Atmospheric Gas Phase Research Articles

Atmospheric Gas-Phase Catalyst Etching of SiO2 for Deep Microfabrication Using HF Gas and Patterned Photoresist.

Micro/nanoscale structure fabrication is an important process for designing miniaturized devices. Recently, three-dimensional (3D) integrated circuits using SiO2 via-holes interlayer filling by copper have attracted attention to extend the lifetime of Moore's law. However, the fabrication of vertical and smooth-sidewall via-hole structures on SiO2 has not been achieved using the conventional dry etching method due to the limitation of the selective etching ratio of SiO2 and hard mask materials. In this study, we developed a unique method for the deep anisotropic dry etching of SiO2 using atmospheric gas-phase HF and a patterned photoresist. The hydroxyl groups in the photoresist catalyzed the HF gas-phase dry etching of SiO2 at high-temperature conditions. Therefore, fabrication of vertical with smooth-sidewall deep microstructures was demonstrated in the photoresist-covered area on SiO2 at a processing rate of 1.3 μm/min, which is 2-3 times faster than the conventional dry etching method. Additionally, the chemical reaction pathway in the photoresist-covered area on SiO2 with HF gas was revealed via density functional theory (DFT) calculations. This simple and high-speed microfabrication process will expand the commercial application scope of next-generation microfabricated SiO2-based devices.

Understanding the Formation and Growth of New Atmospheric Particles at the Molecular Level through Laboratory Molecular Beam Experiments.

Atmospheric new particle formation (NPF), which exerts comprehensive implications for climate, air quality and human health, has received extensive attention. From molecule to cluster is the initial and most important stage of the nucleation process of atmospheric new particles. However, due to the complexity of the nucleation process and limitations of experimental characterization techniques, there is still a great uncertainty in understanding the nucleation mechanism at the molecular level. Laboratory-based molecular beam methods can experimentally implement the generation and growth of typical atmospheric gas-phase nucleation precursors to nanoscale clusters, characterize the key physical and chemical properties of clusters such as structure and composition, and obtain a series of their physicochemical parameters, including association rate coefficients, electron binding energy, pickup cross section and pickup probability and so on. These parameters can quantitatively illustrate the physicochemical properties of the cluster, and evaluate the effect of different gas phase nucleation precursors on the formation and growth of atmospheric new particles. We review the present literatures on atmospheric cluster formation and reaction employing the experimental method of laboratory molecular beam. The experimental apparatuses were classified and summarized from three aspects of cluster generation, growth and detection processes. Focus of this review is on the properties of nucleation clusters involving different precursor molecules of water, sulfuric acid, nitric acid and NxOy, respectively. We hope this review will provide a deep insight for effects of cluster physicochemical properties on nucleation, and reveal the formation and growth mechanism of atmospheric new particle at the molecular level.

Theoretical analysis of the OH-initiated atmospheric oxidation reactions of imidazole.

Imidazoles are present in Earth's atmosphere in both the gas-phase and in aerosol particles, and have been implicated in the formation of brown carbon aerosols. The gas-phase oxidation of imidazole (C3N2H4) by hydroxyl radicals has been shown to be preferentially initiated via OH-addition to position C5, producing the 5-hydroxyimidazolyl radical adduct. However, the fate of this adduct upon reaction with O2 in the atmospheric gas-phase is currently unknown. We employed an automated approach to investigate the reaction mechanism and kinetics of imidazole's OH-initiated gas-phase oxidation, in the presence of O2 and NOx. The explored mechanism included reactions available to first-generation RO2 radicals, as well as alkoxyl radicals produced from RO2 + NO reactions. Product distributions were obtained by assembling and solving a master equation, under conditions relevant to the Earth's atmosphere. Our calculations show a complex, branched reaction mechanism, which nevertheless converges to yield two major closed-shell products: 4H-imidazol-4-ol (4H-4ol) and N,N'-diformylformamidine (FMF). At 298 K and 1 atm, we estimate the yields of 4H-4ol and FMF from imidazole oxidation initiated via OH-addition to position C5 to be 34 : 66, 12 : 85 and 2 : 95 under 10 ppt, 100 ppt and 1 ppb of NO respectively. This work also revealed O2-migration pathways between the α-N-imino peroxyl radical isomers. This reaction channel is fast for the first-generation RO2 radicals, and may be important during the atmospheric oxidation of other unsaturated organic nitrogen compounds as well.

Hydrocarbons in the atmospheric gas phase of a coastal city in Tunisia: Levels, gas–particle partitioning, and health risk assessment

Many studies have focused on aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (AHs and PAHs) in different environmental compartments, especially atmospheric particles (aerosols), due to their adverse effects on the environment and human health. However, much less information is currently available on the content of AHs and PAHs in the atmospheric gas phase, which is a major reservoir of volatile and photoreactive compounds. Here, for the first time, we assessed the levels, gas–particle partitioning, human health risks and seasonal variations of AHs and PAHs in the atmospheric gas-phase of Bizerte city (Tunisia, North Africa) over a one-year period (March 2015–January 2016). Σ34PAH concentration in the gas phase over the period ranged from 6.7 to 90.6 ng m−3 and on average was 2.5 times higher in the cold season than in the warm season. Σ28AH concentration in the gas phase over the period ranged from 14.0 to 35.9 ng m−3, with no clear seasonal variations. In the gas phase, hydrocarbons were dominated by low-molecular-weight (LMW) compounds, i.e. 3- and 4-ring for PAHs and < n-C24 for AHs. Gas-phase concentrations of PAHs and AHs accounted for up to 80 % of the total (gas + particle phases) atmospheric concentrations of PAHs and AHs. Further analysis of gas–particle partitioning showed that LMW hydrocarbons preferential accumulated in the gas phase, and that gas–particle partitioning was not in equilibrium but dominated by absorption processes into the aerosol organic matter. Benzo[a]pyrene toxic equivalency quotient (BaP-TEQ) in the gas phase represented on average 37 % of the total atmospheric BaP-TEQ concentration, which was always higher in the cold season. Atmospheric gas is a significant factor in the risks of cancer associated with inhalation of ambient air. The Monte Carlo simulation-based exposure assessment model predicted that outdoor air exposure to PAHs does not pose a cancer risk to infants, but the children, adolescent, and adult populations may face a lower cancer risk during the warm season and a higher risk in the cold season.

Atmospheric fate of typical liquid crystal monomers in the tropospheric gas, liquid, and granular phases

Mineral aerosol particles significantly impact environmental risk prediction of liquid crystal monomers (LCMs). In this work, we investigated the reaction mechanisms and kinetics of three typical LCMs (4-cyano-3,5-difluorophenyl 4-ethylbenzoate (CEB-2F), 4-cyano-3-fluorophenyl 4-ethylbenzoate (CEB-F), and 4-cyanophenyl 4-ethylbenzoate (CEB)) with ozone (O3) in the atmospheric gas, liquid, and particle phases employing density functional theory (DFT). Here, O3 is prone to add to the benzene ring without F atom(s) in the selected LCMs. The ozonolysis products are aldehydes, carboxylic acids, epoxides, and unsaturated hydrocarbons containing aromatic rings. Those products undergo secondary ozonolysis to generate small molecular compounds such as glyoxal, which is beneficial for generating secondary organic aerosol (SOA). Titanium dioxide (TiO2), an essential component of mineral aerosol particles, has good adsorption properties for LCMs; however, it slightly reduces the reactivity with O3. At 298 K, the reaction rate constant of the selected LCMs reacting with O3 in the gas and atmospheric liquid phases is (2.74‒5.53) × 10−24 cm3/(mol·sec) and 5.58 × 10−3‒39.1 L/(mol·sec), while CEB-2F reacting with O3 on (TiO2)6 cluster is 1.84 × 10−24 cm3/(mol·sec). The existence of TiO2 clusters increases the persistence and long-distance transportability of LCMs, which enlarges the contaminated area of LCMs.

Passive water sampling and air–water diffusive exchange of long-range transported semi-volatile organic pollutants in high-mountain lakes

The concentrations of legacy and currently emitted organic pollutants were determined in the freely dissolved phase of water from six high-mountain lakes in the Pyrenees (1619–2453 m) by passive water sampling. Low-density polyethylene (LDPE) and silicone rubber (SR) sheets were exposed for three consecutive periods lasting each one year between 2017 and 2020 for the study of polychlorinated biphenyls (PCBs), organophosphate esters (OPEs), polycyclic aromatic hydrocarbons (PAHs), and other organochlorine compounds (e.g., hexachlorobenzene, HCB). HCB concentrations (1.0–14 pg L−1) remained essentially the same as those measured with pumping systems over two decades ago in the same area. ƩPAHs (35–920 pg L−1) were around half of those observed in the past, which agrees with reductions in European atmospheric emissions. ƩPCB concentrations (1.2–2.2 pg L−1) were substantially lower, although unexpectedly large differences could be due to comparing yearly averages from the present study to seasonally variable (i.e., affected by snowmelt, stratification, and colloidal organic matter) episodic pumping measurements from previous studies. ƩOPEs (139–2849 pg L−1) were measured for the first time in this area and were found at high concentrations in some sites. Concentrations of most compounds obtained with LDPE and SR samplers agreed with each other by ratios generally lower than three or four times, except for a few PAHs and OPEs. Diffusive exchange flux calculations between the atmospheric gas phase and the freely dissolved water phase revealed net deposition of pollutants from air to water, except for some OPEs and PCBs presenting equilibrium conditions, and HCB with volatilization fluxes. Atmospheric degradation fluxes of PAHs and OPEs pointed at competing removal mechanisms that support the air-to-water direction of their diffusive exchange, while PCBs and organochlorines were not affected by photodegradation. In their current state, these remote lakes accumulate many emerging and legacy pollutants subject to long-range atmospheric transport.

Reactive Uptake of Gas-Phase NO2 by Urban Road Dust in the Dark.

Road dust constitutes a prominent source of anthropogenic particulate matter, making its heterogeneous interactions with common atmospheric gas-phase compounds important. Here, we show that three distinct samples of urban road dust-including dust samples collected from city streets in summer and winter, and an urban park in summer-react with NO2 in the dark, forming NO and surface nitrite. The loss of NO2 ranged from ∼2 to 13% of its gas-phase concentration and scaled with its concentration as well as with the mass of the road dust sample. The uptake of NO2 by the winter dust was ∼4 times greater than that seen from summer street dust, which was in turn greater than that by the park dust. The conversion ratio of NO2 → NO ranged from 0.06 to 0.8 NO produced per NO2 lost and was greatest for the summer park dust. Exposure of the summer road dust to NO2 roughly doubles the concentration of inorganic nitrite anion in the dust but does not produce nitrate. The formation of NO and photolabile nitrite products means that heterogeneous NO x reactions occurring on the surface of road dust in the dark could have wide implications for the oxidative potential of urban areas.

Atmospheric gas-phase composition over the Indian Ocean

Abstract. The Indian Ocean is coupled to atmospheric dynamics and chemical composition via several unique mechanisms, such as the seasonally varying monsoon circulation. During the winter monsoon season, high pollution levels are regularly observed over the entire northern Indian Ocean, while during the summer monsoon, clean air dominates the atmospheric composition, leading to distinct chemical regimes. The changing atmospheric composition over the Indian Ocean can interact with oceanic biogeochemical cycles and impact marine ecosystems, resulting in potential climate feedbacks. Here, we review current progress in detecting and understanding atmospheric gas-phase composition over the Indian Ocean and its local and global impacts. The review considers results from recent Indian Ocean ship campaigns, satellite measurements, station data, and information on continental and oceanic trace gas emissions. The distribution of all major pollutants and greenhouse gases shows pronounced differences between the landmass source regions and the Indian Ocean, with strong gradients over the coastal areas. Surface pollution and ozone are highest during the winter monsoon over the Bay of Bengal and the Arabian Sea coastal waters due to air mass advection from the Indo-Gangetic Plain and continental outflow from Southeast Asia. We observe, however, that unusual types of wind patterns can lead to pronounced deviations of the typical trace gas distributions. For example, the ozone distribution maxima shift to different regions under wind scenarios that differ from the regular seasonal transport patterns. The distribution of greenhouse gases over the Indian Ocean shows many similarities when compared to the pollution fields, but also some differences of the latitudinal and seasonal variations resulting from their long lifetimes and biogenic sources. Mixing ratios of greenhouse gases such as methane show positive trends over the Indian Ocean, but long-term changes in pollution and ozone due to changing emissions and transport patterns require further investigation. Although we know that changing atmospheric composition and perturbations within the Indian Ocean affect each other, the impacts of atmospheric pollution on oceanic biogeochemistry and trace gas cycling are severely understudied. We highlight potential mechanisms, future research topics, and observational requirements that need to be explored in order to fully understand such interactions and feedbacks in the Indian Ocean region.

Atmospheric Chemistry of N-Methylmethanimine (CH3N═CH2): A Theoretical and Experimental Study.

The OH-initiated photo-oxidation of N-methylmethanimine, CH3N=CH2, was investigated in the 200 m3 EUPHORE atmospheric simulation chamber and in a 240 L stainless steel photochemical reactor employing time-resolved online FTIR and high-resolution PTR-ToF-MS instrumentation and in theoretical calculations based on quantum chemistry results and master equation modeling of the pivotal reaction steps. The quantum chemistry calculations forecast the OH reaction to primarily proceed via H-abstraction from the =CH2 group and π-system C-addition, whereas H-abstraction from the −CH3 group is a minor route and forecast that N-addition can be disregarded under atmospheric conditions. Theoretical studies of CH3N=CH2 photolysis and the CH3N=CH2 + O3 reaction show that these removal processes are too slow to be important in the troposphere. A detailed mechanism for OH-initiated atmospheric degradation of CH3N=CH2 was obtained as part of the theoretical study. The photo-oxidation experiments, obstructed in part by the CH3N=CH2 monomer–trimer equilibrium, surface reactions, and particle formation, find CH2=NCHO and CH3N=CHOH/CH2=NCH2OH as the major primary products in a ratio 18:82 ± 3 (3σ-limit). Alignment of the theoretical results to the experimental product distribution results in a rate coefficient, showing a minor pressure dependency under tropospheric conditions and that can be parametrized k(T) = 5.70 × 10–14 × (T/298 K)3.18 × exp(1245 K/T) cm3 molecule–1 s–1 with k298 = 3.7 × 10–12 cm3 molecule–1 s–1. The atmospheric fate of CH3N=CH2 is discussed, and it is concluded that, on a global scale, hydrolysis in the atmospheric aqueous phase to give CH3NH2 + CH2O will constitute a dominant loss process. N2O will not be formed in the atmospheric gas phase degradation, and there are no indications of nitrosamines and nitramines formed as primary products.

Changes and distribution of gas-phase polycyclic aromatic hydrocarbons and organochlorine compounds in a high-mountain gradient over a three-year period (Pyrenees, 2017–2020)

The atmospheric gas-phase concentrations of several polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), hexachlorobenzene (HCB), and pentachlorobenzene (PeCB) were measured in six high-mountain sites in the Pyrenees (1619–2453 m). Polyurethane foam passive air samplers were used for this purpose, providing continuous records spanning over three years (2017–2020). The mean concentrations of ∑PCBs, HCB, and PeCB, 13 ± 4 pg m−3, 44 ± 18 pg m−3, and 23 ± 20 pg m−3, respectively, were of the order of those reported in other mountain sites and similar to those measured 20 years ago in the same area, evidencing the persistence of these compounds despite the international regulatory actions. The mean concentration of ∑PAHs was 631 ± 238 pg m−3, representing between two- and three-times lower values than 20 years ago in the same area, but still in the range of other mountain regions. Statistically significant increases in gas-phase concentrations at higher temperatures were observed for most compounds. The experimental phase-change pseudo-enthalpies calculated from the slopes of the regressions between the natural logarithm of the concentrations and the reciprocal of temperature were lower than the reference values for nearly all compounds. This difference suggested a main contribution of long-range atmospheric transport of the gas-phase PAH and organochlorine concentrations in this mountain area. However, the less volatile compounds such as benz[a]anthracene, PCB138, and PCB180 showed a closer similarity between experimental and laboratory enthalpies, indicating that a significant portion of the variations in concentration of these compounds originated from temperature-dependent diffusive exchange by re-volatilization from local surfaces. The concentrations found in these sentinel ecosystems demonstrate that long-range transport of organic pollutants remains a risk in remote continental environments.

Seasonal variation and deposition of atmospheric organophosphate esters in the coastal region of Shanghai, China

The coastal megacity Shanghai is located in the center of the Yangtze River Delta, a dominant flame retardants (FRs) production region in China, especially for organophosphate esters (OPEs). This prompted us to investigate occurrence and seasonal changes of atmospheric OPEs in Shanghai, as well as to evaluate their sources, environmental behavior and fate as a case study for global coastal regions. Atmospheric gas and particle phase OPEs were weekly collected at two coastal sites - the emerging town Lingang New Area (LGNA), and the chemical-industry zone Jinshan Area (JSA) from July 2016–June 2017. Total atmospheric concentrations of the observed OPEs were significantly higher in JSA (median of 1800 pg m−3) than LGNA (median of 580 pg m−3). Tris(1-chloro-2-propyl) phosphate (TCPP) was the most abundant compound, and the proportion of three chlorinated OPEs were higher in the particle phase (55%) than in the gas phase (39%). The year-round median contribution of particle phase OPEs was 33%, which changed strongly with seasons, accounting for 10% in summer in contrast to 62% in winter. Gas and particle phase OPEs in JSA exhibited significant correlations with inverse of temperature, respectively, indicating the importance of local/secondary volatilization sources. The estimated fluxes of gaseous absorption were almost 2 orders of magnitude higher than those of particle phase deposition, which could act as sources of organic phosphorus to coastal and open ocean waters.

Kinetic Study of Methanol Dehydration to Dimethyl Ether in Catalytic Packed Bed Reactor over Resin

Dimethyl ether (DME) is considered as a significant fuel alternative with a critical manufacturing process. Only a few authors have presented the kinetic analysis of attractive and alternative catalysts to Al2O3 and/or zeolite in DME production, despite the fact that there is a large library of kinetic studies for these commercial catalysts. The purpose of this research was to contribute to this direction by conducting a catalytic test to determine kinetic parameters for methanol dehydration over sulfonic acid catalysts (resin). However, due to the relevance of the mathematical description of this process in the industry was also studied, a study of kinetics parameters and mathematical modeling of methanol dehydration in an atmospheric gas phase in a fixed bed reactor with a temperature range (90&degC - 120&degC) was examined. The Langmuir-Hinshelwood (L-H) model provides the best fit to experimental data, with an excellent R2 = 0.9997, and the experimental results were compared to those predicted by these models with very small deviations. The kinetic parameters were found to be in good agreement with the Arrhenius equation, with acceptable straight-line graphs. The activation energy E was computed and found to be 27.66 kJ/mole, with an average variation of 0.32 percent between the predicted and calculated results. Simple mathematical continuum models (plug flow reactor PFR) showed an acceptable agreement with the experimental data.

Occurrence and temperature dependence of atmospheric gas-phase organophosphate esters in high-mountain areas (Pyrenees)

The air concentrations of organophosphate esters (OPEs) were studied in a network of six remote high-mountain areas of the Pyrenees located along an altitudinal profile between 1619 m and 2453 m above sea level on a restricted planar surface to assess their vertical distribution based on long-range atmospheric transport and temperature gradients. Polyurethane foam passive samplers were used in five periods spanning over three years (September 2017–October 2020). The sum of concentrations of five OPEs were between 5.3 and 100 pg m−3, averaging 16–53 pg m−3 across campaigns at the different locations. These concentrations were much lower than those observed in areas under anthropogenic influence but also than those found in low altitude remote continental sites. A significant progressive change in predominant compounds was observed along the altitudinal gradient, with prevalence of tris(1-chloro-2-propyl) phosphate (TCIPP) or tris(2-chloroethyl) phosphate (TCEP) below or above 2300 m above sea level, respectively. This trend was consistent with the higher volatility of TCEP, which was retained at greater extent at lower environmental temperatures (higher altitude).A significant temperature dependence of the gas phase concentrations was observed for TCEP, TCIPP and triphenyl phosphate (TPHP), which could be explained by retention in the cold periods, predominantly adsorbed in snow, and their release to the atmosphere during snowmelt. This mechanism was consistent with the good agreement found between the vaporization enthalpies measured under laboratory conditions and the experimental values obtained from the slopes of the significant linear regressions when representing the vertical gradients.

A closer look into the contribution of atmospheric gas-phase pathways in the formation of perfluorocarboxylic acids

The potential synthesis of the notorious perfluorocarboxylic acids (PFCAs, CF3(CF2)nC(O)OH) from the atmospheric degradation of fluorotelomer alcohols (FTOHs, CF3(CF2)nCH2CH2OH), has been a focal point of debate with many intriguing questions appearing unanswered. In addition to transport by ocean currents, the atmospheric “precursor” pathway provides a likely source for the observed alarming load of PFCAs in remote regions; most notably the Arctic circle. However, pertinent smog chambers experiments that established the FTOHs → PFCAs route, were carried out under conditions that are not typically encountered in the ambient atmosphere (i.e., excessive or absence of NO/HO2 concentrations). To underpin the underlying chemical phenomena and the plausible formation of PFCAs (and other perfluorinated compounds), we report herein a detail chemistry kinetic model into the OH-initiated decomposition of 4:2 FTOH as a model compound of fluorotelomer alcohols. The underlying aim is to illustrate pathways that govern the production of fluorotelomers acids (CF3(CF2)nCH2C(O)OH, FTCAs), fluorotelomer aldehydes (CF3(CF2)nCH2C(O)H, FTALs), perfluorinated aldehydes (CF3(CF2)nC(O)H, PFALs), and PFCAs. Time-dependent molar yields of a large array of species were attained against representative atmospheric compositions that reflect urban, ocean, and arctic environments. A fast decarbonylation of the CF3(CF2)3CO radicals significantly diminishes the gas-phase formation of the CF3(CF2)3CO(OH) compound. Overall, it is concluded that the widely accepted formation of PFCAs in the atmosphere may take place through non-gas phase routes. Metals-rich silicate particles in aerosols and dust, could mediate formation of FTCAs and PFCAs in the atmosphere from FTOHs.

Emulation of an atmospheric gas-phase chemistry solver through deep learning: Case study of Chinese Mainland

The solution of atmospheric chemical kinetics is considered as the dominant computationally intensive task in chemical transport models. Reported strategies for improving computational efficiency have not changed the essence of solving ordinary differential equations. In this study, we emulate a typical gas-phase chemistry solver implemented in chemical transport models in Chinese Mainland using a 28-layer residual regression neural network. Validation results have a total R2 of 0.985 with the original numerical solution for 194 species during a single timestep. Multiple-timestep test for one month verified the accuracy and stability of our model while no exponential accumulated bias was observed, though a slow accumulation of biases existed. There were 102 species with R2 values higher than 0.90 and 137 species with daily NMB values below 30% among the 194 species throughout the month. Meanwhile, the computational efficiency of gas-phase chemistry using the deep learning emulator was promoted by 10.6 times on one CPU and 85.2 times on one GPU. Our study confirms the feasibility of emulating an atmospheric chemical kinetic solver with data-driven models through deep learning and represents a step towards a deep learning solver being used in a chemical transport model. The deep learning emulator is expected to not only accelerate atmospheric chemical kinetic solutions by orders of magnitude but also provide a promising pathway for implementing near-explicit rather than lumped chemical mechanisms in chemical transport models.

A novel smoothed particle hydrodynamics formulation for thermo-capillary phase change problems with focus on metal additive manufacturing melt pool modeling

Laser-based metal processing including welding and three dimensional printing, involves localized melting of solid or granular raw material, surface tension-driven melt flow and significant evaporation of melt due to the applied very high energy densities. The present work proposes a weakly compressible smoothed particle hydrodynamics formulation for thermo-capillary phase change problems involving solid, liquid and gaseous phases with special focus on selective laser melting, an emerging metal additive manufacturing technique. Evaporation-induced recoil pressure, temperature-dependent surface tension and wetting forces are considered as mechanical interface fluxes, while a Gaussian laser beam heat source and evaporation-induced heat losses are considered as thermal interface fluxes. A novel interface stabilization scheme is proposed, which is shown to allow for a stable and smooth liquid–gas interface by effectively damping spurious interface flows as typically occurring in continuum surface force approaches. Moreover, discretization strategies for the tangential projection of the temperature gradient, as required for the discrete Marangoni forces, are critically reviewed. The proposed formulation is deemed especially suitable for modeling of the melt pool dynamics in metal additive manufacturing because the full range of relevant interface forces is considered and the explicit resolution of the atmospheric gas phase enables a consistent description of pore formation by gas inclusion. The accuracy and robustness of the individual model and method building blocks is verified by means of several selected examples in the context of the selective laser melting process.

Reduction of Ionic Silver by Sulfur Dioxide as a Source of Silver Nanoparticles in the Environment.

The natural formation of silver nanoparticles (AgNPs) via biotic and abiotic pathways in water and soil media contributes to the biogeochemical cycle of silver metal in the environment. However, the formation of AgNPs in the atmosphere has not been reported. Here, we describe a previously unreported source of AgNPs via the reduction of Ag(I) by SO2 in the atmosphere, especially in moist environments, using multipronged advanced analytical and surface techniques. The rapid reduction of Ag(I) in the atmospheric aqueous phase was mainly caused by the sulfite ions formed from the dissolution of SO2 in water, which contributed to the formation of AgNPs and was consistent with the Finke-Watzky model with a major contribution of the reduction-nucleation process. Sunlight irradiation excited SO2 to form triplet SO2, which reacted with water to form H2SO3 and greatly enhanced Ag(I) reduction and AgNP formation. Different pH values affected the speciation of Ag(I) and S(IV), which were jointly involved in the reduction of Ag(I). The formation of AgNPs was also observed in the atmospheric gas phase via direct reduction of Ag(I) by SO2(gas), which occurred even in 50 ppbv SO2(gas). The natural occurrence of AgNPs in the atmosphere may also be involved in silver corrosion, AgNP transformation and regeneration, detoxification of gaseous pollutants, and the sulfur cycle in the environment.

Quantification and risk assessment of pesticides in southern Brazilian air samples using low-volume sampling and rapid ultrasound-assisted extraction.

Brazil is one of the largest pesticide consumers in the world. In the last few years, the use of permissive environmental laws and newly authorized pesticide formulations has been enlarged. Thus, the intensive and inadequate use of pesticides may present a risk to human health since these compounds may move between environmental compartments. Outdoor air samples were collected using low-volume samplers at Arapongas city in the state of Paraná, Brazil, between February and November of 2017. Polyurethane foam (PUF) cartridges were presented as a good choice to collect pesticides from atmospheric gas phase samples when compared to styrene-divinylbenzene (XAD-2). Lower limits of quantitation were obtained with PUF cartridges, which allowed a greater number of samples to be quantified in PUF than in XAD-2. Atrazine and trifluralin were quantified for the first time in Brazilian air samples. The levels of concentration ranged between 192-1731 pg m-3 (chlorpyrifos), 136-1345 pg m-3 (atrazine) and 184-1189 pg m-3 (trifluralin). Alachlor has been out of market in Brazil since 2013, and thus it was not detected in any gas phase sample. The highest daily inhalation exposure was observed in infants, 1 × 10-6 mg kg-1 d-1 for atrazine, chlorpyrifos and trifluralin. None of the analyzed pesticides were associated with a hazardous quotient (HQ) > 1, considering the worst-case scenario for infants, indicating that there is no risk associated with the exposed population. Cancer risk assessment for trifluralin resulted in values below 1 × 10-6, therefore not indicating any significant risk to human health.

Sources apportionment and carcinogenic risk of polycyclic aromatic hydrocarbons in gas phase of urban Shanghai: Based on high volume solid phase extraction (Hi-volume SPE).

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants, posing potentially serious threats to human health. This study analyzed compositional characteristics, sources, and carcinogenic risks of PAHs in the atmospheric gas phase at an urban site in Shanghai, East China. Seventy-four gas phase samples were collected during the warm months of May-October 2018 using a high-volume solid phase extraction (Hi-volume SPE) technique. The total concentration of sixteen priority PAHs (ΣPAHs) was in the range of 5.54-182.05ngm-3 (average 34.47ngm-3) and the total of seven carcinogenic PAHs (ΣCPAHs) was in range of 0.03-1.49ngm-3 (average 0.48ngm-3), accounting for 1.47% of ΣPAHs and indicating low carcinogenic potential. Redundancy analyses indicated positive correlations between ΣPAHs and air quality, and ΣCPAHs and average high temperature, and a negative correlation between ΣPAHs and wind speed. Four possible sources, namely petroleum and petrogenic sources, traffic emissions, coal combustion, and mixed gasoline and coal combustion sources, were identified by positive matrix factorization (PMF), accounting for 62.84%, 19.31%, 10.15%, and 7.69% of ΣPAHs, respectively. The overall lifetime lung cancer risk (LLCR) through inhalation of PAHs was estimated to be at a low risk level of 1.61×10-5. The LLCR based on PMF apportionment decreased in the order of mixed gasoline and coal combustion sources (47.07%)>traffic emissions (35.10%)>petroleum and petrogenic sources (11.06%)>coal combustion (6.74%). This study demonstrates the effectiveness of Hi-volume SPE in collecting and analyzing atmospheric gas phase PAHs.

Strong Even/Odd Pattern in the Computed Gas-Phase Stability of Dicarboxylic Acid Dimers: Implications for Condensation Thermodynamics.

The physical properties of small straight-chain dicarboxylic acids are well known to exhibit even/odd alternations with respect to the carbon chain length. For example, odd numbered diacids have lower melting points and higher saturation vapor pressures than adjacent even numbered diacids. This alternation has previously been explained in terms of solid-state properties, such as higher torsional strain of odd number diacids. Using quantum chemical methods, we demonstrate an additional contribution to this alternation in properties resulting from gas-phase dimer formation. Due to a combination of hydrogen bond strength and torsional strain, dimer formation in the gas phase occurs efficiently for glutaric acid (C5) and pimelic acid (C7) but is unfavorable for succinic acid (C4) and adipic acid (C6). Our results indicate that a significant fraction of the total atmospheric gas-phase concentration of glutaric and pimelic acid may consist of dimers.