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Abstract. Volatile organic compounds (VOCs) contribute to air pollution both directly, as hazardous gases, and through their reactionswith common atmospheric oxidants to produce ozone, particulate matter, andother hazardous air pollutants. There are enormous ranges of structures andreaction rates among VOCs, and there is consequently a need to accuratelycharacterize the spatial and temporal distribution of individual identifiedcompounds. Current VOC measurements are often made with complex, expensiveinstrumentation that provides high chemical detail but is limited in itsportability and requires high expense (e.g., mobile labs) for spatiallyresolved measurements. Alternatively, periodic collection of samples oncartridges is inexpensive but demands significant operator interaction thatcan limit possibilities for time-resolved measurements or distributedmeasurements across a spatial area. Thus, there is a need for simple,portable devices that can sample with limited operator presence to enabletemporally and/or spatially resolved measurements. In this work, we describenew portable and programmable VOC samplers that enable simultaneouscollection of samples across a spatially distributed network, validate theirreproducibility, and demonstrate their utility. Validation experimentsconfirmed high precision between samplers as well as the ability ofminiature ozone scrubbers to preserve reactive analytes collected oncommercially available adsorbent gas sampling cartridges, supportingsimultaneous field deployment across multiple locations. In indoorenvironments, 24 h integrated samples demonstrate observable day-to-dayvariability, as well as variability across very short spatial scales(meters). The utility of the samplers was further demonstrated by locatingoutdoor point sources of analytes through the development of a new mappingapproach that employs a group of the portable samplers and back-projectiontechniques to assess a sampling area with higher resolution than stationarysampling. As with all gas sampling, the limits of detection depend onsampling times and the properties of sorbents and analytes. The limit of detectionof the analytical system used in this work is on the order of nanograms,corresponding to mixing ratios of 1–10 pptv after 1 h of sampling atthe programmable flow rate of 50–250 sccm enabled by the developed system.The portable VOC samplers described and validated here provide a simple,low-cost sampling solution for spatially and/or temporally variablemeasurements of any organic gases that are collectable on currentlyavailable sampling media.

 

Volatile organic compounds (VOCs) range in their reaction rates with atmospheric oxidants by several orders of magnitude. Therefore, studying their atmospheric concentrations across seasons and years requires isomer resolution to fully understand their impact on oxidant budgets and secondary organic aerosol formation. An automated gas chromatograph/flame ionization detector (GC-FID) was developed for hourly sampling and analysis of C 5 –C 15 hydrocarbons at remote locations. Samples are collected on an air-cooled multibed adsorbent trap for preconcentration of hydrocarbons in the target volatility range, specifically designed to minimize dead volume and enable rapid heating and sample flushing. Instrument control uses custom electronics designed to allow flexible autonomous operation at moderate cost, with automated data transfer and processing. The instrument has been deployed for over two years with samples collected mid-canopy from the Virginia Forest Laboratory located in the Pace research forest in central Virginia. We present here the design of the instrument itself, control electronics, and calibration and data analysis approaches to facilitate the development of similar systems by the atmospheric chemistry community. Detection limits of all species are in the range of a few to tens of ppt and the instrument is suitable for detection of a wide range of biogenic, lightly oxygenated, and anthropogenic (predominantly hydrocarbon) compounds. Data from calibrations are examined to provide understanding of instrument stability and quantify uncertainty. In this work, we present challenges and recommendations for future deployments, as well as suggested adaptions to decrease required maintenance and increase instrument up-time. The presented design is particularly suitable for long-term and remote deployment campaigns where access, maintenance, and transport of materials are difficult. 

Abstract. Emissions from natural sources are driven by various external stimuli such as sunlight, temperature, and soil moisture. Once biogenic volatile organic compounds (BVOCs) are emitted into the atmosphere, they rapidly react with atmospheric oxidants, which has significant impacts on ozone and aerosol budgets. However, diurnal, seasonal, and interannual variability in these species are poorly captured in emissions models due to a lack of long-term, chemically speciated measurements. Therefore, increasing the monitoring of these emissions will improve the modeling of ozone and secondary organic aerosol concentrations. Using 2 years of speciated hourly BVOC data collected at the Virginia Forest Research Lab (VFRL) in Fluvanna County, Virginia, USA, we examine how minor changes in the composition of monoterpenes between seasons are found to have profound impacts on ozone and OH reactivity. The concentrations of a range of BVOCs in the summer were found to have two different diurnal profiles, which, we demonstrate, appear to be driven by light-dependent versus light-independent emissions. Factor analysis was used to separate the two observed diurnal profiles and determine the contribution from each emission type. Highly reactive BVOCs were found to have a large influence on atmospheric reactivity in the summer, particularly during the daytime. These findings reveal the need to monitor species with high atmospheric reactivity, even though they have low concentrations, to more accurately capture their emission trends in models. 

Biogenic volatile organic compounds (BVOCs) contribute the majority of reactive organic carbon to the atmosphere and lead to aerosol formation through reaction with atmospheric oxidants including ozone and hydroxyl radicals. One class of BVOCs, sesquiterpenes, have a high reactivity with ozone but exist at lower concentrations compared to other BVOCs, and there are relatively few measurements of their concentrations in different environments or their importance in the atmospheric oxidant budget. To help close this knowledge gap, we examine concentrations of isomer-resolved sesquiterpene concentrations collected hourly at two sites in Virginia that are representative of different ecosystems in the southeastern US. Sesquiterpene concentrations are presented and discussed in relation to their diurnal patterns and used to estimate their contribution to reactivity with common gas-phase oxidants. Twenty-four sesquiterpenes were identified at the sites, eleven of which were observed at both sites. Total sesquiterpene concentrations were found to range between 0.8 and 2 ppt with no single isomer dominating throughout. Hydroxyl activity is similarly diverse, with no particular isomer dominating activity at either site. Ozone reactivity, however, was found to be dominated (∼3/4 total reactivity) by β-caryophyllene and humulene despite these compounds representing roughly only 10% of total sesquiterpene mass, highlighting their importance as the major driver of sesquiterpene-ozone reactivity. Average reaction rate constants for sesquiterpenes with ozone and hydroxyl radicals were calculated for both sites as a method to simplify future atmospheric modelling concerning sesquiterpenes. This work provides broad insight into the composition and impacts of sesquiterpenes, suggesting that sesquiterpene composition is relatively similar between sites. Furthermore, while the calculated average sesquiterpene-ozone reaction rate constants are at least an order of magnitude higher than that of more prevalent BVOC classes (isoprene and monoterpenes), their low concentrations suggest their impacts on atmospheric reactivity are expected to be limited to periods of high emissions. 

Abstract. Despite the significant contribution of biogenic volatileorganic compounds (BVOCs) to organic aerosol formation and ozone productionand loss, there are few long-term, year-round, ongoing measurements oftheir volume mixing ratios and quantification of their impacts onatmospheric reactivity. To address this gap, we present 1 year of hourlymeasurements of chemically resolved BVOCs between 15 September 2019 and15 September 2020, collected at a research tower in Central Virginiain a mixed forest representative of ecosystems in the Southeastern US.Mixing ratios of isoprene, isoprene oxidation products, monoterpenes, andsesquiterpenes are described and examined for their impact on the hydroxyradical (OH), ozone, and nitrate reactivity. Mixing ratios of isoprene rangefrom negligible in the winter to typical summertime 24 h averages of 4–6 ppb, while monoterpenes have more stable mixing ratios in the range of tenths of a part per billion up to ∼2 ppb year-round. Sesquiterpenes aretypically observed at mixing ratios of <10 ppt, but this representsa lower bound in their abundance. In the growing season, isoprene dominatesOH reactivity but is less important for ozone and nitrate reactivity.Monoterpenes are the most important BVOCs for ozone and nitrate reactivitythroughout the year and for OH reactivity outside of the growing season. Tobetter understand the impact of this compound class on OH, ozone, andnitrate reactivity, the role of individual monoterpenes is examined. Despitethe dominant contribution of α-pinene to total monoterpene mass, theaverage reaction rate of the monoterpene mixture with atmospheric oxidantsis between 25 % and 30 % faster than α-pinene due to thecontribution of more reactive but less abundant compounds. A majority ofreactivity comes from α-pinene and limonene (the most significantlow-mixing-ratio, high-reactivity isomer), highlighting the importance ofboth mixing ratio and structure in assessing atmospheric impacts ofemissions. 

Abstract. Urbanization and deforestation have important impacts on atmosphericparticulate matter (PM) over Amazonia. This study presents observations andanalysis of PM₁ concentration, composition, and opticalproperties in central Amazonia during the dry season, focusing on theanthropogenic impacts. The primary study site was located 70&thinsp;km downwind ofManaus, a city of over 2 million people in Brazil, as part of theGoAmazon2014/5 experiment. A high-resolution time-of-flight aerosol massspectrometer (AMS) provided data on PM₁ composition, and aethalometermeasurements were used to derive the absorption coefficient b_abs,BrC ofbrown carbon (BrC) at 370&thinsp;nm. Non-refractory PM₁ mass concentrationsaveraged 12.2&thinsp;µg&thinsp;m⁻³ at the primary study site, dominated byorganics (83&thinsp;%), followed by sulfate (11&thinsp;%). A decrease inb_abs,BrC was observed as the mass concentration of nitrogen-containingorganic compounds decreased and the organic PM₁ O:C ratio increased,suggesting atmospheric bleaching of the BrC components. The organic PM₁was separated into six different classes by positive-matrix factorization(PMF), and the mass absorption efficiency E_abs associated with eachfactor was estimated through multivariate linear regression ofb_abs,BrC on the factor loadings. The largest E_abs values wereassociated with urban (2.04±0.14&thinsp;m²&thinsp;g⁻¹) and biomass-burning(0.82±0.04 to 1.50±0.07&thinsp;m²&thinsp;g⁻¹) sources. Together, these sources contributed at least 80&thinsp;% ofb_abs,BrC while accounting for 30&thinsp;% to 40&thinsp;% of the organic PM₁ massconcentration. In addition, a comparison of organic PM₁ compositionbetween wet and dry seasons revealed that only part of the 9-foldincrease in mass concentration between the seasons can be attributed tobiomass burning. Biomass-burning factor loadings increased by 30-fold,elevating its relative contribution to organic PM₁ from about 10&thinsp;% inthe wet season to 30&thinsp;% in the dry season. However, most of the PM₁mass (&gt;60&thinsp;%) in both seasons was accounted for by biogenicsecondary organic sources, which in turn showed an 8-fold seasonalincrease in factor loadings. A combination of decreased wet deposition andincreased emissions and oxidant concentrations, as well as a positivefeedback on larger mass concentrations are thought to play a role in theobserved increases. Furthermore, fuzzy c-means clustering identified threeclusters, namely “baseline”, “event”, and “urban” to representdifferent pollution influences during the dry season. The baseline cluster,representing the dry season background, was associated with a mean massconcentration of 9±3&thinsp;µg&thinsp;m⁻³. This concentration increasedon average by 3&thinsp;µg&thinsp;m⁻³ for both the urban and the event clusters.The event cluster, representing an increased influence of biomass burningand long-range transport of African volcanic emissions, was characterized byremarkably high sulfate concentrations. The urban cluster, representing theinfluence of Manaus emissions on top of the baseline, was characterized byan organic PM₁ composition that differed from the other two clusters.The differences discussed suggest a shift in oxidation pathways as well asan accelerated oxidation cycle due to urban emissions, in agreement withfindings for the wet season.