surface active organics in seawater and marine aerosol particles, here we show cationic surface active organics may make up a large fraction of the total surface active molecules in estuarine water (43%–47%).     

A large-scale outdoor atmospheric simulation smog chamber for studying atmospheric photochemical processes: Characterization and preliminary application

Understanding the formation mechanisms of secondary air pollution is very important for the formulation of air pollution control countermeasures in China. Thus, a large-scale outdoor atmospheric simulation smog chamber was constructed at Chinese Research Academy of Environmental Sciences (the CRAES Chamber), which was designed for simulating the atmospheric photochemical processes under the conditions close to the real atmospheric environment. The chamber consisted of a 56-m³ fluorinated ethylene propylene (FEP) Teflon film reactor, an electrically-driven stainless steel alloy shield, an auxiliary system, and multiple detection instrumentations. By performing a series of characterization experiments, we obtained basic parameters of the CRAES chamber, such as the mixing ability, the background reactivity, and the wall loss rates of gaseous compounds (propene, NO, NO₂, ozone) and aerosols (ammonium sulfate). Oxidation experiments were also performed to study the formation of ozone and secondary organic aerosol (SOA), including α-pinene ozonolysis, propene and 1,3,5-trimethylbenzene photooxidation. Temperature and seed effects on the vapor wall loss and SOA yields were obtained in this work: higher temperature and the presence of seed could reduce the vapor wall loss; SOA yield was found to depend inversely on temperature, and the presence of seed could increase SOA yield. The seed was suggested to be used in the chamber to reduce the interaction between the gas phase and chamber walls. The results above showed that the CRAES chamber was reliable and could meet the demands for investigating tropospheric chemistry.     

Review of the influencing factors of secondary organic aerosol formation and aging mechanism based on photochemical smog chamber simulation methods

The formation and aging mechanism of secondary organic aerosol (SOA) and its influencing factors have attracted increasing attention in recent years because of their effects on climate change, atmospheric quality and human health. However, there are still large errors between air quality model simulation results and field observations. The currently undetected components during the formation and aging of SOA due to the limitation of current monitoring techniques and the interactions among multiple SOA formation influencing factors might be the main reasons for the differences. In this paper, we present a detailed review of the complex dynamic physical and chemical processes and the corresponding influencing factors involved in SOA formation and aging. And all these results were mainly based the studies of photochemical smog chamber simulation. Although the properties of precursor volatile organic compounds (VOCs), oxidants (such as OH radicals), and atmospheric environmental factors (such as NO_x, SO₂, NH₃, light intensity, temperature, humidity and seed aerosols) jointly influence the products and yield of SOA, the nucleation and vapor pressure of these products were found to be the most fundamental aspects when interpreting the dynamics of the SOA formation and aging process. The development of techniques for measuring intermediate species in SOA generation processes and the study of SOA generation and aging mechanism in complex systems should be important topics of future SOA research.     

Roles of semivolatile and intermediate-volatility organic compounds in secondary organic aerosol formation and its implication: A review

Secondary organic aerosol(SOA) is a very important component of fine particulate matter(PM_2.5) in the atmosphere. However, the simulations of SOA, which could help to elucidate the detailed mechanism of SOA formation and quantify the roles of various precursors, remains unsatisfactory, as SOA levels are frequently underestimated. It has been found that the performance of SOA formation models can be significantly improved by incorporating the emission and evolution of semivolatile and ...     

Understanding the risks of mercury sulfide nanoparticles in the environment: Formation, presence, and environmental behaviors

Mercury (Hg) could be microbially methylated to the bioaccumulative neurotoxin methylmercury (MeHg), raising health concerns. Understanding the methylation of various Hg species is thus critical in predicting the MeHg risk. Among the known Hg species, mercury sulfide (HgS) is the largest Hg reservoir in the lithosphere and has long been considered to be highly inert. However, with advances in the analytical methods of nanoparticles, HgS nanoparticles (HgS NPs) have recently been detected in various environmental matrices or organisms. Furthermore, pioneering laboratory studies have reported the high bioavailability of HgS NPs. The formation, presence, and transformation (e.g., methylation) of HgS NPs are intricately related to several environmental factors, especially dissolved organic matter (DOM). The complexity of the behavior of HgS NPs and the heterogeneity of DOM prevent us from comprehensively understanding and predicting the risk of HgS NPs. To reveal the role of HgS NPs in Hg biogeochemical cycling, research needs should focus on the following aspects: the formation pathways, the presence, and the environmental behaviors of HgS NPs impacted by the dominant influential factor of DOM. We thus summarized the latest progress in these aspects and proposed future research priorities, e.g., developing the detection techniques of HgS NPs and probing HgS NPs in various matrices, further exploring the interactions between DOM and HgS NPs. Besides, as most of the previous studies were conducted in laboratories, our current knowledge should be further refreshed through field observations, which would help to gain better insights into predicting the Hg risks in natural environment.     

Exploring the formation potential and optical properties of secondary organic aerosol from the photooxidation of selected short aliphatic ethers

Secondary organic aerosol(SOA) formation potential for six kinds of short aliphatic ethers has been studied.The size distribution,mass concentration,and yield of SOA formed by ethers photooxidation were determined under different conditions.The results showed that all six ethers can generate SOA via reaction with OH radicals even under no seed and NO_xfree condition.The mass concentration for six seedless experiments was less than 10 μg/m³ and the SOA yields were all below 1...     

Primary and secondary organic aerosol in an urban/industrial site: Sources, health implications and the role of plastic enriched waste burning

PM10 samples were collected from an urban/industrial site nearby Athens, where uncontrolled burning activities occur. PAHs, monocarboxylic, dicarboxylic, hydroxycarboxylic and aromatic acids, tracers from BVOC oxidation, biomass burning tracers and bisphenol A were determined. PAH, monocarboxylic acids, biomass burning tracers and bisphenol A were increased during autumn/winter, while BSOA tracers, dicarboxylic- and hydroxycarboxylic acids during summer. Regarding aromatic acids, different sources and formation mechanisms were indicated as benzoic, phthalic and trimellitic acids were peaked during summer whereas p-toluic, isophthalic and terephthalic were more abundant during autumn/winter. The Benzo[a]pyrene-equivalent carcinogenic power, carcinogenic and mutagenic activities were calculated showing significant (p < 0.05) increases during the colder months. Palmitic, succinic and malic acids were the most abundant monocarboxylic, dicarboxylic and hydrocarboxylic acids during the entire sampling period. Isoprene oxidation was the most significant contributor to BSOA as the isoprene-SOA compounds were two times more abundant than the pinene-SOA (13.4 ± 12.3 and 6.1 ± 2.9 ng/m³, respectively). Ozone has significant impact on the formation of many studied compounds showing significant correlations with: isoprene-SOA (r = 0.77), hydrocarboxylic acids (r = 0.69), pinene-SOA (r = 0.63),dicarboxylic acids (r = 0.58), and the sum of phthalic, benzoic and trimellitic acids (r = 0.44). PCA demonstrated five factors that could explain sources including plastic enriched waste burning (30.8%), oxidation of unsaturated fatty acids (23.0%), vehicle missions and cooking (9.2%), biomass burning (7.7%) and oxidation of VOCs (5.8%). The results highlight the significant contribution of plastic waste uncontrolled burning to the overall air quality degradation.     

Insights into multidimensional transport flux from vertical observation and numerical simulation in two cities in North China

This study represents the first quantitative evaluation of pollution transport budget within the boundary layer of typical cities in the Beijing-Tianjin-Hebei (BTH) region from the perspective of horizontal and vertical exchanges and further discusses the impact of the atmospheric boundary layer (ABL)-free troposphere (FT) exchange on concentration of fine particulate matter (PM_2.5) within the ABL during heavy pollution. From the perspective of the transport flux balance relationship, differences in pollution transport characteristics between the two cities is mainly reflected in the ABL-FT exchange effect. The FT mainly flowed into the ABL in BJ, while in SJZ, the outflow from the ABL to the FT was more intense. Combined with an analysis of vertical wind profile distribution, BJ was found to be more susceptible to the influence of northwest cold high prevailing in winter, while sinking of strong cold air allowed the FT flowing into the ABL influence the vertical exchange over BJ. In addition, we selected a typical pollution event for targeted analysis to understand mechanistic details of the influence of ABL-FT exchange on the pollution event. These results showed that ABL-FT interaction played an important role in PM_2.5 concentration within the ABL during heavy pollution. Especially in the early stage of heavy pollution, FT transport contributed as much as 82.74% of PM_2.5 within the ABL. These findings are significant for improving our understanding of pollution transport characteristics within the boundary layer and the effect of ABL-FT exchange on air quality.