Emerging investigator series: secondary organic aerosol formation from photooxidation of acyclic terpenes in an oxidation flow reactor.

One major challenge in predicting secondary organic aerosol (SOA) formation in the atmosphere is incomplete representation of biogenic volatile organic compounds (BVOCs) emitted from plants, particularly those that are emitted as a result of stress - a condition that is becoming more frequent in a rapidly changing climate. One of the most common types of BVOCs emitted by plants in response to environmental stress are acyclic terpenes. In this work, SOA is generated from the photooxidation of acyclic terpenes in an oxidation flow reactor and compared to SOA production from a reference cyclic terpene - α-pinene. The acyclic terpenes used as SOA precursors included ß-myrcene, ß-ocimene, and linalool. Results showed that oxidation of all acyclic terpenes had lower SOA yields measured after 4 days photochemical age, in comparison to α-pinene. However, there was also evidence that the condensed organic products that formed, while a smaller amount overall, had a higher oligomeric content. In particular, ß-ocimene SOA had higher oligomeric content than all the other chemical systems studied. SOA composition data from ultra-high performance liquid chromatography with electrospray ionization mass spectrometry (UHPLC-ESI-MS) was combined with mechanistic modeling using the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to explore chemical mechanisms that could lead to this oligomer formation. Calculations based on composition data suggested that ß-ocimene SOA was more viscous with a higher glass transition temperature than other SOA generated from acyclic terpene oxidation. This was attributed to a higher oligomeric content compared to other SOA systems studied. These results contribute to novel chemical insights about SOA formation from acyclic terpenes and relevant chemistry processes, highlighting the importance of improving underrepresented biogenic SOA formation in chemical transport models.

Missing Measurements of Sesquiterpene Ozonolysis Rates and Composition Limit Understanding of Atmospheric Reactivity.

Emissions of biogenic reactive carbon significantly influence atmospheric chemistry, contributing to the formation and destruction of secondary pollutants, such as secondary organic aerosol and ozone. While isoprene and monoterpenes are a major fraction of emissions and have been extensively studied, substantially less is known about the atmospheric impacts of higher-molecular-weight terpenes such as sesquiterpenes. In particular, sesquiterpenes have been proposed to play a significant role in ozone chemical loss due to the very high ozone reaction rates of certain isomers. However, relatively little data are available on the isomer-resolved composition of this compound class or its role in ozone chemistry. This study examines the chemical diversity of sesquiterpenes and availability of ozone reaction rate constants to evaluate the current understanding of their ozone reactivity. Sesquiterpenes are found to be highly diverse, with 72 different isomers reported and relatively few isomers that contribute a large mass fraction across all studies. For the small number of isomers with known ozone reaction rates, estimated rates may be 25 times higher or lower than measurements, indicating that estimated reaction rates are highly uncertain. Isomers with known ozone reaction rates make up approximately half of the mass of sesquiterpenes in concentration and emission measurements. Consequently, the current state of the knowledge suggests that the total ozone reactivity of sesquiterpenes cannot be quantified without very high uncertainty, even if isomer-resolved composition is known. These results are in contrast to monoterpenes, which are less diverse and for which ozone reaction rates are well-known, and in contrast to hydroxyl reactivity of monoterpenes and sesquiterpenes, for which reaction rates can be reasonably well estimated. Improved measurements of a relatively small number of sesquiterpene isomers would reduce uncertainties and improve our understanding of their role in regional and global ozone chemistry.

Limonene Enantiomeric Ratios from Anthropogenic and Biogenic Emission Sources.

Emissions from volatile chemical products (VCPs) have been identified as contributors to air quality degradation in urban areas. Limonene can be a tracer compound for VCPs containing fragrances in densely populated regions, but limonene is also emitted from conifers that are planted in urban areas. This creates challenges for using limonene to estimate VCP emissions. In this study, the -/+ enantiomeric ratios of limonene from VCP and conifer emission sources were quantified to evaluate if this measurement could be used to aid in source apportionment and emission inventory development. Samples were analyzed using a gas chromatograph equipped with a chiral column and mass spectrometry. The results demonstrate that limonene exhibits distinct enantiomeric ratios when sourced from VCPs versus conifers. (+)-Limonene was dominant in VCP sources (>97%), which was not universally true for conifer sources. The results were compared to those of air samples collected outside at two locations and indoors. The levels of (-)-limonene in outdoor air in Irvine and Portland and in indoor air were 50%, 22%, and 4%, respectively. This suggests outdoor limonene had both VCP and plant emission sources while indoor air was dominated by VCP sources. This study demonstrates the potential utility of enantiomeric analysis for improving VCP emission estimates in urban areas.

Insect Infestation Increases Viscosity of Biogenic Secondary Organic Aerosol.

Plant stress alters emissions of volatile organic compounds. However, little is known about how this could influence climate-relevant properties of secondary organic aerosol (SOA), particularly from complex mixtures such as real plant emissions. In this study, the chemical composition and viscosity were examined for SOA generated from real healthy and aphid-stressed Canary Island pine (Pinus canariensis) trees, which are commonly used for landscaping in Southern California. Healthy Canary Island pine (HCIP) and stressed Canary Island pine (SCIP) aerosols were generated in a 5 m3 environmental chamber at 35-84% relative humidity and room temperature via OH-initiated oxidation. Viscosities of the collected particles were measured using an offline poke-flow method, after conditioning the particles in a humidified air flow. SCIP particles were consistently more viscous than HCIP particles. The largest differences in particle viscosity were observed in particles conditioned at 50% relative humidity where the viscosity of SCIP particles was an order of magnitude larger than that of HCIP particles. The increased viscosity for the aphid-stressed pine tree SOA was attributed to the increased fraction of sesquiterpenes in the emission profile. The real pine SOA particles, both healthy and aphid-stressed, were more viscous than α-pinene SOA particles, demonstrating the limitation of using a single monoterpene as a model compound to predict the physicochemical properties of real biogenic SOA. However, synthetic mixtures composed of only a few major compounds present in emissions (<10 compounds) can reproduce the viscosities of SOA observed from the more complex real plant emissions.

Effects of Anthropogenic and Biogenic Volatile Organic Compounds on Los Angeles Air Quality.

Assessing the role of volatile organic compounds (VOCs) in production of ozone and secondary organic aerosol (SOA) is especially important in light of ongoing policy goals. Here, we estimated the ozone formation potential (OFP) and SOA formation potential (SOAP) of anthropogenic and biogenic VOC emissions to evaluate (1) anthropogenic VOCs and associated sectors that dominate OFP and SOAP and (2) the potential impacts of enhanced biogenic VOCs from urban greening programs on air quality in Los Angeles county. In the present-day scenario, ethylene had the largest OFP followed by m & p-xylene, toluene, propylene, and formaldehyde. The top five contributors to SOAP were toluene, mineral spirits, benzene, heptadecane, and hexadecane. Mobile and solvent sources were the dominant VOC sources for both OFP and SOAP. The potential increases in biogenic VOC emissions due to future urban greening had significant effects on urban air quality that offset the benefits of reducing anthropogenic VOC emissions. This study demonstrates that urban greening programs in Los Angeles county, and likely other cities as well, need to account for both anthropogenic and biogenic VOC contributions to secondary pollution, and greening cities should consider using vegetation types with low VOC emissions to avoid further degradation to urban air quality.

Crops for Carbon Farming.

Agricultural cropping systems and pasture comprise one third of the world's arable land and have the potential to draw down a considerable amount of atmospheric CO2 for storage as soil organic carbon (SOC) and improving the soil carbon budget. An improved soil carbon budget serves the dual purpose of promoting soil health, which supports crop productivity, and constituting a pool from which carbon can be converted to recalcitrant forms for long-term storage as a mitigation measure for global warming. In this perspective, we propose the design of crop ideotypes with the dual functionality of being highly productive for the purposes of food, feed, and fuel, while at the same time being able to facilitate higher contribution to soil carbon and improve the below ground ecology. We advocate a holistic approach of the integrated plant-microbe-soil system and suggest that significant improvements in soil carbon storage can be achieved by a three-pronged approach: (1) design plants with an increased root strength to further allocation of carbon belowground; (2) balance the increase in belowground carbon allocation with increased source strength for enhanced photosynthesis and biomass accumulation; and (3) design soil microbial consortia for increased rhizosphere sink strength and plant growth-promoting (PGP) properties.

Floral Scent Composition and Fine-Scale Timing in Two Moth-Pollinated Hawaiian Schiedea (Caryophyllaceae).

Floral scent often intensifies during periods of pollinator activity, but the degree of this synchrony may vary among scent compounds depending on their function. Related plant species with the same pollinator may exhibit similar timing and composition of floral scent. We compared timing and composition of floral volatiles for two endemic Hawaiian plant species, Schiedea kaalae and S. hookeri (Caryophyllaceae). For S. kaalae, we also compared the daily timing of emission of floral volatiles to evening visits of their shared pollinator, an endemic Hawaiian moth (Pseudoschrankia brevipalpis; Erebidae). The identity and amount of floral volatiles were measured in the greenhouse during day and evening periods with dynamic headspace sampling and GC-MS (gas chromatography - mass spectrometry). The timing of emissions (daily rise, peak, and fall) was measured by sampling continuously for multiple days in a growth chamber with PTR-MS (proton transfer reaction mass spectrometry). Nearly all volatiles detected underwent strong daily cycles in emission. Timings of floral volatile emissions were similar for S. kaalae and S. hookeri, as expected for two species sharing the same pollinator. For S. kaalae, many volatiles known to attract moths, including several linalool oxides and 2-phenylacetaldehyde, peaked within 2 h of the peak visitation time of the moth which pollinates both species. Floral volatiles of both species that peaked in the evening were also emitted several hours before and after the brief window of pollinator activity. Few volatiles followed a daytime emission pattern, consistent with increased apparency to visitors only at night. The scent blends of the two species differed in their major components and were most distinct from each other in the evening. The qualitative difference in evening scent composition between the two Schiedea species may reflect their distinct evolutionary history and may indicate that the moth species uses several different floral cues to locate rewards.

Secondary Organic Aerosol Formation from Healthy and Aphid-Stressed Scots Pine Emissions.

One barrier to predicting biogenic secondary organic aerosol (SOA) formation in a changing climate can be attributed to the complex nature of plant volatile emissions. Plant volatile emissions are dynamic over space and time, and change in response to environmental stressors. This study investigated SOA production from emissions of healthy and aphid-stressed Scots pine saplings via dark ozonolysis and photooxidation chemistry. Laboratory experiments using a batch reaction chamber were used to investigate SOA production from different plant volatile mixtures. The volatile mixture from healthy plants included monoterpenes, aromatics, and a small amount of sesquiterpenes. The biggest change in the volatile mixture for aphid-stressed plants was a large increase (from 1.4 to 7.9 ppb) in sesquiterpenes-particularly acyclic sesquiterpenes, such as the farnesene isomers. Acyclic sesquiterpenes had different effects on SOA production depending on the chemical mechanism. Farnesenes suppressed SOA formation from ozonolysis with a 9.7-14.6% SOA mass yield from healthy plant emissions and a 6.9-10.4% SOA mass yield from aphid-stressed plant emissions. Ozonolysis of volatile mixtures containing more farnesenes promoted fragmentation reactions, which produced higher volatility oxidation products. In contrast, plant volatile mixtures containing more farnesenes did not appreciably change SOA production from photooxidation. SOA mass yields ranged from 10.8 to 23.2% from healthy plant emissions and 17.8-26.8% for aphid-stressed plant emissions. This study highlights the potential importance of acyclic terpene chemistry in a future climate regime with an increased presence of plant stress volatiles.

Factors controlling the evaporation of secondary organic aerosol from α-pinene ozonolysis.

Secondary organic aerosols (SOA) forms a major fraction of organic aerosols in the atmosphere. Knowledge of SOA properties that affect their dynamics in the atmosphere is needed for improving climate models. By combining experimental and modeling techniques, we investigated the factors controlling SOA evaporation under different humidity conditions. Our experiments support the conclusion of particle phase diffusivity limiting the evaporation under dry conditions. Viscosity of particles at dry conditions was estimated to increase several orders of magnitude during evaporation, up to 109 Pa s. However, at atmospherically relevant relative humidity and time scales, our results show that diffusion limitations may have a minor effect on evaporation of the studied α-pinene SOA particles. Based on previous studies and our model simulations, we suggest that, in warm environments dominated by biogenic emissions, the major uncertainty in models describing the SOA particle evaporation is related to the volatility of SOA constituents.

Effect of Pellet Boiler Exhaust on Secondary Organic Aerosol Formation from α-Pinene.

Interactions between anthropogenic and biogenic emissions, and implications for aerosol production, have raised particular scientific interest. Despite active research in this area, real anthropogenic emission sources have not been exploited for anthropogenic-biogenic interaction studies until now. This work examines these interactions using α-pinene and pellet boiler emissions as a model test system. The impact of pellet boiler emissions on secondary organic aerosol (SOA) formation from α-pinene photo-oxidation was studied under atmospherically relevant conditions in an environmental chamber. The aim of this study was to identify which of the major pellet exhaust components (including high nitrogen oxide (NOx), primary particles, or a combination of the two) affected SOA formation from α-pinene. Results demonstrated that high NOx concentrations emitted by the pellet boiler reduced SOA yields from α-pinene, whereas the chemical properties of the primary particles emitted by the pellet boiler had no effect on observed SOA yields. The maximum SOA yield of α-pinene in the presence of pellet boiler exhaust (under high-NOx conditions) was 18.7% and in the absence of pellet boiler exhaust (under low-NOx conditions) was 34.1%. The reduced SOA yield under high-NOx conditions was caused by changes in gas-phase chemistry that led to the formation of organonitrate compounds.

SOA formation potential of emissions from soil and leaf litter.

Soil and leaf litter are significant global sources of small oxidized volatile organic compounds, VOCs (e.g., methanol and acetaldehyde). They may also be significant sources of larger VOCs that could act as precursors to secondary organic aerosol (SOA) formation. To investigate this, soil and leaf litter samples were collected from the University of Idaho Experimental Forest and transported to the laboratory. There, the VOC emissions were characterized and used to drive SOA formation via dark, ozone-initiated reactions. Monoterpenes dominated the emission profile with emission rates as high as 228 µg-C m(-2) h(-1). The composition of the SOA produced was similar to biogenic SOA formed from oxidation of ponderosa pine emissions and α-pinene. Measured soil and litter monoterpene emission rates were compared with modeled canopy emissions. Results suggest surface soil and litter monoterpene emissions could range from 12 to 136% of canopy emissions in spring and fall. Thus, emissions from leaf litter may potentially extend the biogenic emissions season, contributing to significant organic aerosol formation in the spring and fall when reduced solar radiation and temperatures reduce emissions from living vegetation.

Community-based inquiry improves critical thinking in general education biology.

National stakeholders are becoming increasingly concerned about the inability of college graduates to think critically. Research shows that, while both faculty and students deem critical thinking essential, only a small fraction of graduates can demonstrate the thinking skills necessary for academic and professional success. Many faculty are considering nontraditional teaching methods that incorporate undergraduate research because they more closely align with the process of doing investigative science. This study compared a research-focused teaching method called community-based inquiry (CBI) with traditional lecture/laboratory in general education biology to discover which method would elicit greater gains in critical thinking. Results showed significant critical-thinking gains in the CBI group but decreases in a traditional group and a mixed CBI/traditional group. Prior critical-thinking skill, instructor, and ethnicity also significantly influenced critical-thinking gains, with nearly all ethnicities in the CBI group outperforming peers in both the mixed and traditional groups. Females, who showed decreased critical thinking in traditional courses relative to males, outperformed their male counterparts in CBI courses. Through the results of this study, it is hoped that faculty who value both research and critical thinking will consider using the CBI method.