Organosulfate Formation in Biogenic Secondary Organic Aerosol

Organosulfates of isoprene, α-pinene, and β-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive series of laboratory photooxidation (i.e., OH-initiated oxidation) and nighttime oxidation (i.e., NO3-initiated oxidation under dark conditions) experiments using nine monoterpenes (α-pinene, β-pinene, d-limonene, l-limonene, α-terpinene, γ-terpinene, terpinolene, Δ3-carene, and β-phellandrene) and three monoterpenes (α-pinene, d-limonene, and l-limonene), respectively. Organosulfates were characterized using liquid chromatographic techniques coupled to electrospray ionization combined with both linear ion trap and high-resolution time-of-flight mass spectrometry. Organosulfates are formed only when monoterpenes are oxidized in the presence of acidified sulfate seed aerosol, a result consistent with prior work. Archived laboratory-generated isoprene SOA and ambient filter samples collected from the southeastern U.S. were reexamined for organosulfates. By comparing the tandem mass spectrometric and accurate mass measurements collected for both the laboratory-generated and ambient aerosol, previously uncharacterized ambient organic aerosol components are found to be organosulfates of isoprene, α-pinene, β-pinene, and limonene-like monoterpenes (e.g., myrcene), demonstrating the ubiquity of organosulfate formation in ambient SOA. Several of the organosulfates of isoprene and of the monoterpenes characterized in this study are ambient tracer compounds for the occurrence of biogenic SOA formation under acidic conditions. Furthermore, the nighttime oxidation experiments conducted under highly acidic conditions reveal a viable mechanism for the formation of previously identified nitrooxy organosulfates found in ambient nighttime aerosol samples. We estimate that the organosulfate contribution to the total organic mass fraction of ambient aerosol collected from K-puszta, Hungary, a field site with a similar organosulfate composition as that found in the present study for the southeastern U.S., can be as high as 30%

Evaluation of Three Trap Types and Five Lures for Monitoring \u3ci\u3eHylurgus Ligniperda\u3c/i\u3e (Coleoptera: Scolytidae) and Other Local Scolytids in New York

Hylurgus ligniperda (Coleoptera: Scolytidae) is a pine (Pinus spp.) pest native to Eurasia and northern Africa. In December 2000, an established population of H. ligniperda was discovered in Monroe County, New York. When surveys were initiated to determine the distribution of H. ligniperda, questions arose regarding the most effective trap and lure for survey purposes. We conducted a study in April-May 2001 to compare the effectiveness of commercially available scolytid traps and lures for attracting and capturing H. ligniperda. Traps tested included: 1) 12-unit Lindgren funnel trap, 2) Intercept panel trap, and 3) Theysohn slot-trap. Lures tested included: 1) α-pinene high release (750 mg/day) and ethanol (280 mg/ day), 2) α-pinene low release (300 mg/day) and ethanol, 3) β-pinene high release (2000 mg/day) and ethanol, 4) α-pinene low release, and 5) the “exotic bark beetle lure” [ipsdienol (0.15 mg/day), cis-verbenol (0.35 mg/day), and methylbutenol (10 mg/day)]. All three trap designs captured H. ligniperda, however, the Lindgren funnel trap caught significantly higher numbers. Capture rates of Tomicus piniperda (Coleoptera: Scolytidae) and Hylastes opacus were highest in Lindgren funnel traps; whereas Orthotomicus caelatus collections were highest in Theysohn traps. Capture rates of Ips grandicollis and Xyleborinus saxeseni did not vary significantly among trap types. Behavioral differences among scolytid species such as visual stimuli, flight and landing behavior, and host selection may explain some of these differences. Lures containing α-pinene or β-pinene and ethanol were most attractive to H. ligniperda adults, with ethanol and high-release α-pinene attracting the highest numbers in absolute terms. The exotic bark beetle lure was the least attractive lure to H. ligniperda. Attractiveness of the lures tested varied significantly for other Scolytidae, including Dendroctonus valens, H. opacus, Ips calligraphus, I. grandicollis, I. pini, O. caelatus, T. piniperda, and X. saxeseni. These differences likely were due to variation in lure release rates, host preferences, and/or species-specific pheromone attraction

Nanoparticle growth following photochemical α‐ and β‐pinene oxidation at Appledore Island during International Consortium for Research on Transport and Transformation/Chemistry of Halogens at the Isles of Shoals 2004

Nanoparticle events were observed 48 times in particle size distributions at Appledore Island during the International Consortium for Atmospheric Research on Transport and Transformation/Chemistry of Halogens on the Isles of Shoals (ICARTT/CHAiOS) field campaign from 2 July to 12 August of 2004. Eighteen of the nanoparticle events showed particle growth and occurred during mornings when peaks in mixing ratios of α‐ and β‐pinene and ozone made production of condensable products from photochemical oxidation probable. Many pollutants and other potential precursors for aerosol formation were also at elevated mixing ratios during these events, including NO, HNO3, NH3, HCl, propane, and several other volatile organic carbon compounds. There were no consistent changes in particle composition, although both submicron and supermicron particles included high maximum concentrations of methane sulfonate, sulfate, iodide, nitrate, and ammonium during these events. Nanoparticle growth continued over several hours with a nearly linear rate of increase of diameter with time. The observed nanoparticle growth rates varied from 3 to 13 nm h−1. Apparent nanoparticle aerosol mass fractions (yields) were estimated to range from less than 0.0005 to almost 1 using α‐ and β‐pinene as the presumed particle source. These apparent high aerosol mass fractions (yields) at low changes in aerosol mass are up to two orders of magnitude greater than predictions from extrapolated laboratory parameterizations and may provide a more accurate assessment of secondary organic aerosol formation for estimating the growth of nanoparticles in global models

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO_x environments

The gas-phase oxidation of α-pinene produces a large amount of secondary organic aerosol (SOA) in the atmosphere. A number of carboxylic acids, organosulfates and nitrooxy organosulfates associated with α-pinene have been found in field samples and some are used as tracers of α-pinene oxidation. α-pinene reacts readily with OH and O_3 in the atmosphere followed by reactions with both HO_2 and NO. Due to the large number of potential reaction pathways, it can be difficult to determine what conditions lead to SOA. To better understand the SOA yield and chemical composition from low- and high-NO_x OH oxidation of α-pinene, studies were conducted in the Caltech atmospheric chamber under controlled chemical conditions. Experiments used low O_3 concentrations to ensure that OH was the main oxidant and low α-pinene concentrations such that the peroxy radical (RO_2) reacted primarily with either HO_2 under low-NO_x conditions or NO under high-NO_x conditions. SOA yield was suppressed under conditions of high-NO_x. SOA yield under high-NO_x conditions was greater when ammonium sulfate/sulfuric acid seed particles (highly acidic) were present prior to the onset of growth than when ammonium sulfate seed particles (mildly acidic) were present; this dependence was not observed under low-NO_x conditions. When aerosol seed particles were introduced after OH oxidation, allowing for later generation species to be exposed to fresh inorganic seed particles, a number of low-NO_x products partitioned to the highly acidic aerosol. This indicates that the effect of seed acidity and SOA yield might be under-estimated in traditional experiments where aerosol seed particles are introduced prior to oxidation. We also identify the presence of a number of carboxylic acids that are used as tracer compounds of α-pinene oxidation in the field as well as the formation of organosulfates and nitrooxy organosulfates. A number of the carboxylic acids were observed under all conditions, however, pinic and pinonic acid were only observed under low-NO_x conditions. Evidence is provided for particle-phase sulfate esterification of multi-functional alcohols

Terpenylic Acid and Related Compounds from the Oxidation of α-Pinene: Implications for New Particle Formation and Growth above Forests

Novel secondary organic aerosol (SOA) products from the monoterpene α-pinene with unique dimer-forming properties have been identified as lactone-containing terpenoic acids, i.e., terpenylic and 2-hydroxyterpenylic acid, and diaterpenylic acid acetate. The structural characterizations were based on the synthesis of reference compounds and detailed interpretation of mass spectral data. Terpenylic acid and diaterpenylic acid acetate are early oxidation products generated upon both photooxidation and ozonolysis, while 2-hydroxyterpenylic acid is an abundant SOA tracer in ambient fine aerosol that can be explained by further oxidation of terpenylic acid. Quantum chemical calculations support that noncovalent dimer formation involving double hydrogen bonding interactions between carboxyl groups of the monomers is energetically favorable. The molecular properties allow us to explain initial particle formation in laboratory chamber experiments and are suggested to play a role in new particle formation and growth above forests, a natural phenomenon that has fascinated scientists for more than a century

Disruptant Effects of 4-Allylanisole and Verbenone on \u3ci\u3eTomicus Piniperda\u3c/i\u3e (Coleoptera: Scolytidae) Response to Baited Traps and Logs

We assessed the inhibitory effects of the host compound 4-allylanisole (release rates = 1 and 2 mg/d in 1994, and 1 and 10 mg/d in 2001) on the response of the pine shoot beetle, Tomicus piniperda (L.), adults to funnel traps baited with the attractant host compound α-pinene (release rate = 150 mg/d) in two pine Christmas tree plantations in Michigan in spring 1994 and two other plantations in spring 2001. In three of the four plantations, all doses of 4- allylanisole significantly reduced T. piniperda attraction to α-pinene-baited traps by 46 to 76%. We also tested the inhibitory effect of the antiaggregation pheromone verbenone (release rates = 2 and 4 mg/d) on T. piniperda attack density on pine bolts (average bolt length was 62 cm and diameter was 19 cm) at three sites (two pine forest stands and one Christmas tree plantation) in Michigan in 1994. Verbenone significantly reduced T. piniperda attack density by 37 to 60% at the two pine stands, but not at the Christmas tree plantation

Modeling of secondary organic aerosol yields from laboratory chamber data

Laboratory chamber data serve as the basis for constraining models of secondary organic aerosol (SOA) formation. Current models fall into three categories: empirical two-product (Odum), product-specific, and volatility basis set. The product-specific and volatility basis set models are applied here to represent laboratory data on the ozonolysis of α-pinene under dry, dark, and low-NOx conditions in the presence of ammonium sulfate seed aerosol. Using five major identified products, the model is fit to the chamber data. From the optimal fitting, SOA oxygen-to-carbon (O/C) and hydrogen-to-carbon (H/C) ratios are modeled. The discrepancy between measured H/C ratios and those based on the oxidation products used in the model fitting suggests the potential importance of particle-phase reactions. Data fitting is also carried out using the volatility basis set, wherein oxidation products are parsed into volatility bins. The product-specific model is most likely hindered by lack of explicit inclusion of particle-phase accretion compounds. While prospects for identification of the majority of SOA products for major volatile organic compounds (VOCs) classes remain promising, for the near future empirical product or volatility basis set models remain the approaches of choice