Low Volatile Organic Compounds Research Articles

An integrated study on air mitigation potential of urban vegetation: From a multi-trait approach to modeling

The ecosystem services provided by urban forests contribute to ameliorate air quality and human well-being in cities. An integrated approach based on direct measurements of leaf functional multi-traits and on estimation of the plant mitigation potential was used for predicting the species-specific impact on air quality of 29 species, including trees and shrubs, commonly present in the urban context. In addition, volatile organic compound (VOC) emissions and ozone forming potential (OFP) of each species were evaluated. At plant levels, pollution deposition equations and the i-Tree Eco model were applied for estimating particulate (PM10) and ozone (O3) removal potential and for calculating carbon dioxide (CO2) storage and sequestration by the studied species. The results highlight the plant species-specific ability to capture atmospheric pollutants based on their physiological (CO2 assimilation and stomatal conductance) and morphological (stomata, trichomes, waxes and cuticular ornamentation) leaf traits. Trees with abundant trichomes, waxes and wrinkled leaf surfaces are considered more suitable for capturing pollutants. Most of the studied species are suitable for urban planning programs as they result for the majority low VOC emitters and consequently are characterized by low or moderate OFP. Annual O3 and PM10 removal of the investigated trees species ranged from about 58–140 g plant−1 yr−1 and from about 17–139 g plant−1 yr−1, respectively. Total tree CO2 storage ranged from about 164–215 kg plant−1 and gross annual CO2 sequestration from 11 to 20 kg plant−1 year−1. Liriodendron tulipifera, Celtis australis, Acer campestre and Acer platanoides, were efficient species in capturing PM10 and absorbing O3. Prunus cerasifera, Quercus cerris, together with Celtis australis, Acer campestre and Acer platanoides, were efficient for carbon sequestration and storage. As aspected, lower potential of pollutant removal and CO2 storage and sequestration were estimated for shrubs, due to their smaller leaf area and structure.

Daytime atmospheric oxidation capacity in four Chinese megacities during the photochemically polluted season: a case study based on box model simulation

Abstract. Atmospheric oxidation capacity is the basis for converting freshly emitted substances into secondary products and is dominated by reactions involving hydroxyl radicals (OH) during daytime. In this study, we present in situ measurements of ROx radical (hydroxy OH, hydroperoxy HO2, and organic peroxy RO2) precursors and products; the measurements are carried out in four Chinese megacities (Beijing, Shanghai, Guangzhou, and Chongqing) during photochemically polluted seasons. The atmospheric oxidation capacity is evaluated using an observation-based model and radical chemistry precursor measurements as input. The radical budget analysis illustrates the importance of HONO and HCHO photolysis, which account for ∼50 % of the total primary radical sources. The radical propagation is efficient due to abundant NO in urban environments. Hence, the production rate of secondary pollutants, that is, ozone (and fine-particle precursors (H2SO4, HNO3, and extremely low volatility organic compounds, ELVOCs) is rapid, resulting in secondary air pollution. The ozone budget demonstrates its high production in urban areas; also, its rapid transport to downwind areas results in rapid increase in local ozone concentrations. The O3–NOx–VOC (volatile organic compound) sensitivity tests show that ozone production is VOC-limited and that alkenes and aromatics should be mitigated first for ozone pollution control in the four studied megacities. In contrast, NOx emission control (that is, a decrease in NOx) leads to more severe ozone pollution. With respect to fine-particle pollution, the role of the HNO3–NO3 partitioning system is investigated using a thermal dynamic model (ISORROPIA 2). Under high relative humidity (RH) and ammonia-rich conditions, nitric acid converts into nitrates. This study highlights the efficient radical chemistry that maintains the atmospheric oxidation capacity in Chinese megacities and results in secondary pollution characterized by ozone and fine particles.

Modelling and testing of VOC source suppression effect of building materials modified with adsorbents

Volatile organic compounds (VOCs) emitted from decorative building materials are the main source of indoor air pollution, which endangers human health. Source control is the most direct method to reduce the amount of harmful substances emitted from a material. In view of the excellent adsorption performance and effective fixation of the adsorbent on VOC molecules, small amounts of adsorbents can be blended into the raw materials used in the production of building materials, which results in the manufacture of modified building materials with low VOC emissions. According to the type and ratio of additional adsorbents, the VOC emission characteristics of the modified building materials vary. Based on the analysis of the multi-component and multi-scale mass transfer mechanism, a prediction system for the VOC emission characteristics of modified building materials was proposed. Four types of adsorbents, namely, wood-based activated carbon (WAC), shell activated carbon (SAC), coconut shell activated carbon (CSAC), and potassium permanganate impregnated alumina (PIA) were used to manufacture the modified medium density fiberboards. Moreover, pore structure characterization tests and environmental chamber tests were conducted to verify the accuracy of the theoretical prediction system. The results revealed that an absorbent with a high partition coefficient has a more significant source suppression effect. The proposed VOC emission characteristic prediction system for modified building materials can optimize the type and ratio of adsorbents for engineering applications and therefore, provide a basis for the selection of effective VOC source control strategies.

A cool comparison of black and white pepper grades

Black pepper (BP) is globally the most widely used spice and is appreciated for its aroma and taste qualities. Its aroma is influenced by various factors. In the current study, we examined a reference set of 90 quality BP and 40 quality white pepper (WP) samples from the EU spice industry for their volatile organic compounds (VOC) by Proton Transfer Reaction - Mass Spectrometry, as well as 10 low-grade pepper (LG) samples (light berries, rejects, spent). Furthermore, 50 retail BP and 30 WP samples were compared with the reference set. The predominant VOC measured were terpenes. BP presented the most abundant VOC profiles, followed by the WP group, and - at some distance - by the LG pepper material. Reference BP exhibited significantly higher intensities for 41% of the masses compared to WP, and the LG group lower intensities than both BP and WP for 27% of the masses. When using mass 137, the monoterpenes marker, retail samples presented significantly lower VOC intensities than their reference counterparts in case of 42% of the retail BP and 70% of the WP samples. Those samples may have suffered from poor storage conditions during production or potential adulteration or substitution with LG material.

Characterization of Volatile Organic Compound Metabolites in Cigarette Smokers, Electronic Nicotine Device Users, Dual Users, and Nonusers of Tobacco.

Limited research exists about the possible cardiovascular effects of electronic nicotine delivery systems (ENDS). We therefore sought to compare exposure to known or potentially cardiotoxic volatile organic compounds (VOCs) in ENDS users, smokers, and dual users. A total of 371 individuals from the Cardiovascular Injury due to Tobacco Use study, a cross-sectional study of healthy participants aged 21-45 years, were categorized as nonusers of tobacco (n = 87), sole ENDS users (n = 17), cigarette smokers (n = 237), and dual users (n = 30) based on 30-day self-reported tobacco product use patterns. Participants provided urine samples for VOC and nicotine metabolite measurement. We assessed associations between tobacco product use and VOC metabolite measures using multivariable-adjusted linear regression models. Mean (SD) age of the population was 32 (±6.8) years, 55% men. Mean urinary cotinine level in nonusers of tobacco was 2.6 ng/mg creatinine, whereas cotinine levels were similar across all tobacco product use categories (851.6-910.9 ng/mg creatinine). In multivariable-adjusted models, sole ENDS users had higher levels of metabolites of acrolein, acrylamide, acrylonitrile, and xylene compared with nonusers of tobacco, but lower levels of most VOC metabolites compared with cigarette smokers or dual users. In direct comparison of cigarettes smokers and dual users, we found lower levels of metabolites of styrene and xylene in dual users. Although sole ENDS use may be associated with lower VOC exposure compared to cigarette smoking, further study is required to determine the potential health effects of the higher levels of certain reactive aldehydes, including acrolein, in ENDS users compared with nonusers of tobacco. ENDS use in conjunction with other tobacco products may not significantly reduce exposure to VOC, but sole use does generally reduce some VOC exposure and warrants more in-depth studies.

Direct pathway cloning of the sodorifen biosynthetic gene cluster and recombinant generation of its product in E. coli

BackgroundSerratia plymuthica WS3236 was selected for whole genome sequencing based on preliminary genetic and chemical screening indicating the presence of multiple natural product pathways. This led to the identification of a putative sodorifen biosynthetic gene cluster (BGC). The natural product sodorifen is a volatile organic compound (VOC) with an unusual polymethylated hydrocarbon bicyclic structure (C16H26) produced by selected strains of S. plymuthica. The BGC encoding sodorifen consists of four genes, two of which (sodA, sodB) are homologs of genes encoding enzymes of the non-mevalonate pathway and are thought to enhance the amounts of available farnesyl pyrophosphate (FPP), the precursor of sodorifen. Proceeding from FPP, only two enzymes are necessary to produce sodorifen: an S-adenosyl methionine dependent methyltransferase (SodC) with additional cyclisation activity and a terpene-cyclase (SodD). Previous analysis of S. plymuthica found sodorifen production titers are generally low and vary significantly among different producer strains. This precludes studies on the still elusive biological function of this structurally and biosynthetically fascinating bacterial terpene.ResultsSequencing and mining of the S. plymuthica WS3236 genome revealed the presence of 38 BGCs according to antiSMASH analysis, including a putative sodorifen BGC. Further genome mining for sodorifen and sodorifen-like BGCs throughout bacteria was performed using SodC and SodD as queries and identified a total of 28 sod-like gene clusters. Using direct pathway cloning (DiPaC) we intercepted the 4.6 kb candidate sodorifen BGC from S. plymuthica WS3236 (sodA–D) and transformed it into Escherichia coli BL21. Heterologous expression under the control of the tetracycline inducible PtetO promoter firmly linked this BGC to sodorifen production. By utilizing this newly established expression system, we increased the production yields by approximately 26-fold when compared to the native producer. In addition, sodorifen was easily isolated in high purity by simple head-space sampling.ConclusionsGenome mining of all available genomes within the NCBI and JGI IMG databases led to the identification of a wealth of sod-like pathways which may be responsible for producing a range of structurally unknown sodorifen analogs. Introduction of the S. plymuthica WS3236 sodorifen BGC into the fast-growing heterologous expression host E. coli with a very low VOC background led to a significant increase in both sodorifen product yield and purity compared to the native producer. By providing a reliable, high-level production system, this study sets the stage for future investigations of the biological role and function of sodorifen and for functionally unlocking the bioinformatically identified putative sod-like pathways.

Coating aerosolized nanoparticles with low-volatile organic compound (LVOC) vapors modifies surface functionality and oxidative reactivity

Engineered nanoparticles (ENPs) released into the environment have a high probability of interacting with other pollutants before human exposure. These interactions can modify the physicochemical characteristics of ENPs' surface functionality. The toxicity of ENPs can thus largely depend on the coatings picked up in the environment rather than particle core alone. We built a dynamic system to simulate this barely-studied scenario and open up a novel and convenient way to form hydrophobic coatings directly on airborne ENPs. We coated airborne ENPs with low-volatile organic compounds (LVOCs)—common pollutants that exhibit a high affinity for surfaces. Measurement of airborne particle size distribution showed an increase in particle size after coating. The coating thickness was adjustable by controlling the parameters of LVOC generator, namely the reaction temperature and the flow rate through LVOC reservoir, to create 5–90 nm coatings. Transmission electron microscopy images and nanotracking analyses of ENPs suspended in liquid were used to further characterize the coating thickness. Both methods suggested that the system yielded stable, replicable, and well controlled surface coatings. ROS generation of the coated ENPs significantly depended on the type and thickness of LVOC coating. Chemically non-reactive coatings led to significantly reduced ROS generation of silver-ENPs with a 20 nm inert coating quenching close to 100% of ROS generation; this was attributed to the blocked reactive zones on the ENP surfaces. Chemically reactive anthracene coatings, in contrast, first passivated the surface but then contributed to the redox cycle, leading to an increased generation of ROS, which was at a 90 nm coating thickness comparable to that of bare ENPs. Our results add to the understanding of ENP surface functionality—an important aspect of nanotoxicity. Furthermore, the high controllability of our ENP coating system makes it useful for other applications in inducing hydrophobic coating on airborne ENPs.

Formation of Secondary Organic Aerosols by Germicidal Ultraviolet Light

Ultraviolet (UV) light with a wavelength of 254 nm is known to be germicidal, and thus has been increasingly employed as a method of disinfection for indoor environments. Solar UV wavelengths (300 to 400 nm) are known to initiate the formation of secondary organic aerosol (SOA) particles from the photo-oxidation of volatile organic compounds (VOC) in the atmosphere, but germicidal wavelengths have not been extensively studied for indoor environments. In this work, toluene was exposed to 254 nm UV light in a laboratory photoreactor while varying the conditions of the air, the duration of UV exposure, and the duration of post-UV time. The number of particles formed in the fine particulate matter (PM2.5) size range was measured, and significant levels of particle formation were observed for UV exposure periods of as short as 5 min. The particle formation ranged from 2.4 × 106 particles/m3 for 5 min of UV exposure, to 163.2 × 106 particles/m3 for 15 min of UV exposure, for toluene concentrations in the range of 55 to 85 mg/m3. Particle formation was found to increase at a relative humidity of approximately 20% and higher. Variations in the initial number of particles present did not appear to have a significant effect on the particle formation, suggesting that nucleation was not a controlling factor under these conditions. However, tests in a commercial environment at much lower VOC concentrations and lower UV fluence rates showed no detectable PM2.5 formation, indicating that SOA formation during the intermittent use of germicidal UV may not significantly affect indoor air quality under normal conditions.

Characterization of aerosol chemical composition from urban pollution in Brazil and its possible impacts on the aerosol hygroscopicity and size distribution

We studied the effect of aerosols inorganic chemical composition on the aerosol hygroscopicity of urban pollution in Brazil, where biofuels have been used in large scale. We applied size segregated inorganic chemical composition analysis using ISORROPIA II model and κ-Köhler theory to determine the hygroscopicity parameter (κ) of submicrometer aerosols measured in São Paulo city. The size dependence of organic and black carbon (BC) mass were estimated by chemical mass balance and mean observed values.Results showed ultrafine mode particles with diameter smaller than 100 nm with a relatively K2SO4 and Na2SO4 large amount inducing further growth by diffusive condensation and coagulation of low-volatile organic compounds. The process could lead to modifications of aerosol size distribution and also to formation of more active Cloud Condensation Nuclei (CCN) due to the formation of aerosols with considerably increase of hygroscopicity (>40%). The contribution from BC can decreases up to 40% of the observed hygroscopicities values of particles around 100 nm in diameter.Moreover, we present a parameterization based on aerosol mass fraction to accurately predict κ derived from data of Aerosol Mass Spectrometer (AMS) collected in urban pollution in Brazil. Results are compared to hygroscopicity derived from observations of the pollution plume downwind Manaus, on the northern region of Brazil. Both cases were analogous indicating that, despite the fact of receiving influences of organic components from the forest, the pollution plume of Manaus shows the same characteristics of hygroscopicity, and can be modeled following the same parameterization.

Heterogeneous Ozonolysis of Endocyclic Unsaturated Organic Aerosol Proxies: Implications for Criegee Intermediate Dynamics and Later-Generation Reactions

Unsaturated low-volatile organic compounds have been observed in atmospheric aerosol particles (e.g., aerosols from plants, cooking, and biomass burning) and human skin. Understanding their chemical fates through reactions with ozone at the relevant interfaces is crucial to elucidating the multiphase chemical mechanisms and predicting their environmental and health impacts. In this work, heterogeneous ozonolysis of two endocyclic unsaturated organic aerosol proxies (4-cyclohexene-1,2-diacid and shikimic acid) were studied in a flow tube reactor under different O3 exposure levels and relative humidities (30%, 60%, and 90%). Our results show strong RH dependence for the oxidation kinetics due to aerosol phase state change and secondary chemistry (e.g., parent acids reacting with the produced Criegee Intermediates). The observed multifunctional products are explained by the various Criegee Intermediates mechanisms and later-generation reactions. Three processes that lead to the evolution of first-generation ...

Functionalized nitrogen-doped carbon dot-modified yolk-shell ZnFe2O4 nanospheres with highly efficient light harvesting and superior catalytic activity.

Volatile organic compounds (VOCs), as hazardous gaseous pollutants, have attracted much attention due to their potential threat to both human health and the environment. Accordingly, photocatalysis technology is seen as a promising technology to control low concentration VOCs due to its mild operation conditions, low energy consumption, and mineralization ability. However, there are some issues with photocatalysts, such as low light utility and fast photogenerated carrier recombination, which need to be addressed for practical applications. In this work, novel nitrogen-doped carbon dot (NCD)-modified ZnFe2O4 yolk-shell nanostructure photocatalysts were fabricated for the first time. The yolk-shell structure of ZnFe2O4 efficiently shortened the photogenerated carrier migration path and enhanced light scattering in its void, while the decorated NCDs accelerated the charge transfer from the bulk to the surface. A series of characterizations was conducted to investigate the crystal structure, elemental status, optical properties, and photocatalytic performance of the obtained composite photocatalysts. The NCD-modified ZnFe2O4 yolk-shell photocatalysts exhibited both a wide spectral absorbance and low carrier recombination, resulting in high photocatalytic activity and degradation ability towards gaseous o-dichlorobenzene. Density functional theory (DFT) calculations further revealed that the NCDs effectively promoted charge transfer and weakened the recombination of photo-generated electron-hole pairs. Additionally, in situ Fourier transform infrared (FTIR) spectroscopy was performed to investigate the degradation path in the photocatalytic process, and an electron paramagnetic resonance (EPR) radical trapping experiment was conducted to unveil the reactive oxygen species involved in the system. Combining the results obtained, the synergistic effect in the enhancement of photocatalysis between NCDs and yolk-shell ZnFe2O4 was schematically proposed.

Models for assessment of volatile organic compound diffusivities in leather or leather imitates by mercury intrusion porosimetry test

Recent studies have been conducted on the characteristics of volatile organic compound emissions; most of them are focused on wood-based building materials, scarcely mentioned about leather or leather imitates. The volatile organic compound emissions of these products may cause poor indoor (vehicle cabins included) air quality. This article takes formaldehyde as an example to study its diffusion in leather. The porous structure of leather was characterized by carrying out mercury intrusion porosimetry test. The formaldehyde diffusivities in leather was assessed by Blondeau et al.’s, Ataka et al.’s, and Xiong et al.’s models which represent parallel, equivalent, and series interconnection of pores, respectively, and validated through independent liquid inner tube diffusion film emission experiments. The results demonstrated that the fractal dimension of leather is 2.19, which indicated it is a porous medium with self-similar pore structure. Most of the pores in leather were macro pores with average diameter 16.56 μm which contributed to 95.9% of whole porosity and the meso pore with average diameter 0.60 μm which contributed to 4.1%. As far as the liquid inner tube diffusion film emission experiment shows, the Xiong model agrees much better with the experimental results than the other two. The two kinds of pores were considered to be serially connected. It is useful for predicting volatile organic compounds diffusion coefficient in a short time and can be applied to the design and development of low volatile organic compound emission leather or leather imitates within further research.

Fabrication of Perovskite Films with Long Carrier Lifetime for Efficient Perovskite Solar Cells from Low-Toxicity 1-Ethyl-2-Pyrrolidone

High-quality perovskite films with large grains and long carrier lifetime are crucial for efficient solar cells. It is a simple and effective way to increase the perovskite grain size by adding some additives in the precursor solution. Here, we use a low-toxicity and low-volatility organic compound of 1-ethyl-2-pyrrolidone (NEP) as an additive in the PbI2(PbBr2)/dimethylformamide precursor solution to form a Lewis adduct of PbI2·NEP, which facilitate forming perovskite intermediate embedded with NEP molecules. The residual NEP molecules are kept in the narrow space between the intermediate film and substrate during annealing by using a closed-steam annealing method, which prolong the dissolution-recrystallization process. With assistance of the residual NEP, high-quality perovskite films with smooth surface, PbI2 free, high crystallinity, large columnar grains, and long carrier lifetime are fabricated. Correspondingly, the power conversion efficiency of the best perovskite solar cells is enhanced signific...

Comprehensive organic emission profiles for gasoline, diesel, and gas-turbine engines including intermediate and semi-volatile organic compound emissions

Abstract. Emissions from mobile sources are important contributors to both primary and secondary organic aerosols (POA and SOA) in urban environments. We compiled recently published data to create comprehensive model-ready organic emission profiles for on- and off-road gasoline, gas-turbine, and diesel engines. The profiles span the entire volatility range, including volatile organic compounds (VOCs, effective saturation concentration C*=107–1011 µg m−3), intermediate-volatile organic compounds (IVOCs, C*=103–106 µg m−3), semi-volatile organic compounds (SVOCs, C*=1–102 µg m−3), low-volatile organic compounds (LVOCs, C*≤0.1 µg m−3) and non-volatile organic compounds (NVOCs). Although our profiles are comprehensive, this paper focuses on the IVOC and SVOC fractions to improve predictions of SOA formation. Organic emissions from all three source categories feature tri-modal volatility distributions (“by-product” mode, “fuel” mode, and “lubricant oil” mode). Despite wide variations in emission factors for total organics, the mass fractions of IVOCs and SVOCs are relatively consistent across sources using the same fuel type, for example, contributing 4.5 % (2.4 %–9.6 % as 10th to 90th percentiles) and 1.1 % (0.4 %–3.6 %) for a diverse fleet of light duty gasoline vehicles tested over the cold-start unified cycle, respectively. This consistency indicates that a limited number of profiles are needed to construct emissions inventories. We define five distinct profiles: (i) cold-start and off-road gasoline, (ii) hot-operation gasoline, (iii) gas-turbine, (iv) traditional diesel and (v) diesel-particulate-filter equipped diesel. These profiles are designed to be directly implemented into chemical transport models and inventories. We compare emissions to unburned fuel; gasoline and gas-turbine emissions are enriched in IVOCs relative to unburned fuel. The new profiles predict that IVOCs and SVOC vapour will contribute significantly to SOA production. We compare our new profiles to traditional source profiles and various scaling approaches used previously to estimate IVOC emissions. These comparisons reveal large errors in these different approaches, ranging from failure to account for IVOC emissions (traditional source profiles) to assuming source-invariant scaling ratios (most IVOC scaling approaches).

Preparation of water-dispersible corrosion inhibitors for composite lacquer coatings with excellent properties

Corrosion resistant coatings based on eco-friendly and low-volatile organic compounds have received attention in recent years. In this work, the water-dispersible corrosion inhibitors were prepared from lignin, aniline, and 4-fluoroaniline. We achieved different polymer inhibitors with excellent optimum synergistic effects, and the resulting was shown that the excellent dispersion of inhibitors in deionized water were stable for 3 h, compared to polyaniline (PANI) after 10 min of storage. Then, those inhibitors subsequently composited into the natural lacquer to generate anti-corrosion coatings. As revealed by electrochemical measurements, including Tafel polarization curves and electrochemical impedance spectroscopy (EIS), the composite coatings were exhibited outstanding chemical properties in different corrosive medium. The resulting showed that the corrosion performance of composite lacquer coatings were remarkably improved compared with pure lacquer coating, especially L/PF-73-10 coating.

End-of-life of silicon PV panels: A sustainable materials recovery process

In this paper, the management of end-of-life PV modules based on an advanced eco-sustainable process has been presented and discussed. The thermal removal of the polymeric compounds contained in c-Si PV modules has been investigated to separate and recover Si, Ag, Cu, Al and glass. A two-step thermal process has been employed. In the first step, the rear polymeric layer has been removed without emissions of dangerous fluorinated substances. In the second step, the remaining polymers have been completely removed with low volatile organic compounds (VOCs) emissions. The polymers degradation has been studied at combustion equivalent ratios Φ varying from 0.5 to 2 and at 500 °C.The materials recovery has been evaluated from an environmental point of view and optimized by considering the energy cost, through the identification of the best operating conditions, in terms of temperature, time, atmosphere and gas flow. One hour of heat treatment and a slightly oxidizing atmosphere have been enabled to separate and recover the different materials of the module. The elemental compositions of the PV sample and the residue condensed organic products have been determined. The gaseous degradation products have been characterized by gas chromatographic analysis (GC).

Ambient Volatile Organic Compounds and Racial/Ethnic Disparities in Gestational Diabetes Mellitus: Are Asian/Pacific Islander Women at Greater Risk?

US Asian/Pacific Islander (API) communities experience high air pollution levels. APIs may be predisposed to pancreatic β-cell dysfunction and have the highest prevalence of gestational diabetes mellitus (GDM) compared with other racial/ethnic groups. Exposure to high levels of volatile organic compounds (VOCs) impairs pancreatic β-cell function, leading to insulin resistance, but racial/ethnic differences in this association are unexamined. We analyzed singleton deliveries (n = 220,065) from the Consortium on Safe Labor (2002-2008). Exposure to 14 VOCs in each hospital referral region was based on modified Community Multiscale Air Quality models. Logistic regression estimated odds ratios for GDM associated with high (≥75th percentile) versus low (<75th percentile) VOC exposure 3 months before conception and during the first trimester of pregnancy. Preconception and first-trimester exposure to high VOC levels was associated with increased odds of GDM among whites and APIs. GDM risk was significantly higher for APIs than whites for most VOCs. Preconception benzene exposure was associated with 29% (95% confidence interval: 12, 47) increased odds of GDM among whites compared with 45% (95% confidence interval: 16, 81) increased odds among APIs. These findings highlight environmental health disparities affecting pregnant women. Increased focus on GDM risk in US API communities is warranted.

Quantitative constraints on autoxidation and dimer formation from direct probing of monoterpene-derived peroxy radical chemistry

Organic peroxy radicals (RO2) are key intermediates in the atmospheric degradation of organic matter and fuel combustion, but to date, few direct studies of specific RO2 in complex reaction systems exist, leading to large gaps in our understanding of their fate. We show, using direct, speciated measurements of a suite of RO2 and gas-phase dimers from O3-initiated oxidation of α-pinene, that ∼150 gaseous dimers (C16-20H24-34O4-13) are primarily formed through RO2 cross-reactions, with a typical rate constant of 0.75-2 × 10-12 cm3 molecule-1 s-1 and a lower-limit dimer formation branching ratio of 4%. These findings imply a gaseous dimer yield that varies strongly with nitric oxide (NO) concentrations, of at least 0.2-2.5% by mole (0.5-6.6% by mass) for conditions typical of forested regions with low to moderate anthropogenic influence (i.e., ≤50-parts per trillion NO). Given their very low volatility, the gaseous C16-20 dimers provide a potentially important organic medium for initial particle formation, and alone can explain 5-60% of α-pinene secondary organic aerosol mass yields measured at atmospherically relevant particle mass loadings. The responses of RO2, dimers, and highly oxygenated multifunctional compounds (HOM) to reacted α-pinene concentration and NO imply that an average ∼20% of primary α-pinene RO2 from OH reaction and 10% from ozonolysis autoxidize at 3-10 s-1 and ≥1 s-1, respectively, confirming both oxidation pathways produce HOM efficiently, even at higher NO concentrations typical of urban areas. Thus, gas-phase dimer formation and RO2 autoxidation are ubiquitous sources of low-volatility organic compounds capable of driving atmospheric particle formation and growth.

Influence of relative humidity on the heterogeneous oxidation of secondary organic aerosol

Abstract. Secondary organic aerosol (SOA) is a complex mixture of hundreds of semi-volatile to extremely low-volatility organic compounds that are chemically processed in the atmosphere, including via heterogeneous oxidation by gas-phase radicals. Relative humidity (RH) has a substantial impact on particle phase, which can affect how SOA evolves in the atmosphere. In this study, SOA from dark α-pinene ozonolysis is heterogeneously aged by OH radicals in a flow tube at low and high RH. At high RH (RH =89 %) there is substantial loss of particle volume (∼60 %) at an equivalent atmospheric OH exposure of 3 weeks. In contrast, at low RH (RH =25 %) there is little mass loss (&lt;20 %) at the same OH exposure. Mass spectra of the SOA particles were measured as a function of OH exposure using a vacuum ultraviolet aerosol mass spectrometer (VUV-AMS). The mass spectra observed at low RH overall exhibit minor changes with oxidation and negligible further changes above an OH exposure =2×1012 molecule cm−3 s suggesting limited impact of oxidation on the particle composition. In contrast, the mass spectra observed at high RH exhibit substantial and continuous changes as a function of OH exposure. Further, at high RH clusters of peaks in the mass spectra exhibit unique decay patterns, suggesting different responses of various species to oxidation. A model of heterogeneous oxidation has been developed to understand the origin of the difference in aging between the low- and high-RH experiments. Differences in diffusivity of the SOA between the low- and high-RH experiments alone can explain the difference in compositional change but cannot explain the difference in mass loss. Instead, the difference in mass loss is attributable to RH-dependent differences in the OH uptake coefficient and/or the net probability of fragmentation, with either or both larger at high RH compared to low RH. These results illustrate the important impact of relative humidity on the fate of SOA in the atmosphere.

Aerosol size distribution measurement of electronic cigarette emissions using combined differential mobility and inertial impaction methods: Smoking machine and puff topography influence.

A combination of a real-time high resolution aerosol differential mobility spectrometer (DMS500) and an electrical low pressure impactor (used as a traditional impactor) was applied to simultaneously collect real-time data and analyze particle size by weighing the mass of the aerosol collected on the impactor stages. Nonrefillable fixed-power as well as refillable and power adjustable e-cigarettes (e-cigs) were tested at various puffing flow rates. Two types of smoking machines were used: a smoke cycle simulator that provides instantaneous straight sample delivery to the analyzer and a Human Profile Pump that utilizes two synchronized pistons and operates by sample pull-push mode. Chemical analysis of the major components of e-liquid (propylene glycol, vegetable glycerol, water, and nicotine) was made using a proton nuclear magnetic resonance method. Limited amounts of samples collected on impactor stages were analyzed by liquid chromatography time-of-flight mass-spectrometry to find newly formed semi- or low-volatile organic compounds in e-cig aerosol and by transmission electron microscopy to check for the presence of nanoparticles in e-cig emissions. Differential mobility and inertial impaction methods showed comparable particle size results. Method of aerosol generation (type of the smoking machine) as well as puffing topography affected the e-cig particle size. Newly formed semi- or low-volatile organic compounds as well as metal nanoparticles were found in e-cig aerosol.