Enhancement of Benzene Emissions in Special Combinations of Electronic Nicotine Delivery System Liquid Mixtures.

Electronic nicotine delivery systems (ENDS) are battery-powered devices introduced to the market as safer alternatives to combustible cigarettes. Upon heating the electronic liquid (e-liquid), aerosols are released, including several toxicants, such as volatile organic compounds (VOCs). Benzene has been given great attention as a major component of the VOCs group as it increases cancer risk upon inhalation. In this study, several basic e-liquids were tested for benzene emissions. The Aerosol Lab Vaping Instrument was used to generate aerosols from ENDS composed of different e-liquid combinations: vegetable glycerin (VG), propylene glycol (PG), nicotine (nic), and benzoic acid (BA). The tested mixtures included PG, PG + nic + BA, VG, VG + nic + BA, 30/70 PG/VG, and 30/70 PG/VG + nic + BA. A carboxen polydimethylsiloxane fiber for a solid-phase microextraction was placed in a gas cell to trap benzene emitted from a Sub-Ohm Minibox C device. Benzene was adsorbed on the fiber during the puffing process and for an extra 15 min until it reached equilibrium, and then it was determined using gas chromatography-mass spectrometry. Benzene was quantified in VG but not in PG or the 30/70 PG/VG mixtures. However, benzene concentration increased in all tested mixtures upon the addition of nicotine benzoate salt. Interestingly, benzene was emitted at the highest concentration when BA was added to PG. However, lower concentrations were found in the 30/70 PG/VG and VG mixtures with BA. Both VG and BA are sources of benzene. Enhanced emissions, however, are mostly noticeable when BA is mixed with PG and not VG.

Carrier Solvents of Electronic Nicotine Delivery Systems Alter Pulmonary Surfactant.

In late 2019, hundreds of users of electronic products that aerosolize a liquid for inhalation were hospitalized with a variety of respiratory and gastrointestinal symptoms. While some investigations have attributed the disease to the presence of vitamin E acetate in liquids that also contained tetrahydrocannabinol, some evidence suggests that chronic inhalation of two common solvents used in electronic nicotine delivery systems (ENDS), propylene glycol (PG) and vegetable glycerin (VG), can interfere with the lipid components of pulmonary surfactant and cause or exacerbate pulmonary injury. The interaction between PG, VG, and lung surfactant is not yet understood. This study presents an examination of the molecular interactions of PG and VG with lung surfactant mimicked by 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). The interaction of DPPC and PG-VG is studied by attenuated total reflectance fourier transform infrared spectroscopy. The results showed that PG and VG altered the molecular alignment of the DPPC surfactant. The orientation of the surfactant at the surface of the lung affects the surface tension at the air-water interface, thereby influencing breathing. These findings suggest that chronic aerosolization of the primary solvents in ENDS might alter the function of pulmonary surfactant.

Atmospheric Photosensitization: A New Pathway for Sulfate Formation.

Northern China is regularly subjected to intense wintertime "haze events", with high levels of fine particles that threaten millions of inhabitants. While sulfate is a known major component of these fine haze particles, its formation mechanism remains unclear especially under highly polluted conditions, with state-of-the-art air quality models unable to reproduce or predict field observations. These haze conditions are generally characterized by simultaneous high emissions of SO2 and photosensitizing materials. In this study, we find that the excited triplet states of photosensitizers could induce a direct photosensitized oxidation of hydrated SO2 and bisulfite into sulfate S(VI) through energy transfer, electron transfer, or hydrogen atom abstraction. This photosensitized pathway appears to be a new and ubiquitous chemical route for atmospheric sulfate production. Compared to other aqueous-phase sulfate formation pathways with ozone, hydrogen peroxide, nitrogen dioxide, or transition-metal ions, the results also show that this photosensitized oxidation of S(IV) could make an important contribution to aerosol sulfate formation in Asian countries, particularly in China.

Interfacial photochemistry of biogenic surfactants: a major source of abiotic volatile organic compounds.

Films of biogenic compounds exposed to the atmosphere are ubiquitously found on the surfaces of cloud droplets, aerosol particles, buildings, plants, soils and the ocean. These air/water interfaces host countless amphiphilic compounds concentrated there with respect to in bulk water, leading to a unique chemical environment. Here, photochemical processes at the air/water interface of biofilm-containing solutions were studied, demonstrating abiotic VOC production from authentic biogenic surfactants under ambient conditions. Using a combination of online-APCI-HRMS and PTR-ToF-MS, unsaturated and functionalized VOCs were identified and quantified, giving emission fluxes comparable to previous field and laboratory observations. Interestingly, VOC fluxes increased with the decay of microbial cells in the samples, indicating that cell lysis due to cell death was the main source for surfactants and VOC production. In particular, irradiation of samples containing solely biofilm cells without matrix components exhibited the strongest VOC production upon irradiation. In agreement with previous studies, LC-MS measurements of the liquid phase suggested the presence of fatty acids and known photosensitizers, possibly inducing the observed VOC production via peroxy radical chemistry. Up to now, such VOC emissions were directly accounted to high biological activity in surface waters. However, the results obtained suggest that abiotic photochemistry can lead to similar emissions into the atmosphere, especially in less biologically-active regions. Furthermore, chamber experiments suggest that oxidation (O3/OH radicals) of the photochemically-produced VOCs leads to aerosol formation and growth, possibly affecting atmospheric chemistry and climate-related processes, such as cloud formation or the Earth's radiation budget.

Poor regulation implications in a low and middle income country based on PAH source apportionment and cancer risk assessment.

Ambient particle-bound polycyclic aromatic hydrocarbons (PAHs) were collected for one year at an urban background site, and spatially and temporally compared to yearly averages in three coastal cities in Lebanon. The samples were quantified using gas chromatography-mass spectrometry (GC-MS) and source apportioned with an optimized robust method using positive matrix factorization (PMF). Three major sources were found to contribute to PAH emissions at the urban background site, namely, traffic (48%), diesel generators (23%), and incineration (29%). The cancer risk was found higher than what was measured at the same site in previous years with an increase of 35%. Improper regulations of the sources (incineration, power plant, diesel generators and traffic) identified in the different sites resulted in PAH intraurban variability. It is essential to study the chemical components of particulate matter (PM) in order to assess toxicity. In particular, particle-bound PAHs and their oxidation products are known for their carcinogenicity as well as their persistence in the atmosphere, which facilitate their transport to new locations. In the absence of law enforcement, unregulated sources and their total contribution to ambient PAHs present a major health risk. This calls for the attention of development funding agencies and their need to implement sustainable "carbon-free" funding strategies in support of urban development of low and middle-income countries (LMICs).

Author Correction: Interfacial photochemistry at the ocean surface is a global source of organic vapors and aerosols.

The authors became aware of a mistake in the data displayed in the original version of the paper. Specifically, for the calculation of the total emission estimates (i.e., from an average molecular weight and summed laboratory production values for all VOCs), the authors mistakenly added seasonal estimates to the annual estimates because both values are stored in the same variable of the code. Eventually, this additional sum resulted in a doubling of emission estimates.As a result of this, the following changes have been made to the originally published version of this Article:The fifth sentence of the abstract originally read "Our results indicate global emissions of 46.4-184 Tg C yr-1 of organic vapors from the oceans into the marine atmosphere and a potential contribution to organic aerosol mass of more than 60% over the remote ocean." In the corrected version "46.4-184 Tg C yr-1" is replaced by "23.2-91.9 Tg C yr-1"The seventh sentence of the second paragraph of the Introduction originally read "We infer global emissions of 65.0-257 Tg yr-1 (46.4-184 Tg C yr-1) of organic vapors from the oceans into the marine atmosphere." In the corrected version, "65.0-257 Tg yr-1 (46.4-184 Tg C yr-1)" is replaced by "32.5-129 Tg C yr-1 (23.2-91.9 Tg C yr-1)".The last sentence of the first paragraph of the Results subheading "Marine isoprene emissions from interfacial photochemistry" originally read "In the same way, we infer total emissions of organic vapors from abiotic interfacial photochemistry in the range of 65.0-257 Tg yr-1 (46.4-184 Tg C yr-1), hence, contributing significantly to marine VOC emissions." In the corrected version, "65.0-257 Tg yr-1 (46.4-184 Tg C yr-1)" is replaced by "32.5-129 Tg C yr-1 (23.2-91.9 Tg C yr-1)".This has been corrected in both the PDF and the HTML versions of the Article. While the new estimates are lower than previously reported this error does not affect the original discussion or conclusions of the Article. The authors apologize for the confusion caused by this mistake.

Interfacial photochemistry at the ocean surface is a global source of organic vapors and aerosols.

The surface of the oceans acts as a global sink and source for trace gases and aerosol particles. Recent studies suggest that photochemical reactions at this air/water interface produce organic vapors, enhancing particle formation in the atmosphere. However, current model calculations neglect this abiotic source of reactive compounds and account only for biological emissions. Here we show that interfacial photochemistry serves as a major abiotic source of volatile organic compounds (VOCs) on a global scale, capable to compete with emissions from marine biology. Our results indicate global emissions of 46.4-184 Tg C yr-1 of organic vapors from the oceans into the marine atmosphere and a potential contribution to organic aerosol mass of more than 60% over the remote ocean. Moreover, we provide global distributions of VOC formation potentials, which can be used as simple tools for field studies to estimate photochemical VOC emissions depending on location and season.

Development of an analytical methodology for obtaining quantitative mass concentrations from LAAP-ToF-MS measurements.

Laser ablation aerosol particle-time of flight mass spectrometer (LAAP-ToF-MS) measures the size number of particles, and chemical composition of individual particles in real-time. LAAP-ToF-MS measurements of chemical composition are difficult to quantify, mostly because the instrument sensitivities to various chemical species in the multicomponent atmospheric aerosol particles are unknown. In this study, we investigate a field-based approach for quantitative measurements of ammonium, nitrate, sulfate, OC, and EC, in size-segregated atmospheric aerosols, by LAAP-ToF-MS using concurrent measurements from high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), and multi-angle absorption photometer (MAAP). An optical particle counter (OPC) and a high-resolution nanoparticle sizer (scanning mobility particle sizer, or SMPS), were used to measure the particle size distributions of the particles in order to correct the number concentrations. The intercomparison reveals that the degree of agreement of the mass concentrations of each compound measured with LAAP-ToF-MS and HR-ToF-AMS/MAAP increases in the following order NH4+ < SO42- < NO3- < EC < OC < Cl- with r2 values in the range of 0.4-0.95 and linear regression slopes ranging between 0.62 and 1.2. The factors that affect the mass concentrations measured by LAAP-ToF-MS are also discussed in details. Yet, the matrix effect remains one of the strongest limiting factor to achieve an absolute quantification of the aerosol chemical composition. In the future we suggest the development of a methodology based on the calculation of the response factors generated by different types of particles, which could possibly resolve certain difficulties associated with the matrix effect.

Validation of Direct Analysis Real Time source/Time-of-Flight Mass Spectrometry for organophosphate quantitation on wafer surface.

Microelectronic wafers are exposed to airborne molecular contamination (AMC) during the fabrication process of microelectronic components. The organophosphate compounds belonging to the dopant group are one of the most harmful groups. Once adsorbed on the wafer surface these compounds hardly desorb and could diffuse in the bulk of the wafer and invert the wafer from p-type to n-type. The presence of these compounds on wafer surface could have electrical effect on the microelectronic components. For these reasons, it is of importance to control the amount of these compounds on the surface of the wafer. As a result, a fast quantitative and qualitative analytical method, nondestructive for the wafers, is needed to be able to adjust the process and avoid the loss of an important quantity of processed wafers due to the contamination by organophosphate compounds. Here we developed and validated an analytical method for the determination of organic compounds adsorbed on the surface of microelectronic wafers using the Direct Analysis in Real Time-Time of Flight-Mass Spectrometry (DART-ToF-MS) system. Specifically, the developed methodology concerns the organophosphate group.

Validation of thermodesorption method for analysis of semi-volatile organic compounds adsorbed on wafer surface.

To prevent the degradation of the device characteristics it is important to detect the organic contaminants adsorbed on the wafers. In this respect, a reliable qualitative and quantitative analytical method for analysis of semi-volatile organic compounds which can adsorb on wafer surfaces is of paramount importance. Here, we present a new analytical method based on Wafer Outgassing System (WOS) coupled to Automated Thermal Desorber-Gas chromatography-Mass spectrometry (ATD-GC-MS) to identify and quantify volatile and semi-volatile organic compounds from 6", 8" and 12" wafers. WOS technique allows the desorption of organic compounds from one side of the wafers. This method was tested on three important airborne contaminants in cleanroom i.e. tris-(2-chloroethyl) phosphate (TCEP), tris-(2-chloroisopropyl) phosphate (TCPP) and diethyl phthalate (DEP). In addition, we validated this method for the analysis and quantification of DEP, TCEP and TCPP and we estimated the backside organic contamination which may contribute to the front side of the contaminated wafers. We are demonstrating that WOS/ATD-GC-MS is a suitable and highly efficient technique for desorption and quantitative analysis of organophosphorous compounds and phthalate ester which could be found on the wafer surface.

Chemometric tools to highlight possible migration of compounds from packaging to sunflower oils.

Polyethylene terephthalate (PET) could be considered for the packaging of vegetable oils taking into account the impact of its oxygen permeability on the oxidation of the oil and the migration of volatile organic compounds (VOC) from the polymer matrix. After accelerated aging tests at 40 °C for 10, 20, and 30 days, the headspace of three sunflower oils packed in PET with high density polyethylene caps was carried out using solid phase microextraction. VOCs such as benzene hydrocarbons, ethylbenzene, xylene isomers and diethyl phthalate were identified in vegetable oils by gas chromatography coupled to mass spectrometry. Chemometric tools such as principal components analysis (PCA), independent components analysis (ICA), and a multiblocks analysis, common components and specific weight analysis (CCSWA) applied to analytical data were revealed to be very efficient to discriminate between samples according to oil oxidation products (hexanal, heptanal, 2-pentenal) and to the migration of packaging contaminants (xylene).