Cis-pinonic Acid Research Articles

Col Margherita Observatory: A background site in the Eastern Italian Alps for investigating the chemical composition of atmospheric aerosols

The chemical composition of atmospheric aerosol collected at the Col Margherita Atmospheric Observatory (46° 22ˈ 0.059ˈˈ N, 11° 47ˈ 30.911ˈˈ E, 2543 m a.s.l.) was investigated during spring and summer 2018. This is the first study of this area and should lead to a better understanding of the aerosol chemical composition in the Southern slope of the Eastern Italian Alps, with the aim of proposing this high altitude site as a background station. Aerosol samples were analyzed to determine several water soluble components (Cl−, Br−, I−, NO3−, SO42−, K+, Mg2+, Na+, NH4+, Ca2+), organic acids (methanesulfonic acid and C2–C7 carboxylic acids), monosaccharides, alcohol-sugars, levoglucosan and its isomers, sucrose, phenolic compounds, free L- and D-amino acids and photo-oxidation products of α-pinene (cis-pinonic acid and pinic acid). The majority of the mass concentration is explained by ionic species, but the other investigated compounds allow us to study other processes or identify the potential sources. Carboxylic acids and photochemical products of α-pinene were used to study photochemical or oxidative processes. Biomass burning input was evaluated using two specific classes of biomarkers: anhydrosugars and phenolic compounds, while biogenic inputs were studied using sugars and free amino acids. None of these water soluble organic compounds have been properly investigated previously in alpine sites because their concentrations in aerosol are very low.

Laboratory study of the heterogeneous ice nucleation on black-carbon-containing aerosol

Abstract. Soot and black carbon (BC) particles are generated in the incomplete combustion of fossil fuels, biomass, and biofuels. These airborne particles affect air quality, human health, aerosol–cloud interactions, precipitation formation, and climate. At present, the climate effects of BC particles are not well understood. Their role in cloud formation is obscured by their chemical and physical variability and by the internal mixing states of these particles with other compounds. Ice nucleation in field studies is often difficult to interpret. Nonetheless, most field studies seem to suggest that BC particles are not efficient ice-nucleating particles (INPs). On the other hand, laboratory measurements show that in some cases, BC particles can be highly active INPs under certain conditions. By working with well-characterized BC particles, our aim is to systematically establish the factors that govern the ice nucleation activity of BC. The current study focuses on laboratory measurements of the effectiveness of BC-containing aerosol in the formation of ice crystals in temperature and ice supersaturation conditions relevant to cirrus clouds. We examine ice nucleation on BC particles under water-subsaturated cirrus cloud conditions, commonly understood as deposition-mode ice nucleation. We study a series of well-characterized commercial carbon black particles with varying morphologies and surface chemistries as well as ethylene flame-generated combustion soot. The carbon black particles used in this study are proxies for atmospherically relevant BC aerosols. These samples were characterized by electron microscopy, mass spectrometry, and optical scattering measurements. Ice nucleation activity was systematically examined in temperature and saturation conditions in the ranges of 217≤T≤235 K and 1.0≤Sice≤1.5 and 0.59≤Swater≤0.98, respectively, using a SPectrometer for Ice Nuclei (SPIN) instrument, which is a continuous-flow diffusion chamber coupled with instrumentation to measure light scattering and polarization. To study the effect of coatings on INPs, the BC-containing particles were coated with organic acids found in the atmosphere, namely stearic acid, cis-pinonic acid, and oxalic acid. The results show significant variations in ice nucleation activity as a function of size, morphology, and surface chemistry of the BC particles. The measured ice nucleation activity dependencies on temperature, supersaturation conditions, and the physicochemical properties of the BC particles are consistent with an ice nucleation mechanism of pore condensation followed by freezing. Coatings and surface oxidation modify the initial formation efficiency of pristine ice crystals on BC-containing aerosol. Depending on the BC material and the coating, both inhibition and enhancement in INP activity were observed. Our measurements at low temperatures complement published data and highlight the capability of some BC particles to nucleate ice under low ice supersaturation conditions. These results are expected to help refine theories relating to soot INP activation in the atmosphere.

Physicochemical Properties of Pinic, Pinonic, Norpinic, and Norpinonic Acids as Relevant α-Pinene Oxidation Products.

Here, the study is focused on the synthesis and determination of physicochemical properties of four α-pinene secondary organic aerosol (SOA) products: cis-pinic acid, cis-pinonic acid, cis-norpinic acid, and cis-norpinonic acid. These encompass their thermal properties, solid-liquid phase equilibria, and dissociation constant (pKa). Thermal properties, including the melting temperature, enthalpy of fusion, temperature, and enthalpy of the phase transitions, were measured with the differential scanning calorimetry technique. These SOA components exhibit relatively high melting temperatures from 364.32 K for cis-pinic acid to 440.68 K for cis-norpinic acid. The enthalpies of fusion vary from 14.75 kJ·mol-1 for cis-norpinic acid to 30.35 kJ·mol-1 for cis-pinonic acid. The solubility in water was determined with the dynamic method (solid-liquid phase equilibria method), and then experimental results were interpreted and correlated using three different mathematical models: Wilson, non-random two-liquid model, and universal quasichemical equations. The results of the correlation indicate that the Wilson equation appears to work the best for all investigated compounds, giving rise to the lowest value of a standard deviation. cis-Norpinic acid and cis-pinic acid (dicarboxylic acids) show better solubility in the aqueous solution than cis-norpinonic acid and cis-pinonic acid (monocarboxylic acids), which affect the multiphase chemistry of α-pinene SOA processes. For cis-pinonic acid and cis-norpinonic acid, also pH-profile solubility was determined. The intrinsic solubility (S0) for cis-norpinonic acid was measured to be 0.05 mmol·dm-3, while for cis-pinonic acid, it was found to be 0.043 mmol·dm-3. The acidity constants (pKa) at 298 and 310 K using the Bates-Schwarzenbach spectrophotometric method were determined. The pKa values at 298.15 K for cis-norpinonic acid and cis-pinonic acid were found to be 4.56 and 5.19, respectively, whereas at 310.15 K, pKa values were found to be -4.76 and 5.25, respectively.

Infrared Ion Spectroscopy of Environmental Organic Mixtures: Probing the Composition of α-Pinene Secondary Organic Aerosol.

Characterizing the chemical composition of organic aerosols can elucidate aging mechanisms as well as the chemical and physical properties of the aerosol. However, the high chemical complexity and often low atmospheric abundance present a difficult analytical challenge. Milligrams or more of material may be needed for speciated spectroscopic analysis. In contrast, mass spectrometry provides a very sensitive platform but limited structural information. Here, we combine the strengths of mass spectrometry and infrared (IR) action spectroscopy to generate characteristic IR spectra of individual, mass-isolated ion populations. Soft ionization combined with in situ infrared ion spectroscopy, using the tunable free-electron laser FELIX, provides detailed information on molecular structures and functional groups. We apply this technique, along with quantum mechanical modeling, to characterize organic molecules in secondary organic aerosol (SOA) formed from the ozonolysis of α-pinene. Spectral overlap with a standard is used to identify cis-pinonic acid. We also demonstrate the characterization of isomers for multiple SOA products using both quantum mechanical computations and analyses of fragment ion spectra. These results demonstrate the detailed structural information on isolated ions obtained by combining mass spectrometry with fingerprint IR spectroscopy.

Insights into the morphology of multicomponent organic and inorganic aerosols from molecular dynamics simulations

Abstract. We explore the morphologies of multicomponent nanoparticles through atomistic molecular dynamics simulations under atmospherically relevant conditions. The particles investigated consist of both organic (cis-pinonic acid – CPA, 3-methyl-1,2,3-butanetricarboxylic acid – MBTCA, n-C20H42, n-C24H50, n-C30H62 or mixtures thereof) and inorganic (sulfate, ammonium and water) compounds. The effects of relative humidity, organic mass content and type of organic compound present in the nanoparticle are investigated. Phase separation is predicted for almost all simulated nanoparticles either between organics and inorganics or between hydrophobic and hydrophilic constituents. For oxygenated organics, our simulations predict an enrichment of the nanoparticle surface in organics, often in the form of islands depending on the level of humidity and organic mass fraction, giving rise to core–shell structures. In several cases the organics separate from the inorganics, especially from the ions. For particles containing water-insoluble linear alkanes, separate hydrophobic and hydrophilic domains are predicted to develop. The surface partitioning of organics is enhanced as the humidity increases. The presence of organics in the interior of the nanoparticle increases as their overall mass fraction in the nanoparticle increases, but this also depends on the humidity conditions. Apart from the organics–inorganics and hydrophobics–hydrophilics separation, our simulations predict a third type of separation (layering) between CPA and MBTCA molecules under certain conditions.

Theoretical study of the cis-pinonic acid and its atmospheric hydrolysate participation in the atmospheric nucleation

cis-Pinonic acid (CPA), one of the major photooxidation products of α-pinene, is believed to contribute to the formation of aerosols formed over forested areas. In the current study, we implement quantum chemical calculation to investigate the interaction between sulfuric acid (SA) and CPA as well as the hydrolysate of CPA (HCPA) in the presence of water or ammonia in the atmosphere. The lowest free energy configurations, reactants, transition states, intermediates, and products were optimized at 298/278K and 1atm at the M06-2X/6-311+G(3df,3pd) level. Our results show that one CPA molecule might initially nucleate with SA molecules and subsequently participate in the formation and growth of the new particle in the form of HCPA. More than one HCPA molecule may be involved in the critical nuclei. Furthermore, the hydrolysis reaction of CPA can be effectively catalyzed by SA and nitric acid (NA) in presence of water, which significantly increases the HCPA content in the atmosphere and subsequently promotes the particle nucleation. Overall, the current study elucidates a new mechanism of atmospheric nucleation driven by CPA and its hydrolysate.

Molecular Characteristics and Formation Mechanisms of Biogenic Secondary Organic Aerosols in the Summer Atmosphere at Mt. Tai on the North China Plain

ABSTRACT To investigate the molecular characteristics and formation mechanisms of biogenic secondary organic aerosol (BSOA), daytime and nighttime PM2.5 samples were collected at the summit of Mt. Tai during the summer of 2016. The critical indicators of primary sources, such as elemental carbon (EC) and levoglucosan, displayed similar values during the daytime and nighttime, suggesting that changes in the boundary layer heights (BLHs) produced only inconsequential effects during the observation campaign. The molecular distributions of the BSOA were dominated by isoprene SOA tracers (68.5 ± 42.6 ng m–3), followed by monoterpene (43.5 ± 24.4 ng m–3) and β-caryophyllene (16.3 ± 8.6 ng m–3) SOA tracers. Due to the higher diurnal temperatures and solar radiation, the concentrations of all of the tracers were higher during the day than at night. The ratio of the combined cis-pinonic and cis-pinic acid to the MBTCA (P/M) was much lower than in Chinese cities and at the Tibetan background site, indicating that the monoterpene SOA was relatively aged in the mountainous atmosphere, in large part because of the stronger solar radiation at the peak of Mt. Tai. The concentrations of the BSOA products exhibited a significantly positive correlation with the level of ozone during the daytime (R2 = 0.58–0.86) and the temperature over the whole sampling period (R2 = 0.37–0.75), as higher temperatures can accelerate the emission of biogenic volatile organic compounds and the formation of SOA. By contrast, the BSOA tracers displayed a negative linear correlation with the relative humidity (RH) (R2 = 0.43–0.84) and the in situ particle pH (pHis) (R2 = 0.55–0.70) because high RH can inhibit the acid-catalyzed formation of BSOA due to the dilution of the aerosol acidity. No correlation between the BSOA tracers and anthropogenic pollutants (e.g., levoglucosan, SO42–, NO3– and EC) was observed during the daytime or nighttime, suggesting that BSOA tracers in the atmosphere of Mt. Tai during summer were primarily derived from the local oxidation of BVOCs rather than long-distance-transported anthropogenic emissions from the lowlands.

Characterization of the water soluble fraction in ultrafine, fine, and coarse atmospheric aerosol

Water soluble organic carbon significantly contributes to aerosol's carbon mass and its chemical composition is poorly characterized due to the huge number of species. In this study, we determined 94 water-soluble compounds: inorganic ions (Cl−, Br−, I−, NO3−, SO42−,K+, Mg+, Na+, NH4+, Ca2+), organic acids (methanesulfonic acid and C2-C7 carboxylic acids), monosaccharides, alcohol-sugars, levoglucosan and its isomers, sucrose, phenolic compounds, free l- and d-amino acids and photo-oxidation products of α-pinene (cis-pinonic acid and pinic acid). The sampling was conducted using a micro-orifice uniform deposit impactor (MOUDI) at the urban area of Mestre-Venice from March to May 2016. The main aim of this work is to identify the source of each detected compound, evaluating its particle size distribution. Clear differences in size distributions were observed for each class of analyzed compounds.The positive matrix factorization (PMF) model was used to identify six factors related to different sources: a) primary biogenic aerosol particles with particle size > 10 μm; b) secondary sulfate contribution; c) biomass burning; d) primary biogenic aerosol particles distributed between 10 and 1 μm; e) an aged sea salt input and f) SOA pinene. Each factor was also characterized by different composition in waters soluble compounds and different particles size distribution.

Aqueous-Phase Oxidation of Terpene-Derived Acids by Atmospherically Relevant Radicals.

Terpene-derived acids formed through the atmospheric gas-phase oxidation of terpenes are able to efficiently undergo a phase transfer into the aqueous phase. The subsequent aqueous-phase oxidation of such compounds has not been intensely studied. Accordingly, the aqueous-phase second-order rate constants of the oxidation reactions of cis-pinonic acid (CPA) and (+)-camphoric acid (+CA) with hydroxyl radicals (•OH), nitrate radicals (NO3•), and sulfate radicals (SO4•-) were investigated as a function of temperature and pH in the present study. For CPA and +CA the following •OH reaction rate constants at T = 298 K are determined: ksecond(CPA, pH<2) = (2.8 ± 0.1) × 109 L mol-1 s-1, ksecond(CPA, pH>8) = (2.7 ± 0.3) × 109 L mol-1 s-1, ksecond(+CA, pH<2) = (2.1 ± 0.1) × 109 L mol-1 s-1, ksecond(+CA, pH=5.3) = (2.7 ± 0.3) × 109 L mol-1 s-1, ksecond(+CA, pH>8) = (2.7 ± 0.1) × 109 L mol-1 s-1. In order to assess the atmospheric impact of the aqueous-phase oxidation of such compounds, atmospheric aqueous-phase lifetimes were calculated for two model scenarios based on CAPRAM 3.0i. The aqueous-phase oxidation under remote conditions emerges to be the most favored pathway with lifetimes of 5 ± 1 h.

Reactivity of Monoterpene Criegee Intermediates at Gas-Liquid Interfaces.

Biogenic monoterpenes are major sources of Criegee intermediates (CIs) in the troposphere. Recent studies underscored the importance of their heterogeneous chemistry. The study of monoterpene CI reactions on liquid surfaces, however, is challenging due to the lack of suitable probes. Here, we report the first mass spectrometric detection of the intermediates and products, which include labile hydroperoxides, from reactions of CIs of representative monoterpenes (α-terpinene, γ-terpinene, terpinolene, d-limonene, α-pinene) with water, cis-pinonic acid (CPA) and octanoic acid (OA) on the surface of liquid microjets. Significantly, the relative yields of α-hydroxy-hydroperoxides production from CIs hydration at the gas-liquid interface-α-terpinene (1.00) ≫ d-limonene (0.18) > γ-terpinene (0.11) ∼ terpinolene (0.10) ≫ α-pinene (0.01)-do not track the rate constants of their gas-phase ozonolyses. Notably, in contrast with the inertness of the other CIs, the CIs derived from α-terpinene ozonolysis readily react with CPA and OA to produce C20 and C18 ester hydroperoxides, respectively. Present results reveal hitherto unknown structural effects on the reactivities of CIs at aqueous interfaces.

Reactions of Criegee Intermediates with Benzoic Acid at the Gas/Liquid Interface.

Secondary organic aerosol (SOA) found in polluted mega-cities contains benzoic acid (BA) as a major organic acid in addition to a variety of species including alkenes. In polluted air, ozone could be a major oxidizer for SOA and induces subsequent reactions involving Criegee intermediates (CIs, carbonyl oxide, RR'C•-O-O•/RR'C═O+-O-) formed by the -C═C- + O3 reaction at the gas/liquid interface. The possibility that abundant BA could be an effective scavenger of CIs at the interface remains to be investigated by direct experiments. Here, we showed that amphiphilic BA is able to compete with water molecules for the CIs produced in the prompt ozonolysis of β-caryophyllene on the surface of a water/acetonitrile solvent microjet by generating hitherto uncharacterized C22 ester hydroperoxide products. Competition between BA vs octanoic acid vs cis-pinonic acid toward CIs reveals that BA is a much less-efficient scavenger of CIs on aqueous organic surfaces. We attribute it to the surface-specific orientation of BA at the gas/liquid interface, where the reactive -C(O)OH group is fully hydrated and not available for CIs generated at the topmost layers.

Organic molecular tracers in atmospheric PM1 at urban intensive traffic and background sites in two high-insolation European cities

Atmospheric PM1 has an impact on health and the environment, and is highly variable. PM1 filter samples were collected in urban roof and street sites in two Mediterranean cities in Europe (Barcelona and Madrid) to study the spatial and temporal trends of primary and secondary organic tracer compounds. Both cities are exposed to modern urban emission sources with intensive traffic in their centers. Moreover, their geographical situation in the Mediterranean region favors photo-chemical reactions and accumulation of secondary aerosols, due to sunny anti-cyclonic weather conditions. Barcelona is located along the coast with high relative humidity and an active sea-mountain breeze system, while the relative humidity in Madrid is low in summer, due to its location in the center of the Iberian Peninsula. These differences may influence the accumulation of primary air pollutants and the formation of secondary aerosols. In street site samples, the levels of primary organics, such as polycyclic aromatic hydrocarbons, hopanes and nicotine, were about two times higher than those collected simultaneously at roof sites. Primary emitted levoglucosan and isomers from biomass burning were observed in higher concentrations in winter in both urban areas, but without significant difference between the road and roof sites samples, indicating regional transport of biomass smoke to the cities. Similar roof and street site sample concentrations were also observed for secondary organic aerosol (SOA) compounds, i.e. dicarboxylic acids and oxidation products of isoprene and α-pinene. The SOA compound concentrations were ten times higher in summer compared to winter samples, emphasizing the importance of SOA formation processes in summer. More evidence was obtained that linked the presence of cis-pinonic acid in the filter samples to new particle formation during nucleation. The urban organic PM1 is dominated by SOA, while the primary organic aerosol (POA) tracer compounds from combustion sources, including traffic and biomass burning, dominates in winter.

Photo-oxidation products of α-pinene in coarse, fine and ultrafine aerosol: A new high sensitive HPLC-MS/MS method

Oxidation products of α-pinene represent a fraction of organic matter in the environmental aerosol. α-pinene is one of most abundant monoterpenes released in the atmosphere by plants, located typically in boreal, temperate and tropical forests. This primary compound reacts with atmospheric oxidants, such as O3, O2, OH radicals and NOx, through the major tropospheric degradation pathway for many monoterpenes under typical atmospheric condition. Although several studies identified a series of by-products deriving from the α-pinene photo-oxidation in the atmosphere, such as pinic and cis-pinonic acid, the knowledge of the mechanism of this process is partially still lacking. Thus, the investigation of the distribution of these acids in the different size aerosol particles provides additional information on this regard.The aim of this study is twofold. First, we aim to improve the existing analytical methods for the determination of pinic and cis-pinonic acid in aerosol samples, especially in terms of analytical sensitivity and limits of detection (LOD) and quantification (LOQ). We even attempted to increase the knowledge of the α-pinene photo-oxidation processes by analysing, for the first time, the particle-size distribution up to nanoparticle level of pinic and cis-pinonic acid. The analysis of aerosol samples was carried out via high-performance liquid chromatography coupled to a triple quadrupole mass spectrometer. The instrumental LOD values of cis-pinonic and pinic acid are 1.6 and 1.2 ng L−1 while LOQ values are 5.4 and 4.1 ng L−1, respectively. Samples were collected by MOUDI II™ cascade impactor with twelve cut-sizes, from March to May 2016 in the urban area of Mestre-Venice (Italy).The range concentrations in the aerosol samples were from 0.1 to 0.9 ng m−3 for cis-pinonic acid and from 0.1 to 0.8 ng m−3 for pinic acid.

Seasonal variation and size distribution of biogenic secondary organic aerosols at urban and continental background sites of China

Size-resolved biogenic secondary organic aerosols (BSOA) derived from isoprene and monoterpene photooxidation in Qinghai Lake, Tibetan Plateau (a continental background site) and five cities of China were measured using gas chromatography/mass spectrometry (GC/MS). Concentrations of the determined BSOA are higher in the cities than in the background and are also higher in summer than in winter. Moreover, strong positive correlations (R2=0.44–0.90) between BSOA and sulfate were found at the six sites, suggesting that anthropogenic pollution (i.e., sulfate) could enhance SOA formation, because sulfate provides a surface favorable for acid-catalyzed formation of BSOA. Size distribution measurements showed that most of the determined SOA tracers are enriched in the fine mode (<3.3μm) except for cis-pinic and cis-pinonic acids, both presented a comparable mass in the fine and coarse (>3.3μm) modes, respectively. Mass ratio of oxidation products derived from isoprene to those from monoterpene in the five urban regions during summer are much less than those in Qinghai Lake region. In addition, in the five urban regions relative abundances of monoterpene oxidation products to SOA are much higher than those of isoprene. Such phenomena suggest that BSOA derived from monoterpenes are more abundant than those from isoprene in Chinese urban areas.

Direct Sampling and Analysis of Atmospheric Particulate Organic Matter by Proton-Transfer-Reaction Mass Spectrometry.

We report on a new method for analyzing atmospheric submicrometer particulate organic matter which combines direct particle sampling and volatilization with online chemical ionization mass spectrometric analysis. Technically, the method relies on the combined use of a CHARON ("Chemical Analysis of Aerosol Online") particle inlet and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS). Laboratory studies on target analytes showed that the ionization conditions in the PTR-ToF-MS lead to extensive fragmentation of levoglucosan and cis-pinonic acid, while protonated oleic acid and 5α-cholestane molecules remain intact. Potential problems and biases in quantitative and qualitative analyses are discussed. Side-by-side atmospheric comparison measurements of total particulate organic mass and levoglucosan with an aerosol mass spectrometer (AMS) were in good agreement. Complex and clearly distinct organic mass spectra were obtained from atmospheric measurements in three European cities (Lyon, Valencia, Innsbruck). Data visualization in reduced-parameter frameworks (e.g., oxidation state of carbon vs carbon number) revealed that the CHARON-PTR-ToF-MS technique adds significant analytical capabilities for characterizing particulate organic carbon in the Earth's atmosphere. Positive matrix factorization (PMF) was used for apportioning sources of atmospheric particles in late fall in Innsbruck. The m/z signatures of known source marker compounds (levoglucosan and resin acids, polycyclic aromatic hydrocarbons, nicotine) in the mass spectra were used to assign PMF factors to biomass burning, traffic, and smoking emission sources.

Characteristics and contributions of biogenic secondary organic aerosol tracers to PM2.5 in Shanghai, China

To evaluate biogenic secondary organic aerosol (BSOA) tracers from biogenic precursors, fine particles (PM2.5) were collected using filter-based high-volume samplers from spring-summer of 2015 in the central part of Shanghai, China. The results showed that the isoprene SOA tracers exhibited the highest levels (17.64 ± 9.75 ng m−3) and were always observed along with higher temperatures, which results in a higher tracer formation rate and isoprene emission strength. However, the isoprene SOA tracers showed a weak correlation with the relative humidity (p > 0.05). The isoprene SOA tracers showed remarkable correlations with the [H+] because of the enhanced formation of isoprene SOA in the acidic aerosols. On the basis of these results, 2-methylglyceric acid was determined to have weak correlations with other isoprene tracers, which indicated that it had different formation pathways from those of other isoprene SOA tracers. Cis-pinonic acid had negative correlations with other SOA tracers, indicating that it is the first product in the oxidation process. Furthermore, the isoprene-based tracers (SOCisoprene) were calculated to be 0.031–0.299 μg C m−3 (with an average of 0.114 ± 0.062 μg C m−3), which accounted for more than half of the biogenic SOA. The SOC estimation with SOA tracers (SOC tracer-based) averaged 0.155 ± 0.066 μg m−3, with a range from 0.049 to 0.309 μg m−3 during the sampling period, which amounted to 2.73% OC.

Cis-Pinonic Acid Oxidation by Hydroxyl Radicals in the Aqueous Phase under Acidic and Basic Conditions: Kinetics and Mechanism.

Aqueous-phase oxidation of cis-pinonic acid (CPA) by hydroxyl radicals (OH) was studied using a relative rate technique under acidic and basic conditions. Liquid chromatography (LC) coupled to the negative electrospray ionization (ESI) quadrupole tandem mass spectrometry (MS/MS) was used to monitor the concentrations of CPA and reference compounds. The measured second order reaction rate coefficients of CPA with OH were: 3.6 ± 0.3 × 109 M-1 s-1 (pH 2) and 3.0 ± 0.3 × 109 M-1 s-1 (pH 10) - combined uncertainties are 2σ. These results indicated that the lifetimes of CPA in the atmosphere are most likely independent from the aqueous-phase pH. LC-ESI/MS/MS was also used to tentatively identify the CPA oxidation products. Formation of carboxylic acids with molecular weight (MW) 216 Da (most likely C10H16O5) and MW 214 Da (C10H14O5) was confirmed with LC-ESI/MS/MS. When the initial CPA concentration was increased from 0.3 to 10 mM, formation of additional products was observed with MW 188, 200, 204, and 232 Da. Hydroperoxy, hydroxyl and carbonyl-substituted CPA derivatives were tentatively identified among the products. Similar products were formed by the CPA oxidation by OH in the gas-phase, at the air-water interface as well as in the solid phase (dry film). Formation of the stable adduct of CPA and H2O2 was also observed when the reaction mixture was evaporated to dryness and redissolved in water. Acquired mass spectrometric data argues against formation of oligomers.

Structures and energetics of hydrated deprotonated cis-pinonic acid anion clusters and their atmospheric relevance.

Pinonic acid, a C10-monocarboxylic acid with a hydrophilic -CO2H group and a hydrophobic hydrocarbon backbone, is a key intermediate oxidation product of α-pinene - an important monoterpene compound in biogenic emission processes that influences the atmosphere. Molecular interaction between cis-pinonic acid and water is essential for understanding its role in the formation and growth of pinene-derived secondary organic aerosols. In this work, we studied the structures, energetics, and optical properties of hydrated clusters of the cis-pinonate anion (cPA-), the deprotonated form of cis-pinonic acid, by negative ion photoelectron spectroscopy and ab initio theoretical calculations. Our results show that cPA- can adopt two different structural configurations - open and folded. In the absence of waters, the open configuration has the lowest energy and provides the best agreement with the experiment. The added waters, which mainly interact with the negatively charged -CO2- group, gradually stabilize the folded configuration and lower its energy difference relative to the most stable open-configured structure. Thermochemical and equilibrium hydrate distribution analyses suggest that the mono- and di-hydrates are likely to exist in humid atmospheric environments with high populations. The detailed molecular description of cPA- hydrated clusters unraveled in this study provides a valuable reference for understanding the initial nucleation process and aerosol formation involving organics containing both hydrophilic and hydrophobic groups, as well as for analyzing the optical properties of those organic aerosols.

Efficient scavenging of Criegee intermediates on water by surface-active cis-pinonic acid.

cis-Pinonic acid (CPA), the main product of the atmospheric oxidation of biogenic α-pinene emissions and a major component of secondary organic aerosol (SOA), is a potentially key species en route to extremely low volatility compounds. Here, we report that CPA is an exceptionally efficient scavenger of Criegee intermediates (CIs) on aqueous surfaces. Against expectations, millimolar CPA (a surface-active C10 keto-carboxylic acid possessing a rigid skeleton) is able to compete with 23 M bulk water for the CIs produced in the ozonolysis of sesquiterpene solutes by O3(g) on the surface of a water:acetonitrile solvent. The significance of this finding is that CPA reactions with sesquiterpene CIs on the surface of aqueous organic aerosols would directly generate C25 species. The finding that competitive reactions at the air-liquid interface depend on interfacial rather than bulk reactant concentrations should be incorporated in current chemical models dealing with SOA formation, growth and aging.

Transformations of (–)-α-Pinene Peroxide Ozonolysis Products by Hydrazines of HCl and H2SO4

The reactivities of hydrazines of HCl and H2SO4 for (–)-α-pinene peroxide ozonolysis products were studied. It was shown that these reagents were less effective and selective than semicarbazide hydrochloride for transformations into cis-pinonic acid and its esters.