Low Volatile Organic Compounds Research Articles

Nanoporous Semicrystalline Syndiotactic Polystyrene with Sulfonated Amorphous Phase, for a Fast and Efficient Removal of VOC Pollutant Traces From Water

SummarySyndiotactic polystyrene films and aerogels with nanoporous crystalline phase and sulfonated amorphous phase have been prepared and characterized. The nanoporous nature of the crystalline phase confers to these materials a high solubility of volatile organic compounds (VOCs) from aqueous solutions even at low VOC concentrations while the sulfonation of the amorphous phase enhance the VOC sorption kinetics. These combined properties make these materials particularly interesting for a potential use as a sorption medium to remove traces of pollutants from water. Different aspects relative to the preparation, the structure and the transport properties of these innovative polymeric materials are described.

Bio-based waterborne polyurethane/carbon dot nanocomposite as a surface coating material

Abstract Waterborne surface coating materials with low volatile organic compounds (VOCs) are environmentally friendly and hence the most desired materials for the modern society. The present study reports in situ fabricated thermosetting hyperbranched waterborne polyurethane (WPU)/carbon dot (CD) nanocomposites as surface coating materials. CD was used as a nanoreinforcing agent (at 0.25, 0.5 and 1.0 weight percentages) in the nanocomposites. The structures of the waterborne polyurethane and its fabricated thermosetting nanocomposites were analyzed by using different spectroscopic and analytical tools like Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, UV–visible spectroscopy and X-ray diffractometry. The mechanical properties of the pristine thermosetting WPU were significantly improved after incorporation of CD (tensile strength from 4.5 to 8.5 MPa, elongation at break value from 96 to 136%, scratch hardness from 3 to 9 kg, impact strength from 70 to 100 cm). The thermal stability of WPU also enhanced from 250 to 280 °C after incorporation of CD in the matrix. Interestingly, the fabricated nanocomposites demonstrated an excitation wavelength and concentration dependent photoluminance behavior as well as exhibited good transparency. Thus, the fabricated WPU nanocomposites show great potential as low VOC containing environment friendly transparent surface coating material.

Computational Study of Hydrogen Shifts and Ring-Opening Mechanisms in α-Pinene Ozonolysis Products.

Autoxidation by sequential peroxy radical hydrogen shifts (H-shifts) and O2 additions has recently emerged as a promising mechanism for the rapid formation of highly oxidized, low-volatility organic compounds in the atmosphere. A key prerequisite for autoxidation is that the H-shifts of the initial peroxy radicals formed by, e.g., OH or O3 oxidation are fast enough to compete with bimolecular sink reactions. In most atmospheric conditions, these restrict the lifetime of peroxy radicals to be on the order of seconds. We have systematically investigated all potentially important (nonmethyl, sterically unhindered) H-shifts of all four peroxy radicals formed in the ozonolysis of α-pinene using density functional (ωB97XD) and coupled cluster [CCSD(T)-F12] theory. In contrast to the related but chemically simpler cyclohexene ozonolysis system, none of the calculated H-shifts have rate constants above 1 s(-1) at 298 K, and most are below 0.01 s(-1). The low rate constants are connected to the presence of the strained cyclobutyl ring in the α-pinene-derived peroxy radicals, which hinders H-shifts both from and across the ring. For autoxidation to yield the experimentally observed highly oxidized products in the α-pinene ozonolysis system, additional ring-opening reaction mechanisms breaking the cyclobutyl ring are therefore needed. We further investigate possible uni- and bimolecular pathways for opening the cyclobutyl ring in the α-pinene ozonolysis system.

A membrane introduction mass spectrometer utilizing ion-molecule reactions for the on-line speciation and quantitation of volatile organic molecules.

The ability of membrane introduction mass spectrometry to quantitatively resolve low molecular weight volatile organic compounds (VOCs) such as benzene, toluene, ethylbenzene and xylene (BTEX) using electron ionization (EI) can be compromised by isobaric interferences. This work focuses on reducing isobaric interferences with ion-molecule reactions in a portable quadrupole ion trap mass spectrometer for the analysis of VOCs. EI was used to produce reagent ions from precursors (chloroform, methyl iodide, trichloroethylene or chlorobenzene) that were continually infused into the helium acceptor phase upstream of the membrane introduction mass spectrometry (MIMS) sampling interface. The reagent ions were selectively stored in the ion trap, and then allowed to react with target VOC analytes in air samples via ion-molecule reactions within the trap storage volume. A variety of reaction times were examined (50-5000 ms), and the resulting product ions were analyzed in positive ion mode. The detection limits achieved were comparable with those obtained using EI (low ppbv), and in some cases better than for EI coupled with tandem mass spectrometry (MS/MS). For the VOCs studied, isobaric interferences were greatly reduced or eliminated using chloroform as a reagent gas. The predominant ionization mechanism was via adduct formation, although charge transfer and hydride abstractions were also observed. An internal standard was shown to be effective at correcting for signal changes due to consumption of reagent ions when complex mixtures were sampled. Ion-molecule reactions were exploited to eliminate isobaric interferences that are often encountered in direct, real-time analysis strategies for atmospheric VOC mixtures. The use of a continuously infused internal standard will improve quantitative results in field applications where analyte concentration and sample complexity may be wide ranging.

Effect of resin content and substrate on the emission of BTEX and carbonyls from low-VOC water-based wall paint.

The primary aim of this work is to explore the effect of resin content and the effect of substrate on the emission of benzene, toluene, ethylbenzene, and xylene (BTEX) and carbonyls from low-VOC water-based wall paint. Four low-volatile organic compound (VOC) paints include paints A (20% acrylic), B (30% acrylic), C (20% polyvinyl acetate), and D (30% polyvinyl acetate) were painted on stainless steel specimen for the study of resin effect. Green calcium silicate, green cement, and stainless steel were painted with paints A and C for the study of substrate effect. Concentrations of the VOCs in the chamber decreased with the elapsed time. Both resin type and resin quantity in paint had effects on VOC emissions. Paints with acrylic resin emitted less BTEX and carbonyls than paints with polyvinyl acetate resin. However, the effects of resin quantity varied with VOCs. Porous substrates were observed to interact more strongly with paints than inert substrates. Both green calcium silicate and green cement substrates have strong power of adsorption of VOCs from wall paints, namely toluene, formaldehyde, acetaldehyde, 2-butanone, methacrolein, butyraldehyde, and benzaldehyde. Some compounds like toluene, formaldehyde, and butyaldehyde were desorbed very slowly from green calcium silicate and green cement substrates.

Observations of new particle formation in enhanced UV irradiance zones near cumulus clouds

Abstract. During the CARRIBA (Cloud, Aerosol, Radiation and tuRbulence in the trade wInd regime over BArbados) campaign, the interaction between aerosol particles and cloud microphysical properties was investigated in detail, which also includes the influence of clouds on the aerosol formation. During two intensive campaigns in 2010 and 2011, helicopter-borne measurement flights were performed to investigate the thermodynamic, turbulent, microphysical, and radiative properties of trade-wind cumuli over Barbados. During these flights, 91 cases with increased aerosol particle number concentrations near clouds were detected. The majority of these cases are also correlated with enhanced irradiance in the ultraviolet (UV) spectral wavelength range. This enhancement reaches values up to a factor of 3.3 greater compared to background values. Thus, cloud boundaries provide a perfect environment for the production of precursor gases for new particle formation. Another feature of cloud edges is an increased turbulence, which may also enhance nucleation and particle growth. The observed events have a mean length of 100 m, corresponding to a lifetime of less than 300 s. This implies that particles with diameters of at least 7 nm grew several nanometers per minute, which corresponds to the upper end of values in the literature (Kulmala et al., 2004). Such high values cannot be explained by sulfuric acid alone; thus extremely low volatility organic compounds (ELVOCs) are probably involved here.

Modelling the contribution of biogenic volatile organic compounds to new particle formation in the Jülich plant atmosphere chamber

Abstract. We used the Aerosol Dynamics gas- and particle-phase chemistry model for laboratory CHAMber studies (ADCHAM) to simulate the contribution of BVOC plant emissions to the observed new particle formation during photooxidation experiments performed in the Jülich Plant-Atmosphere Chamber and to evaluate how well smog chamber experiments can mimic the atmospheric conditions during new particle formation events. ADCHAM couples the detailed gas-phase chemistry from Master Chemical Mechanism with a novel aerosol dynamics and particle phase chemistry module. Our model simulations reveal that the observed particle growth may have either been controlled by the formation rate of semi- and low-volatility organic compounds in the gas phase or by acid catalysed heterogeneous reactions between semi-volatility organic compounds in the particle surface layer (e.g. peroxyhemiacetal dimer formation). The contribution of extremely low-volatility organic gas-phase compounds to the particle formation and growth was suppressed because of their rapid and irreversible wall losses, which decreased their contribution to the nano-CN formation and growth compared to the atmospheric situation. The best agreement between the modelled and measured total particle number concentration (R2 > 0.95) was achieved if the nano-CN was formed by kinetic nucleation involving both sulphuric acid and organic compounds formed from OH oxidation of BVOCs.

Salinity stress effects on direct and indirect defence metabolites in maize

In nature, plants are often exposed to multiple stress factors at the same time. The effects of single biotic or abiotic stresses on plant metabolism are well documented but how plants respond to a combination of these is little researched. Here we studied the effects of high salinity and herbivory on levels of secondary compounds and gene expression associated with defences against insects. Hydroponically grown maize plants were subjected to sodium chloride (1, 50, 100mM NaCl) and/or damage by caterpillars of Spodoptera exigua. Salt-stressed plants showed stunted growth, reduced chlorophyll fluorescence and enhanced levels of reactive oxygen species and 1,4-benzoxazin-3-one aglycones (aBX). Herbivory induced higher transcript levels of the Zm-Bx1 gene involved in aBX biosynthesis and of the Zm-SerPIN gene coding for a serine proteinase inhibitor which might affect plant feeding insects. Herbivory also triggered the emission of volatile organic compounds (VOCs) that are attractive signals for parasitoids and predators and thus regarded as an indirect defence. Herbivore-induced metabolites were differentially affected in salt-stressed plants. High salinity resulted in transient priming of jasmonic acid while aBX levels were reduced in double-stressed plants. Salt stress led to lower herbivore-induced VOC emission per plant but not per unit biomass. However, quantitative shifts in individual compounds were found in both cases. Our study confirms the notion that combined stresses produce a unique phenotype that cannot be derived from single-stress effects. The ecological implications of these changes for organisms from different trophic levels and for plant fitness remain to be tested.

VOC 분해 플라즈마-덤프 연소기 특성

VOCs (Volatile Organic Compounds) are generally generated in the painting process, or at the company and laundry where use organic solvents. The VOCs consist of various hydrocarbons and has low calorific value due to its dilution with atmospheric air. Therefore, the VOCs are difficult to burn by a conventional fuel combustor. In this study, a novel plasma dump combustor was proposed for the treatment of low calorific VOC gases. This combustor was designed a combination of the characteristics in a plasma burner, a dump combustor and a 3D matrix burner. The combustor has good structure for maintaining enough residence time and reaction temperature for stable flame formation and VOC destruction. For investigating the performance characteristics of the plasma dump combustor, an experiment was achieved for VOC feed rate, VOC injector position, etc. Toluene was used as a surrogate of VOC. The novel combustor gave better performance than a conventional combustor, showing that VOC destruction rate and energy efficiency were 89.64% and 12.27 kg/kWh respectively, at feeding rate of 450 L/min of VOC of 3,000 ppm of toluene concentration.

Temperature dependence of source specific volatility basis sets for motor vehicle exhaust

Recent work on emissions testing has focused on developing source specific volatility distributions which could be used to improve emissions inventories. One problem about these volatility profiles is that they are evaluated only at one temperature which is usually 298 K. This study uses a simple statistical model to evaluate the temperature dependence of the source-resolved volatility basis set, considering gasoline and diesel vehicle exhaust. The steps involved (a) fitting a distribution to the emissions data (b) evaluating the goodness of fit using a statistical test (c) updating the volatility bins using the Clausius–Clayperon equation; calculating the heats of vaporization of each volatility class using a regression model (d) assessing how the volatility of different VOC classes-Extremely Low Volatile, Low Volatile, Semi-Volatile, Intermediate Volatile and Volatile Organic Compounds – are affected by temperature. The results indicated that there could be significant changes in gas-particle partitioning of these emissions. For diesel exhaust at 298 K, the fractions are 5.4 × 10−4 (ELVOC), 0.074 (LVOC), 0.76 (SVOC), 0.17 (IVOC) and 10−5 (VOC) respectively. Looking at a window of ∓20 K, the partitioning for 278 K is 3 × 10−3 (ELVOC), 0.26 (LVOC), 0.67 (SVOC), 0.07 (IVOC) with no VOC fraction; while at 318 K it is 1.5 × 10−7 (ELVOC), 9 × 10−3 (LVOC), 0.64 (SVOC), 0.35 (IVOC) and 2 × 10−5 (VOC); demonstrating a significant change with temperature. The parameterizations developed in this work could be used to improve motor vehicle emissions inventory models such as MOVES.

Preparation of Poly(Lactic Acid) Acrylate for UV-Curable Coating Applications

UV-curable process is widely used for paints, inks and adhesives due to its rapid curing, low energy consumption, high efficiency and low volatile organic compounds (VOCs). The objective of this research is to prepare poly(lactic acid) (PLA) based UV-curable coating by using glycolyzed PLA. PLA was glycolyzed by ethylene glycol (EG) at 170°C for 90 minutes. The obtained glycolyzed PLA was reacted with methacrylic anhydride (MAAH) to provide PLA acrylate oligomer. The obtained PLA acrylate oligomer was used in coating formulations with various amounts of photoinitiator and cured under UV radiation. Physical properties of cured coating film were investigated such as pencil hardness, gloss and haze. The results showed that poly(lactic acid) (PLA) based UV-curable coating provided good physical properties.

Formation of Low Volatility Organic Compounds and Secondary Organic Aerosol from Isoprene Hydroxyhydroperoxide Low-NO Oxidation.

Gas-phase low volatility organic compounds (LVOC), produced from oxidation of isoprene 4-hydroxy-3-hydroperoxide (4,3-ISOPOOH) under low-NO conditions, were observed during the FIXCIT chamber study. Decreases in LVOC directly correspond to appearance and growth in secondary organic aerosol (SOA) of consistent elemental composition, indicating that LVOC condense (at OA below 1 μg m(-3)). This represents the first simultaneous measurement of condensing low volatility species from isoprene oxidation in both the gas and particle phases. The SOA formation in this study is separate from previously described isoprene epoxydiol (IEPOX) uptake. Assigning all condensing LVOC signals to 4,3-ISOPOOH oxidation in the chamber study implies a wall-loss corrected non-IEPOX SOA mass yield of ∼4%. By contrast to monoterpene oxidation, in which extremely low volatility VOC (ELVOC) constitute the organic aerosol, in the isoprene system LVOC with saturation concentrations from 10(-2) to 10 μg m(-3) are the main constituents. These LVOC may be important for the growth of nanoparticles in environments with low OA concentrations. LVOC observed in the chamber were also observed in the atmosphere during SOAS-2013 in the Southeastern United States, with the expected diurnal cycle. This previously uncharacterized aerosol formation pathway could account for ∼5.0 Tg yr(-1) of SOA production, or 3.3% of global SOA.

Computational Study of the Clustering of a Cyclohexene Autoxidation Product C6H8O7 with Itself and Sulfuric Acid.

We investigate the molecular interactions between sulfuric acid and a recently reported C6H8O7 ketodiperoxy acid formed through autoxidation from cyclohexene and ozone. Structurally similar but larger ELVOC (extremely low volatility organic compound) products formed from autoxidation of monoterpenes are believed to play a major role in the formation and early growth of atmospheric aerosol particles. Utilizing density functional theory geometries, with a DLPNO-CCSD(T)/def2-QZVPP single point energy correction, the stepwise Gibbs free energies of formation have been calculated, and the stabilities of the molecular clusters have been evaluated. C6H8O7 interacts weakly with both itself and sulfuric acid, with standard free energies of formation (ΔG at 298 K and 1 atm) around or above 0 kcal/mol. This is due to the presence of strong intramolecular hydrogen bonds in the peroxyacid groups of C6H8O7. These stabilize the isolated molecule with respect to its clusters, and lead to unfavorable interaction energies. The addition of sulfuric acid to clusters containing C6H8O7 is somewhat more favorable, but the formed clusters are still far more likely to evaporate than to grow further in atmospheric conditions. These findings indicate that the O/C ratio cannot exclusively be used as a proxy for volatility in atmospheric new particle formation involving organic compounds. The specific molecular structure, and especially the number of strong hydrogen binding moieties, are equally important. The interaction between the C6H8O7 compound and aqueous phase sulfate ions indicates that ELVOC-type compounds can contribute to aerosol mass by effectively partitioning into the condensed phase.

Long term air quality monitoring in a net-zero energy residence designed with low emitting interior products

The National Institute of Standards and Technology (NIST) constructed a Net Zero Energy Residential Test Facility (NZERTF) to support the development and adoption of cost-effective Net Zero Energy (NZE) designs and technologies. One key design objective was to provide for occupant health and comfort through adequate ventilation and reduced indoor contaminant sources. To improve source control, guidelines were implemented to utilize products with relatively low volatile organic compound (VOC) emissions. Indoor and outdoor concentrations of formaldehyde and 30 other VOCs were measured approximately monthly during the first year of house operation. Indoor temperature and ventilation conditions were relatively constant over the study. Indoor minus outdoor (I–O) concentrations of many VOCs varied with outdoor temperature. Correlation analyses of I–O concentrations versus inverse outdoor temperature (1/K) suggested that some building envelope components were an indoor source of aldehydes (but not formaldehyde) and several other VOCs. Floor area specific emission rates were calculated and compared to values from several prior studies of conventional new houses. The average formaldehyde emission factor of 6.7 μg h−1 m−2 in this study was lower than literature values (29 μg h−1 m−2 to 45 μg h−1 m−2) indicating formaldehyde source control approaches were effective. VOC measurements at other indoor conditions demonstrated that eliminating mechanical ventilation contributed more to an increase in indoor VOC concentrations than an 8 °C increase in the indoor temperature.

Calculating Equilibrium Phase Distribution during the Formation of Secondary Organic Aerosol Using COSMOtherm.

Challenges in the parametrization of compound distribution between the gas and particle phase contribute significantly to the uncertainty in the prediction of secondary organic aerosol (SOA) formation and are rooted in the complexity and variability of atmospheric condensed matter, which includes water, salts, and a multitude of organic oxidation products, often in two separated phases. Here, we explore the use of the commercial quantum-chemistry-based software COSMOtherm to predict equilibrium partitioning and Setchenow coefficients of a suite of oxidation products of α-pinene ozonolysis in an aerosol that is assumed to separate into an organic-enriched phase and an electrolyte-enriched aqueous phase. The predicted coefficients are used to estimate the phase distribution of the organic compounds, water and ammonium sulfate, the resulting phase composition, and the SOA yield. Four scenarios that differ in terms of organic loading, liquid water content, and chemical aging are compared. The organic compounds partition preferentially to the organic phase rather than the aqueous phase for the studied aerosol scenarios, partially due to the salting-out effect. Extremely low volatile organic compounds are predicted to be the dominant species in the organic aerosols at low loadings and an important component at higher loadings. The highest concentration of oxidation products in the condensed phase is predicted for a scenario assuming the presence of non-phase-separated cloud droplets. Partitioning into an organic aerosol phase composed of the oxidation products is predicted to be similar to partitioning into a phase composed of a single organic surrogate molecule, suggesting that the calculation procedure can be simplified without major loss of accuracy. COSMOtherm is shown to produce results that are comparable to those obtained using group contribution methods. COSMOtherm is likely to have a much larger application domain than those group contribution methods because it is based on fundamental principles with little calibration.

Volatile organic compounds emitted from silver birch of different provenances across a latitudinal gradient in Finland.

Climate warming is having an impact on distribution, acclimation and defence capability of plants. We compared the emission rate and composition of volatile organic compounds (VOCs) from silver birch (Betula pendula (Roth)) provenances along a latitudinal gradient in a common garden experiment over the years 2012 and 2013. Micropropagated silver birch saplings from three provenances were acquired along a gradient of 7° latitude and planted at central (Joensuu 62°N) and northern (Kolari 67°N) sites. We collected VOCs emitted by shoots and assessed levels of herbivore damage of three genotypes of each provenance on three occasions at the central site and four occasions at the northern site. In 2012, trees of all provenances growing at the central site had higher total VOC emission rates than the same provenances growing at the northern site; in 2013 the reverse was true, thus indicating a variable effect of latitude. Trees of the southern provenance had lower VOC emission rates than trees of the central and northern provenances during both sampling years. However, northward or southward translocation itself had no significant effect on the total VOC emission rates, and no clear effect on insect herbivore damage. When VOC blend composition was studied, trees of all provenances usually emitted more green leaf volatiles at the northern site and more sesquiterpenes at the central site. The monoterpene composition of emissions from trees of the central provenance was distinct from that of the other provenances. In summary, provenance translocation did not have a clear effect in the short-term on VOC emissions and herbivory was not usually intense at the lower latitude. Our data did not support the hypothesis that trees growing at lower latitudes would experience more intense herbivory, and therefore allocate resources to chemical defence in the form of inducible VOC emissions.

Formation of highly oxidized multifunctional compounds: autoxidation of peroxy radicals formed in the ozonolysis of alkenes – deduced from structure–product relationships

Abstract. It has been postulated that secondary organic particulate matter plays a pivotal role in the early growth of newly formed particles in forest areas. The recently detected class of extremely low volatile organic compounds (ELVOC) provides the missing organic vapors and possibly contributes a significant fraction to atmospheric SOA (secondary organic aerosol). The sequential rearrangement of peroxy radicals and subsequent O2 addition results in ELVOC which are highly oxidized multifunctional molecules (HOM). Key for efficiency of such HOM in early particle growth is that their formation is induced by one attack of the oxidant (here O3), followed by an autoxidation process involving molecular oxygen. Similar mechanisms were recently observed and predicted by quantum mechanical calculations e.g., for isoprene. To assess the atmospheric importance and therewith the potential generality, it is crucial to understand the formation pathway of HOM. To elucidate the formation path of HOM as well as necessary and sufficient structural prerequisites of their formation we studied homologous series of cycloalkenes in comparison to two monoterpenes. We were able to directly observe highly oxidized multifunctional peroxy radicals with 8 or 10 O atoms by an Atmospheric Pressure interface High Resolution Time of Flight Mass Spectrometer (APi-TOF-MS) equipped with a NO3−-chemical ionization (CI) source. In the case of O3 acting as an oxidant, the starting peroxy radical is formed on the so-called vinylhydroperoxide path. HOM peroxy radicals and their termination reactions with other peroxy radicals, including dimerization, allowed for analyzing the observed mass spectra and narrowing down the likely formation path. As consequence, we propose that HOM are multifunctional percarboxylic acids, with carbonyl, hydroperoxy, or hydroxy groups arising from the termination steps. We figured that aldehyde groups facilitate the initial rearrangement steps. In simple molecules like cycloalkenes, autoxidation was limited to both terminal C atoms and two further C atoms in the respective α positions. In more complex molecules containing tertiary H atoms or small, constrained rings, even higher oxidation degrees were possible, either by simple H shift of the tertiary H atom or by initialization of complex ring-opening reactions.

Investigating the links between ozone and organic aerosol chemistry in a biomass burning plume from a prescribed fire in California chaparral

Abstract. Within minutes after emission, complex photochemistry in biomass burning smoke plumes can cause large changes in the concentrations of ozone (O3) and organic aerosol (OA). Being able to understand and simulate this rapid chemical evolution under a wide variety of conditions is a critical part of forecasting the impact of these fires on air quality, atmospheric composition, and climate. Here we use version 2.1 of the Aerosol Simulation Program (ASP) to simulate the evolution of O3 and secondary organic aerosol (SOA) within a young biomass burning smoke plume from the Williams prescribed fire in chaparral, which was sampled over California in November 2009. We demonstrate the use of a method for simultaneously accounting for the impact of the unidentified intermediate volatility, semi-volatile, and extremely low volatility organic compounds (here collectively called "SVOCs") on the formation of OA (using the Volatility Basis Set – VBS) and O3 (using the concept of mechanistic reactivity). We show that this method can successfully simulate the observations of O3, OA, NOx, ethylene (C2H4), and OH to within measurement uncertainty using reasonable assumptions about the average chemistry of the unidentified SVOCs. These assumptions were (1) a reaction rate constant with OH of ~ 10-11 cm3 s−1; (2) a significant fraction (up to ~ 50 %) of the RO2 + NO reaction resulted in fragmentation, rather than functionalization, of the parent SVOC; (3) ~ 1.1 molecules of O3 were formed for every molecule of SVOC that reacted; (4) ~ 60 % of the OH that reacted with the unidentified non-methane organic compounds (NMOC) was regenerated as HO2; and (5) that ~ 50 % of the NO that reacted with the SVOC peroxy radicals was lost, presumably to organic nitrate formation. Additional evidence for the fragmentation pathway is provided by the observed rate of formation of acetic acid (CH3COOH), which is consistent with our assumed fragmentation rate. However, the model overestimates peroxyacetyl nitrate (PAN) formation downwind by about 50 %, suggesting the need for further refinements to the chemistry. This method could provide a way for classifying different smoke plume observations in terms of the average chemistry of their SVOCs, and could be used to study how the chemistry of these compounds (and the O3 and OA they form) varies between plumes.

Modeling the Charging of Highly Oxidized Cyclohexene Ozonolysis Products Using Nitrate-Based Chemical Ionization.

Several extremely low volatility organic compounds (ELVOCs) formed in the ozonolysis of endocyclic alkenes have recently been detected in laboratory and field studies. These experiments have been carried out with chemical ionization atmospheric pressure interface time-of-flight mass spectrometers (CI-APi-TOF) with nitrate ions as reagent ions. The nitrate ion binds to the detected species through hydrogen bonds, but it also binds very strongly to one or two neutral nitric acid molecules. This makes the measurement highly selective when there is an excess amount of neutral nitric acid in the instrument. In this work, we used quantum-chemical methods to calculate the binding energies between a nitrate ion and several highly oxidized ozonolysis products of cyclohexene. These were then compared with the binding energies of nitrate ion-nitric acid clusters. Systematic configurational sampling of the molecules and clusters was carried out at the B3LYP/6-31+G* and ωB97xD/aug-cc-pVTZ levels, and the final single-point energies were calculated with DLPNO-CCSD(T)/def2-QZVPP. The binding energies were used in a kinetic simulation of the measurement system to determine the relative ratios of the detected signals. Our results indicate that at least two hydrogen bond donor functional groups (in this case, hydroperoxide, OOH) are needed for an ELVOC molecule to be detected in a nitrate ion CI-APi-TOF. Also, a double bond in the carbon backbone makes the nitrate cluster formation less favorable.

Highly Oxidized Multifunctional Organic Compounds Observed in Tropospheric Particles: A Field and Laboratory Study.

Very recent studies have reported the existence of highly oxidized multifunctional organic compounds (HOMs) with O/C ratios greater than 0.7. Because of their low vapor pressure, these compounds are often referred as extremely low-volatile organic compounds (ELVOCs), and thus, they are able to contribute significantly to organic mass in tropospheric particles. While HOMs have been successfully detected in the gas phase, their fate after uptake into particles remains unclear to date. Hence, the present study was designed to detect HOMs and related oxidation products in the particle phase and, thus, to shed light on their fate after phase transfer. To this end, aerosol chamber investigations of α-pinene ozonolysis were conducted under near environmental precursor concentrations (2.4 ppb) in a continuous flow reactor. The chemical characterization shows three classes of particle constituents: (1) intact HOMs that contain a carbonyl group, (2) particle-phase decomposition products, and (3) highly oxidized organosulfates (suggested to be addressed as HOOS). Besides chamber studies, HOM formation was also investigated during a measurement campaign conducted in summer 2013 at the TROPOS research station Melpitz. During this field campaign, gas-phase HOM formation was found to be correlated with an increase in the oxidation state of the organic aerosol.