Newly Discovered Components of Dendrolimus pini Sex Pheromone.

The pine-tree lappet moth, D. pini, is a harmful defoliator of pine forests in Europe and Asia and a potentially invasive species in North America. The lures for trapping D. pini males based on two known components of its sex pheromone appeared weakly attractive to male moths. Identification of all components of the sex pheromone might allow for the development of more effective lures. The pheromone was sampled from virgin females using SPME and analyzed using gas chromatography coupled with mass spectrometry. Four new likely components ((Z5)-dodecenal, (Z5)-dodecen-1-ol, (Z5)-decen-1-yl acetate, (Z5)-tetradecen-1-yl acetate) and two known components ((Z5,E7)-dodecadienal, (Z5,E7)-dodecadien-1-ol) were identified based on comparison against authentic standards, Kováts indices and spectra libraries. The samples also contained several sesquiterpenes. Wind tunnel and field experiments showed that some blends of synthetic pheromone components alone or enriched with Scots pine essential oil (SPEO) were attractive to D. pini males. One component-(Z5)-decen-1-yl acetate-had a repelling effect. The presented knowledge of D. pini sex pheromone provides a basis for developing optimal lures for monitoring or controlling insect populations.

Winter sources of PM2.5 pollution in Podkowa Lesna, a Central-European garden town (Mazovia, Poland).

The paper analyzes PM2.5 aerosol samples collected in Podkowa Lesna, a garden town in Mazovia, Central Poland, for 15 days in winter 2019. We determined the mass concentrations in the air of PM2.5 and PM2.5-bound organic carbon, elemental carbon, levoglucosan, and nine polycyclic aromatic hydrocarbons (PAHs). PM2.5 ranged from 11 to 51 µg m-3 (mean 31 µg m-3) and contained less than 32% organic carbon, 4% elemental carbon, 1% levoglucosan, and 0.12% total PAHs. The analysis based on positive matrix factorization (PMF) indicated two sources of PM2.5 of similar strength - burning vehicle fuels and biomass burning for residential heating. Levoglucosan originated exclusively from biomass burning, while 90% of elemental carbon was from vehicle emissions. About 62% of organic carbon, 85% of benzo(a)anthracene and 55-65% of the remaining PAHs originated from biomass burning. Compared to many worldwide locations, PM2.5, organic carbon, elemental carbon, and levoglucosan in Podkowa were among the lowest. The benzo(a)pyrene concentrations were the highest, while other PAHs were intermediate. However, the mass fractions of PAHs in Podkowa PM2.5 were the highest among the four locations available for comparison. That may indicate the low quality of fuel-burning processes. PAH-related inhalation cancer risk based on PAH carcinogenic potency in Podkowa appeared marginal. This work aims to induce local administrative actions to improve air quality in garden towns.

Rapid production of highly oxidized molecules in isoprene aerosol via peroxy and alkoxy radical isomerization pathways in low and high NOx environments: Combined laboratory, computational and field studies.

Recently, we identified seven novel hydroxy-carboxylic acids resulting from gas-phase reactions of isoprene in the presence of nitrogen oxides (NOx), ozone (O3), and/or hydroxyl radicals (OH). In the present study, we provide evidence that hydroxy-carboxylic acids, namely methyltartaric acids (MTA) are: (1) reliable isoprene tracers, (2) likely produced via rapid peroxy radical hydrogen atom (H) shift reactions (autoxidation mechanism) and analogous alkoxy radical H shifts in low and high NOx environments respectively and (3) representative of aged ambient aerosol in the low NOx regime. Firstly, MTA are reliable tracers of isoprene aerosol because they have been identified in numerous chamber experiments involving isoprene conducted under a wide range of conditions and are absent in the oxidation of mono- and sesquiterpenes. They are also present in numerous samples of ambient aerosol collected during the past 20 years at several locations in the U.S. and Europe. Furthermore, MTA concentrations measured during a year-long field study in Research Triangle Park (RTP), NC in 2003 show a seasonal trend consistent with isoprene emissions and photochemical activity. Secondly, an analysis of chemical ionization mass spectrometer (CIMS) data of several chamber experiments in low and high NOx environments show that highly oxidized molecules (HOMs) derived from isoprene that lead to MTAs may be produced rapidly and considered as early generation isoprene oxidation products in the gas phase. Density functional theory calculations show that rapid intramolecular H shifts involving peroxy and alkoxy radicals possess low barriers for methyl-hydroxy-butenals (MHBs) that may represent precursors for MTA. From these results, a viable rapid H shift mechanism is proposed to occur that produces isoprene derived HOMs like MTA. Finally, an analysis of the mechanism shows that autoxidation-like pathways in low and high NOx may produce HOMs in a few OH oxidation steps like commonly detected methyl tetrol (MT) isoprene tracers. The ratio of MTA/MT in isoprene aerosol is also shown to be significantly greater in field versus chamber samples indicating the importance of such pathways in the atmosphere even for smaller hydrocarbons like isoprene.

Tracing the biogenic secondary organic aerosol markers in rain, snow and hail.

The molecular characterization of secondary organic aerosol (SOA) is based mainly on LC-MS analyses of particulate matter (PM) samples collected with aerosol samplers. Several studies have analyzed atmospheric waters, including rain and cloud water, for the presence of SOA components, however, no separation techniques were used making identification of the individual components in these complex mixtures impossible. We have applied our improved UHPLC-HR-MS methodology to analyze atmospheric precipitates (hailstone, rain and snow), as well as SOA collected with high-volume samplers. We achieved sensitivity levels and separation efficiencies that were sufficient for molecular-level identification of individual compounds. Tracing commonly known SOA markers such as organosulfates (OS), C4-C6 dicarboxylic acids and terpenoic acids revealed that the chromatographic profiles for both atmospheric precipitate and PM samples were very similar, with both giving similar component ratios, especially for OS. We also demonstrated that SOA markers can be detected directly from raw rain samples. Our results show that LC-MS techniques are suitable for the convenient analysis of atmospheric precipitates containing SOA markers at the molecular level. It complements traditional SOA analyses and provides additional sampling opportunities which will no doubt allow for better elucidation of chemical transformations of volatile organic compounds in the atmosphere.

Structural Characterization of Lactone-Containing MW 212 Organosulfates Originating from Isoprene Oxidation in Ambient Fine Aerosol.

Isoprene (C5H8) is the main non-methane hydrocarbon emitted into the global atmosphere. Despite intense research, atmospheric transformations of isoprene leading to secondary organic aerosol (SOA) are still not fully understood, including its multiphase chemical reactions. Herein, we report on the detailed structural characterization of atmospherically relevant isoprene-derived organosulfates (OSs) with a molecular weight (MW) of 212 (C5H8SO7), which are abundantly present in both ambient fine aerosol (PM2.5) and laboratory-generated isoprene SOA. The results obtained from smog chamber-generated isoprene SOA and aqueous-phase laboratory experiments coupled to the S(IV)-autooxidation chemistry of isoprene, 3-methyl-2(5H)-furanone, and 4-methyl-2(5H)-furanone, allowed us for the first time to fully elucidate the isomeric structures of the MW 212 OSs. By applying liquid chromatography interfaced to electrospray ionization high-resolution mass spectrometry, we firmly confirmed six positional isomers of the MW 212 OSs in PM2.5 collected from different sites in Europe and the United States. Our results also show that despite the low solubility of isoprene in water, aqueous-phase or multiphase chemistry can play an important role in the formation of OSs from isoprene. Possible formation mechanisms for the MW 212 OSs are also tentatively proposed.

Organic Hydroxy Acids as Highly Oxygenated Molecular (HOM) Tracers for Aged Isoprene Aerosol.

Highly oxygenated molecules (HOMs) are a class of compounds associated with secondary organic aerosols exhibiting high oxygen to carbon (O:C) ratios and often originating from the oxidation of biogenic compounds. Here, the photooxidation and ozonolysis of isoprene were examined under a range of conditions to identify HOM tracers for aged isoprene aerosol. The HOM tracers were identified as silylated derivatives by gas chromatography-mass spectrometry and by detecting their parent compounds by liquid chromatography-high resolution mass spectrometry. In addition to the previously observed methyltetrols and 2-methylglyceric acid, seven tracer compounds were identified, including 2-methyltartronic acid (MTtA), 2-methylerythronic acid (2MeTrA), 3-methylerythronic acid (3MeTrA), 2-methylthreonic acid (2MTrA), 3-methylthreonic acid (3MTrA), erythro-methyltartaric acid (e-MTA), and threo-methyltartaric acid (t-MTA). The molecular structures were confirmed with authentic standards synthesized in the laboratory. The presence of some of these HOMs in the gas and particle phases simultaneously provides evidence of their gas/particle partitioning. To determine the contributions of aged isoprene products to ambient aerosols, we analyzed ambient PM2.5 samples collected in the southeastern United States in summer 2003 and at two European monitoring stations located in Zielonka and Godów (Poland). Our findings show that methyltartaric acids (MTA) and 2- and 3-methylthreonic acids (and their stereoisomers) are representative of aged isoprene aerosol because they occur both in the laboratory chamber aerosol obtained and in ambient PM2.5. On the basis of gas chromatography-mass spectrometry (GC-MS) analysis, their concentrations were found to range from 0.04 ng for 3-methylthreonic acid to 6.3 ng m-3 for methyltartaric acid at the southeast site in Duke Forest, NC, USA.

Radical oxidation of methyl vinyl ketone and methacrolein in aqueous droplets: Characterization of organosulfates and atmospheric implications.

In-cloud processing of volatile organic compounds is one of the significant routes leading to secondary organic aerosol (SOA) in the lower troposphere. In this study, we demonstrate that two atmospherically relevant α,ß-unsaturated carbonyls, i.e., but-3-en-2-on (methyl vinyl ketone, MVK) and 2-methylopropenal (methacrolein, MACR), undergo sulfate radical-induced transformations in dilute aqueous systems under photochemical conditions to form organosulfates previously identified in ambient aerosols and SOA generated in smog chambers. The photooxidation was performed under sun irradiation in unbuffered aqueous solutions containing carbonyl precursors at a concentration of 0.2 mmol and peroxydisulfate as a source of sulfate radicals (SO4-) at a concentration of 0.95 mmol. UV-vis analysis of solutions showed the fast decay of unsaturated carbonyl precursors in the presence of sulfate radicals. The observation confirms the capacity of sulfate radicals to transform the organic compounds into SOA components in atmospheric waters. Detailed interpretation of high-resolution negative ion electrospray ionization tandem mass spectra allowed to assign molecular structures to multiple aqueous organosulfate products, including an abundant isoprene-derived organosulfate C4H8SO7 detected at m/z 199. The results highlight the solar aqueous-phase reactions as a potentially significant route for biogenic SOA production in clouds at locations where isoprene oxidation occurs. A recent modelling study suggests that such processes could likely contribute to 20-30 Tg year-1 production of SOA, referred to as aqSOA, which is a non-negligible addition to the still underestimated budget of atmospheric aerosol.

Improved UHPLC-MS/MS Methods for Analysis of Isoprene-Derived Organosulfates.

Secondary organic aerosol (SOA) is an important yet not fully characterized constituent of atmospheric particulate matter. A number of different techniques and chromatographic methods are currently used for the analysis of SOA, so the comparison of results from different laboratories poses a challenge. So far, tentative structures have been suggested for many organosulfur compounds that have been identified as markers for the formation of SOA, including isoprene-derived organosulfates. Despite the effectiveness and robustness of LC-MS/MS analyses, the structural profiling of positional isomers of recently discovered organosulfates with molecular weights (MWs) of 214 and 212 from isoprene was entirely unsuccessful. Here, we developed a UHPLC combined with high-resolution tandem mass spectrometric method that significantly improves the separation efficiency and detection sensitivity of these compounds in aerosol matrices. We discovered that selection of the proper solvent for SOA extracts was a key factor in improving the separation parameters. Later, we took advantage of the enhanced sensitivity, combined with a short scan time window, to perform detailed structural mass-spectrometric studies. For the first time, we elucidate a number of isomers of the MW 214 and the MW 212 organosulfates and provide strong evidence for their molecular structures. The structure of trihydroxyketone sulfate MW 214 that we propose has not been previously reported. The methods we designed can be easily applied in other laboratories to foster an easy comparison of related qualitative and quantitative data obtained throughout the world.

Atmospheric aqueous phase radical chemistry of the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic acid and acrylic acid--kinetics and product studies.

Kinetic and mechanistic studies were conducted on the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic and acrylic acid reacting with hydroxyl and nitrate radicals and sulfate radical anions in aqueous solution by use of the laser flash photolysis technique and a reversed-rate method for kinetics. High-performance liquid chromatography/mass spectrometry was applied for product analysis. The kinetic investigations show the highest reactivity of the hydroxyl radical followed by sulfate and nitrate radicals. For methacrolein and methyl vinyl ketone the following rate constants have been determined at 298 K: k(OH+methacrolein) = (9.4 ± 0.7) × 10(9) M(-1) s(-1), k(OH+methyl vinyl ketone) = (7.3 ± 0.5) × 10(9) M(-1) s(-1), k(NO3+methacrolein) = (4.0 ± 1.0) × 10(7) M(-1) s(-1), k(NO3+methyl vinyl ketone) = (9.7 ± 3.4) × 10(6) M(-1) s(-1), k(SO4(-)+methacrolein) = (9.9 ± 4.9) × 10(7) M(-1) s(-1) and k(SO4(-)+methyl vinyl ketone) = (1.0 ± 0.2) × 10(8) M(-1) s(-1). Temperature and pH dependencies of the reactions of OH, NO3 and SO4(-) with methacrolein, methyl vinyl ketone, methacrylic and acrylic acid as well as Arrhenius parameters have been obtained and discussed. Product studies were performed on the OH radical induced oxidation of methacrolein and methyl vinyl ketone. In the reaction of methacrolein + OH methylglyoxal and hydroxyacetone were identified as first oxidation products with yields of 0.099 and 0.162. Methylglyoxal was primarily produced in the oxidation of methyl vinyl ketone with a yield of 0.052. For both precursor compounds the formation of glycolaldehyde was observed for the first time with yields of 0.051 and 0.111 in the oxidation of methacrolein and methyl vinyl ketone, respectively. Furthermore, highly functionalised C4 compounds were determined from the oxidation of both precursor compounds, but for the first time for methyl vinyl ketone. Reaction schemes were developed based on known peroxyl radical reaction mechanisms. The aqueous phase conversion of the first generation isoprene oxidation products can potentially contribute to tropospheric aqueous phase budgets of important carbonyl and dicarbonyl components which are expected to be conducive to the formation of aqSOA.

Identification of volatiles from Pinus silvestris attractive for Monochamus galloprovincialis using a SPME-GC/MS platform.

INTRODUCTION: A myriad of volatile organic compounds (VOCs) released by terrestrial vegetation plays an important role in environmental sciences. A thorough chemical identification of these species at the molecular level is essential in various fields, ranging from atmospheric chemistry to ecology of forest ecosystems. In particular, the recognition of VOCs profiles in a context of plant-insect communication is a key issue for the development of forest protection tools. PURPOSE: This work was aimed at the development of a simple, robust and reliable method for the identification of volatiles emitted from plant materials, which can attract or deter pest insects. Specifically, volatiles emitted from the bark of Pinus sylvestris were studied, which might attract the black pine sawyer beetle Monochamus galloprovincialis-a serious pest of the tree and a vector of a parasitic nematode Bursaphelenchus xylophius. METHOD: The volatiles from bark samples were collected using a solid-phase micro-extraction technique, and subsequently analysed by gas-chromatography/mass-spectrometry (GC/MS). The characterisation of the volatile fraction was based on the comparison with data in mass spectral libraries, and in most cases, with the available authentic standards. The identified compounds were screened against the available entomological data to select insect attractors. RESULTS: The identified components included terpenes (α-pinene, ∆-3-carene, and para-cymenene), oxygenated terpenes (α-terpineol and verbenone), sesquiterpenes (α-longipinene, longifolene, E-ß-farnesene, γ-cadinene and pentadecane), and diterpenes (manoyl oxide and (+)-pimaral). Of these, longifolene and (+)-pimaral are of particular interest as plausible attractors for the M. galloprovincialis beetle that might find application in the construction of insect bait traps.