Fluxes Of Volatile Organic Compounds Research Articles

Impact of three decades of warming, increased nutrient availability, and increased cloudiness on the fluxes of greenhouse gases and biogenic volatile organic compounds in a subarctic tundra heath.

Climate change is exposing subarctic ecosystems to higher temperatures, increased nutrient availability, and increasing cloud cover. In this study, we assessed how these factors affect the fluxes of greenhouse gases (GHGs) (i.e., methane (CH4), nitrous oxide (N2O), and carbon dioxide (CO2)), and biogenic volatile organic compounds (BVOCs) in a subarctic mesic heath subjected to 34 years of climate change related manipulations of temperature, nutrient availability, and light. GHGs were sampled from static chambers and gases analyzed with gas chromatograph. BVOCs were measured using the push-pull method and gases analyzed with chromatography-mass spectrometry. The soil temperature and moisture content in the warmed and shaded plots did not differ significantly from that in the controls during GHG and BVOC measurements. Also, the enclosure temperatures during BVOC measurements in the warmed and shaded plots did not differ significantly from temperatures in the controls. Hence, this allowed for assessment of long-term effects of the climate treatment manipulations without interference of temperature and moisture differences at the time of measurements. Warming enhanced CH4 uptake and the emissions of CO2, N2O, and isoprene. Increased nutrient availability increased the emissions of CO2 and N2O but caused no significant changes in the fluxes of CH4 and BVOCs. Shading (simulating increased cloudiness) enhanced CH4 uptake but caused no significant changes in the fluxes of other gases compared to the controls. The results show that climate warming and increased cloudiness will enhance CH4 sink strength of subarctic mesic heath ecosystems, providing negative climate feedback, while climate warming and enhanced nutrient availability will provide positive climate feedback through increased emissions of CO2 and N2O. Climate warming will also indirectly, through vegetation changes, increase the amount of carbon lost as isoprene from subarctic ecosystems.

Real-time monitoring and predictive analysis of VOC flux variations in soil vapor: Integrating PID sensing with machine learning for enhanced vapor intrusion forecasts

In the rapidly evolving domain of vapor intrusion (VI) assessments, traditional methodologies encompass detailed groundwater and soil vapor sampling coupled with comprehensive laboratory measurements. These models, blending empirical data, theoretical equations, and site-specific parameters, evaluate VI risks by considering a spectrum of influential factors, from volatile organic compounds (VOC) concentrations in groundwater to nuanced soil attributes. However, the challenge of variability, influenced by dynamic ambient conditions and intricate soil properties, remains. Our study presents an advanced on-site gas sensing station geared towards real-time VOC flux monitoring, enriched with an array of ambient sensors, and spearheaded by the reliable PID sensor for VOC detection. Integrating this dynamic system with machine learning, we developed predictive models, notably the random forest regression, which boasts an R-squared value exceeding 79 % and mean relative error near 0.25, affirming its capability to predict trichloroethylene (TCE) concentrations in soil vapor accurately. By synergizing real-time monitoring and predictive insights, our methodology refines VI risk assessments, equipping communities with proactive, informed decision-making tools and bolstering environmental safety. Implementing these predictive models can simplify monitoring for residents, reducing dependence on specialized systems. Once proven effective, there's potential to repurpose monitoring stations to other VI-prone regions, expanding their reach and benefit. The developed model can leverage weather forecasting data to predict and provide alerts for future VOC events.

Odorous organic gas emission characteristics from cooked food wastes during aerobic decomposition

Emission of volatile organic compounds (VOCs) from food waste is a key trouble for surrounding residents. Herein, the VOC emission patterns from headspace (gaseous) and produced leachate (aqueous) during decomposition of cooked milk cabbage, tilapia fish, and their mixture (Mix) were investigated in self-made reactors. The average amount of gaseous VOCs from fish (2888.7 mg/kg dry matter (DM)) was higher than Mix (2152.9 mg/kg DM) and cabbage (374.2 mg/kg DM). The dominant VOCs were volatile organic sulfur compounds (VOSCs) and oxygenated VOCs, accounting for 65.8 and 32.5 %, 71.8 and 25.2 %, 39.0 and 36.7 % of total VOC yields in fish, Mix, and cabbage, respectively. From leachate, average leaching fluxes of VOCs followed the order of: Mix (2487.9 μg/(L kg) DM) > fish (2374.7 μg/(L kg) DM) > cabbage (368.7 μg/(L kg) DM). VOSCs were also the major VOCs from leachate, accounting for 87.9, 98.6, and 98.5 % of total VOCs in leachate, respectively. Lactobacillus and Weissella were the dominant genera in cabbage, while Bacteroides were dominant in fish and Mix. Physicochemical factors were significantly related to bacterial composition shifts over time. Furthermore, Lysinibacillus and Vibro were positively correlated with gaseous dimethyl disulfide, while Lactobacillus, Weissella, Savagea, Ignatzschineria, Acinetobacter, and Pseudomonas showed strong relationship with dominant gaseous and aqueous VOCs. These findings provide significant references for understanding distribution and controlling of VOCs released during cooked food waste fermentation.

Volatile organic compound fluxes in the agricultural San Joaquin Valley – spatial distribution, source attribution, and inventory comparison

Abstract. The San Joaquin Valley is an agricultural region in California that suffers from poor air quality. Since traffic emissions are decreasing, other sources of volatile organic compounds (VOCs) are gaining importance in the formation of secondary air pollutants. Using airborne eddy covariance, we conducted direct, spatially resolved flux observations of a wide range of VOCs in the San Joaquin Valley during June 2021 at 23–36 ∘C. Through land-cover-informed footprint disaggregation, we were able to attribute emissions to sources and identify tracers for distinct source types. VOC mass fluxes were dominated by alcohols, mainly from dairy farms, while oak isoprene and citrus monoterpenes were important sources of reactivity. Comparisons with two commonly used inventories showed that isoprene emissions in the croplands were overestimated, while dairy and highway VOC emissions were generally underestimated in the inventories, and important citrus and biofuel VOC point sources were missing from the inventories. This study thus presents unprecedented insights into the VOC sources in an intensive agricultural region and provides much needed information for the improvement of inventories, air quality predictions, and regulations.

Comparison between Spatially Resolved Airborne Flux Measurements and Emission Inventories of Volatile Organic Compounds in Los Angeles.

Los Angeles is a major hotspot for ozone and particulate matter air pollution in the United States. Ozone and PM2.5 in this region have not improved substantially for the past decade, despite a reduction in vehicular emissions of their precursors, NOx and volatile organic compounds (VOCs). This reduction in "traditional" sources has made the current emission mixture of air pollutant precursors more uncertain. To map and quantify emissions of a wide range of VOCs in this urban area, we performed airborne eddy covariance measurements with wavelet analysis. VOC fluxes measured include tracers for source categories, such as traffic, vegetation, and volatile chemical products (VCPs). Mass fluxes were dominated by oxygenated VOCs, with ethanol contributing ∼29% of the total. In terms of OH reactivity and aerosol formation potential, terpenoids contributed more than half. Observed fluxes were compared with two commonly used emission inventories: the California Air Resources Board inventory and the combination of the Biogenic Emission Inventory System with the Fuel-based Inventory of Vehicle Emissions combined with Volatile Chemical Products (FIVE-VCP). The comparison shows mismatches regarding the amount, spatial distribution, and weekend effects of observed VOC emissions with the inventories. The agreement was best for typical transportation related VOCs, while discrepancies were larger for biogenic and VCP-related VOCs.

Impacts of seasonality, drought, nitrogen fertilization, and litter on soil fluxes of biogenic volatile organic compounds in a Mediterranean forest

Biogenic volatile organic compounds (BVOCs) play critical roles in ecosystems at various scales, influencing above- and below-ground interactions and contributing to the atmospheric environment. Nonetheless, there is a lack of research on soil BVOC fluxes and their response to environmental changes. This study aimed to investigate the impact of drought, nitrogen (N) fertilization, and litter manipulation on soil BVOC fluxes in a Mediterranean forest. We assessed the effects of drought and N fertilization on soil BVOC exchanges and soil CO2 fluxes over two consecutive years using a dynamic chamber method, and solid-phase microextraction was utilized to quantify soil BVOCs in one year. Our findings revealed that the soil acted as an annual net sink for isoprenoids (1.30–10.33 μg m−2 h−1), with the highest uptake rates observed during summers (25.90 ± 9.36 μg m−2 h−1). The increased summer uptake can be attributed to the significant concentration gradient of BVOCs between atmosphere and soil. However, strong seasonal dynamics were observed, as the soil acted as a source of BVOCs in spring and autumn. The uptake rate of isoprenoids exhibited a significant positive correlation with soil temperature and atmospheric isoprenoid concentrations, while displaying a negative correlation with soil moisture and soil CO2 flux. The effects of drought and N fertilization on soil BVOCs were influenced by the type of VOCs, litter layer, and season. Specifically, drought significantly affected the exchange rate and quantities of sesquiterpenes. N fertilization led to increased emissions of specific BVOCs (α-pinene and camphene) due to the stimulation of litter emissions. These findings underscore the importance of the soil as a sink for atmospheric BVOCs in this dry Mediterranean ecosystem. Future drought conditions may significantly impact soil water content, resulting in drier soils throughout the year, which will profoundly affect the exchange of soil BVOCs between the soil and atmosphere.

VOCs emission from a final landfill cover system induced by ground surface air temperature and barometric pressure fluctuation

Volatile organic compounds (VOCs) emission flux and their concentration profiles were measured at a final municipal solid waste (MSW) landfill cover in Hangzhou, China. The influencing parameters, especially ground surface air temperature and pressure were monitored concomitantly. Furthermore, a numerical model incorporating coupled thermo-hydro-chemical interaction to assess VOCs emission from this final landfill cover (LFC) system was developed and validated with the field test results. The tested total VOC emission flux from the final cover is 0.0124 μg/m2/s, which indicates that the total amount of VOCs emitted into the atmosphere is 391 mg/m2 annually. Among these, dichloromethane (DCM) dominated VOCs emission flux during May, comprising 51.8% of the total emission flux. The numerical simulation results indicated that the diffusive emission flux of VOCs varied consistently with the fluctuation of atmospheric temperature. Whereas, the advective flux varied inversely with the fluctuation of barometric pressure. The highest difference in diffusive emission flux induced by temperature variation is 183 μg/m2/day and occurred in spring. Moreover, the results demonstrated that the impact of atmospheric temperature and pressure fluctuation on the emission of VOC from final covers is non-negligible when reasonably assessing the risks of landfill and landfill gas emission budget.

Effects of drought and recovery on soil volatile organic compound fluxes in an experimental rainforest

Drought can affect the capacity of soils to emit and consume biogenic volatile organic compounds (VOCs). Here we show the impact of prolonged drought followed by rewetting and recovery on soil VOC fluxes in an experimental rainforest. Under wet conditions the rainforest soil acts as a net VOC sink, in particular for isoprenoids, carbonyls and alcohols. The sink capacity progressively decreases during drought, and at soil moistures below ~19%, the soil becomes a source of several VOCs. Position specific 13C-pyruvate labeling experiments reveal that soil microbes are responsible for the emissions and that the VOC production is higher during drought. Soil rewetting induces a rapid and short abiotic emission peak of carbonyl compounds, and a slow and long biotic emission peak of sulfur-containing compounds. Results show that, the extended drought periods predicted for tropical rainforest regions will strongly affect soil VOC fluxes thereby impacting atmospheric chemistry and climate.

Leaf-level metabolic changes in response to drought affect daytime CO2 emission and isoprenoid synthesis pathways.

In the near future, climate change will cause enhanced frequency and/or severity of droughts in terrestrial ecosystems, including tropical forests. Drought responses by tropical trees may affect their carbon use, including production of volatile organic compounds (VOCs), with implications for carbon cycling and atmospheric chemistry that are challenging to predict. It remains unclear how metabolic adjustments by mature tropical trees in response to drought will affect their carbon fluxes associated with daytime CO2 production and VOC emission. To address this gap, we used position-specific 13C-pyruvate labeling to investigate leaf CO2 and VOC fluxes from four tropical species before and during a controlled drought in the enclosed rainforest of Biosphere 2 (B2). Overall, plants that were more drought-sensitive had greater reductions in daytime CO2 production. Although daytime CO2 production was always dominated by non-mitochondrial processes, the relative contribution of CO2 from the tricarboxylic acid cycle tended to increase under drought. A notable exception was the legume tree Clitoria fairchildiana R.A. Howard, which had less anabolic CO2 production than the other species even under pre-drought conditions, perhaps due to more efficient refixation of CO2 and anaplerotic use for amino acid synthesis. The C. fairchildiana was also the only species to allocate detectable amounts of 13C label to VOCs and was a major source of VOCs in B2. In C. fairchildiana leaves, our data indicate that intermediates from the mevalonic acid (MVA) pathway are used to produce the volatile monoterpene trans-β-ocimene, but not isoprene. This apparent crosstalk between the MVA and methylerythritol phosphate pathways for monoterpene synthesis declined with drought. Finally, although trans-β-ocimene emissions increased under drought, it was increasingly sourced from stored intermediates and not de novo synthesis. Unique metabolic responses of legumes may play a disproportionate role in the overall changes in daytime CO2 and VOC fluxes in tropical forests experiencing drought.

Quantification of Ozone Pollution Transport Based on Four-dimensional Flux Method in Foshan, China

Quantifying the contribution of transport processes to air pollution events has been a prominent challenge and an important need in regional air pollution prevention and control. The WRF-Chem model was used to simulate a typical regional ozone (O3) pollution event in Foshan, and the four-dimensional flux method was applied to quantify the transport fluxes of ozone and its precursors from the surrounding areas to Foshan and to clarify the contributions of the direct transport of ozone and transport of precursors. The average ozone flux from the surrounding areas to Foshan was 120.3 t·h-1, the volatile organic compound (VOCs) flux was 30.2 t·h-1, and the corresponding ozone formation potential (OFP) was 114.8 t·h-1. By counting the transport fluxes of each ozone pollution event, it was found that the city with the largest ozone flux into Foshan during the pollution period was Guangzhou (contributed 44%); the city with the largest input VOCs flux was Zhaoqing (contributed 48%). The analysis of ozone generation potential due to transported VOCs emissions found that oxygenated volatile organic compounds (OVOCs) contributed the most to OFP, accounting for 47% of the "maximum input events." OVOCs and aromatic hydrocarbons such as formaldehyde, xylenes, aldehydes, acetone, and phenols were the top five species contributing to the OFP, contributing more than 50% of the total OFP, mainly from industrial solvent sources.

Improved Darcian streambed measurements to quantify flux and mass discharge of volatile organic compounds from a contaminated aquifer to an urban stream

Quantifying VOC transport from contaminated groundwater to streams is challenging and important for understanding off-site migration of VOCs, cross-media contamination (groundwater to surface water and eventually air), and potential impacts on downstream ecosystems and human populations. A streambed point sampling approach was used to quantify fluxes of water and 14 VOCs from groundwater to an urban stream in North Carolina, USA, during summer (June 2015) and winter (January 2016). The approach is unique in coupling measurements of vertical hydraulic conductivity, vertical hydraulic head gradient, and groundwater VOC concentration at each individual sampling point, reducing or eliminating some potential concerns with other Darcian methods for quantifying VOC inputs to streams.Most results were consistent with discharge of two main VOC plumes on opposite sides of the stream. Plume 1 from the west side was dominated by cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC) at mean concentrations of 19 and 11 μg L−1, respectively. Plume 2 from the east side was dominated by benzene (mean concentration 56 μg L−1). Plume 2 was not previously known, and the improved sampling approach allowed VOC discharge from both plumes to be quantified simultaneously.For 13 of the 14 detected VOCs, the mean VOC flux from groundwater to the stream (fVOC) was higher in January 2016 than in June 2015, mainly because groundwater flux was higher in January. The only exception was cDCE, the most abundant VOC in Plume 1, which had mean fVOC values of 9.8 and 9.5 mg m−2 d−1 in June 2015 and January 2016, respectively. Benzene was the most abundant VOC in Plume 2 and had mean fVOC values of 11 and 37 mg m−2 d−1 in June 2015 and January 2016, respectively. High groundwater flux drove almost all the occurrences of high VOC flux. For a given VOC, the flow-weighted mean concentration (with each VOC concentration weighted by the upward groundwater flux at the VOC sampling point) was generally larger than the unweighted mean concentration. Thus, flow-weighting of concentrations gave a more accurate indication of the average VOC concentration in net groundwater discharge to the stream.An estimate of total VOC mass discharge from groundwater to the study reach of the stream, 3.6 kg of VOC per year, was based on the fVOC results and streambed area in the reach. The bulk of this discharge was due to benzene, cDCE, and VC, with individual mass discharges of 2.1, 0.83, and 0.40 kg yr−1, respectively. Estimates of maximum potential VOC degradation in the streambed suggest that the 3.6 kg yr−1 estimate of mass discharge was not sensitive to potential degradation of VOCs in the streambed sediments above the groundwater sampling depth.

Interfacial photochemistry of marine diatom lipids: Abiotic production of volatile organic compounds and new particle formation

The global importance of abiotic oceanic production of volatile organic compounds (VOCs) still presents a source of high uncertainties related to secondary organic aerosol (SOA) formation. A better understanding of the photochemistry occurring at the ocean-atmosphere interface is particularly important in that regard, as it covers >70% of the Earth's surface. In this work, we focused on the photochemical VOCs production at the air-water interface containing organic material from authentic culture of marine diatom Chaetoceros pseudocurvisetus. Abiotic VOCs production upon irradiation of material originating from total phytoplankton culture as well as the fraction containing only dissolved material was monitored by means of PTR-ToF-MS. Furthermore, isolated dissolved lipid fraction was investigated after its deposition at the air-water interface. All samples acted as a source of VOCs, producing saturated oxygenated compounds such as aldehydes and ketones, as well as unsaturated and functionalized compounds. Additionally, a significant increase in surfactant activity following irradiation experiments observed for all samples implied biogenic material photo-transformation at the air-water interface. The highest VOCs flux normalized per gram of carbon originated from lipid material, and the produced VOCs were introduced into an atmospheric simulation chamber, where particle formation was observed after its gas-phase ozonolysis. This work clearly demonstrates abiotic production of VOCs from phytoplankton derived organic material upon irradiation, facilitated by its presence at the air/water interface, with significant potential for affecting the global climate as a precursor of particle formation.

Seasonal and diel patterns of biogenic volatile organic compound fluxes in a subarctic tundra

In arctic and subarctic regions, rapid climate changes enhance biogenic volatile organic compound (BVOC) emissions from vegetation, with potentially significant influence on atmospheric processes. However, the seasonal and diel patterns of bidirectional exchange (flux) of BVOCs remain poorly studied in these regions. Here, we deployed a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) to investigate ecosystem-level BVOC fluxes over a growing season in a subarctic tundra heath in Abisko, Northern Sweden, and to quantify BVOC emissions from two widespread dwarf shrubs in the high latitudes, Salix myrsinites and Betula nana. As expected, ecosystem fluxes of short-chained oxygenated compounds (e.g., methanol, acetaldehyde and acetone) and terpenoids (e.g., isoprene, monoterpenes and sesquiterpenes) followed different seasonal and diel patterns. For the short-chained oxygenated compounds, net emissions dominated and peaked in the early growing season, while net deposition occurred sporadically, particularly at night. In contrast, terpenoids were almost exclusively emitted from the ecosystem, with maxima occurring in the peak growing season. At the branch level, these compound groups were emitted from both S. myrsinites and B. nana in clear diel patterns with high emissions during the day. S. myrsinites was dominated by isoprene emissions whilst B. nana was dominated by terpene emissions. Methanol, acetaldehyde and acetone were emitted at comparable levels and similar patterns from both species. Both ecosystem fluxes and branch emissions responded exponentially to enclosure temperature and depended on light levels. Compared to the BVOC emission models, however, the temperature responses were steeper for isoprene, monoterpenes, methanol and acetone, but weaker for sesquiterpenes. Apart from the well-known compounds, many other BVOCs, such as some carbonyls and nitrogen-containing compounds, were emitted from both the ecosystem and plants with significant contributions to the season variation in ecosystem fluxes. Overall, our study highlights the complexity of subarctic ecosystem BVOC fluxes, which vary both seasonally and diurnally. Vegetation composition changes triggered by climate change will shift BVOC composition, with important implications for atmospheric processes and local climate.

Real-time air concentrations and turbulent fluxes of volatile organic compounds (VOCs) over historic closed landfills to assess their potential environmental impact

For the first time, emission/deposition fluxes of volatile organic compounds (VOCs) and H2S from a historic closed landfill site in Southern Italy were determined by Eddy Covariance (EC) using Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-TOF-MS). This was done in two field campaigns of one week performed in July and October 2016, where fluxes of CO2 and CH4 were also measured. Many compounds not previously identified in the biogas were detected by PTR-TOF-MS, but only in July some of them produced positive fluxes exceeding the flux limit of detection. Methanol was the most emitted compound with an average flux of 44.20 ± 4.28 μg m−2 h−1, followed by toluene with a mean flux of 18.97 ± 2.47 μg m−2 h−1. Toluene fluxes were 10 times higher than those of benzene, fitting rather well with values previously measured in the biogas. VOCs emission fluxes of monoterpenes and highly reactive arenes did not reflect, however, the biogas composition. This, combined with tiny emissions of VOC oxidation products, suggests that landfill emissions underwent some photochemical degradation before being dispersed in the atmospheric boundary layer (ABL). Deposition fluxes of some VOCs emitted from the sea was also observed in July. No relevant VOC fluxes were instead measured in October, suggesting that temperature was the variable controlling most landfill emission. Albeit small, summer landfill emissions from the investigated site can have an impact on the population living nearby, because they contain or still generate compounds that causing nuisance.

A floating chamber system for VOC sea-to-air flux measurement near the sea surface.

Volatile organic compounds (VOCs) form ozone (O3) and secondary organic aerosols (SOAs) in the atmosphere under favourable conditions. Biogenic VOC levels in the marine atmosphere are significantly lower compared with levels in the atmosphere above terrestrial ecosystems. However, much less is known about the marine biogenic VOC sea-to-air flux, specifically at the sea surface level. Therefore, here we describe a newly developed and cost-effective floating chamber system that has the capacity to measure the VOC sea-to-air flux near the sea surface (< 1m). The floating chamber is coupled with adsorbent cartridges, and samples were analysed in the laboratory using commercial thermal desorption and gas chromatography mass spectrometry (TD-GC-MS). The structural performance of the floating flux chamber was evaluated, and it was shown to have the capacity to stay continuously afloat for up to 72h in various conditions (e.g., rainy, windy) and with wave heights up to approximately 1m in coastal waters. Preliminary measurements of isoprene (3-Methyl-1,2-butadiene) (C5H8) sea-to-air flux using the floating flux chamber in the coastal waters off the east coast of Peninsular Malaysia found values in the region of 107 molecules/cm2/s, comparable with most published values based on various flux measurement techniques. We suggest the proposed floating chamber system could serve as a cost-effective VOC flux technique that allows measurements near the sea surface.

Plasma Polymerized Coatings on Hollow Fiber Membranes-Applications and Their Aging Characteristics in Different Media.

In the past 30 years, plasma polymerization has emerged as a versatile technique for depositing ultrathin nanocoating on a variety of substrates for applications that range from providing lubricity to the substrate, protection from harsh environments, promoting adhesion, surface modification to applications of coating in ultrafiltration and gas separation membranes. Applications in the field of volatile organic compound (VOC) recovery and membrane distillation have also gained importance in recent years. Most of these applications use silicone and fluorosilicone-based plasma polymers that provide versatility, good separation characteristics, and long-term stability to the membrane. However, plasma polymers are known to age with time. The current study focuses on the aging behavior of silicone and fluorosilicone plasma polymers in different environments that include air, ionized air, heat, aqueous solutions of inorganic chemicals, as well as harsh solvents such as hexane, dichloromethane (DCM), and toluene. Membrane gas permeance and gas selectivity were used to quantitatively measure the aging behavior of the coatings on gas separation membranes, while water and VOC flux were used to measure the effect of aging for membranes designed for membrane distillation and VOC separation. It was found that while all plasma polymers of this study showed changes in membrane gas permeance on exposure to air, they fundamentally retained their membrane separation characteristics in all the studied environments. Significant changes in gas permeability characteristics were observed on exposure of the membranes to organic solvents like dichloromethane, 2-propanol, hexane, and toluene, which are attributed to dimensional changes in the hollow fiber substrate rather than changes in plasma polymer characteristics. Ionized air was also found to have a significant effect on the gas permeability characteristic of the membranes, reducing the gas permeance by as much as 50% in some cases. This is attributed to accelerated oxidation and crosslinking of the polymer in ionized air. XPS studies showed an increase in the oxygen content of the polymer on aging. Differences were found in the aging behavior of polymer coatings made from different monomers with long-chain monomers such as hexamethyltrisiloxane offering more stable coatings. The cross-link density of the polymer also influenced the aging behavior, with the more cross-linked polymer showing a lesser influence on aging in a chemical environment. No significant effect of aging was found on applications of these polymer coatings in the field of membrane distillation, pervaporation, and VOC removal, and a stable performance was observed over a long period of time. It was also noted that the selection of co-monomers played a significant role in membrane distillation, with polymers forming fluoro co-monomers giving better results. The current study also demonstrated the usefulness of plasma polymers in controlling the pore size of microporous membranes that can find useful applications in bio-filtration and VOC recovery.

Bidirectional Exchange of Biogenic Volatile Organic Compounds in Subarctic Heath Mesocosms During Autumn Climate Scenarios.

Biogenic volatile organic compound (BVOC) flux dynamics during the subarctic autumn are largely unexplored and have been considered insignificant due to the relatively low biological activity expected during autumn. Here, we exposed subarctic heath ecosystems to predicted future autumn climate scenarios (ambient, warming, and colder, dark conditions), changes in light availability, and flooding, to mimic the more extreme rainfall or snowmelt events expected in the future. We used climate chambers to measure the net ecosystem fluxes and bidirectional exchange of BVOCs from intact heath mesocosms using a dynamic enclosure technique coupled to a proton‐transfer‐reaction time‐of‐flight mass spectrometer (PTR–ToF–MS). We focused on six BVOCs (methanol, acetic acid, acetaldehyde, acetone, isoprene, and monoterpenes) that were among the most dominant and that were previously identified in arctic tundra ecosystems. Warming increased ecosystem respiration and resulted in either net BVOC release or increased uptake compared to the ambient scenario. None of the targeted BVOCs showed net release in the cold and dark scenario. Acetic acid exhibited significantly lower net uptake in the cold and dark scenario than in the ambient scenario, which suggests reduced microbial activity. Flooding was characterized by net uptake of the targeted BVOCs and overruled any temperature effects conferred by the climate scenarios. Monoterpenes were mainly taken up by the mesocosms and their fluxes were not affected by the climate scenarios or flooding. This study shows that although autumn BVOC fluxes on a subarctic heath are generally low, changes in future climate may strongly modify them.

Role of water in unexpectedly large changes in emission flux of volatile organic compounds in soils under dynamic temperature conditions

Understanding the diffusive transport behavior of volatile organic compounds (VOCs) in near-surface soils is important because soil VOC emissions affect atmospheric conditions and climate. Previous studies have suggested that temperature changes affect the transport behavior; however, the effect of these changes are poorly understood. Indeed, under dynamic temperature conditions, the change in VOC flux is much larger than that expected from the temperature dependency of the diffusion coefficient of VOCs in air. However, the mechanism is not well understood, although water in soil has been considered to play an important role. Here, we present the results of experiments for the upward vertical vapor-phase diffusive transport of two VOCs (benzene and tetrachloroethylene) in sandy soil under sinusoidal temperature variations of 20–30 °C, as well as its numerical representation. The results clarify that the unexpectedly large changes in emission flux can occur as a result of changes in the VOC concentration gradient due to VOC release (volatilization) from/trapping (dissolution) into water, and that such flux changes may occur in various environments. This study suggests the importance of a global evaluation of soil VOC emissions by continuous measurements in various soil environments and/or predictions through numerical simulations with thorough consideration of the role of water in dynamic soil environments.

Volatile organic compound fluxes over a winter wheat field by PTR-Qi-TOF-MS and eddy covariance

Abstract. Volatile organic compounds (VOCs) contribute to air pollution through the formation of secondary aerosols and ozone and extend the lifetime of methane in the atmosphere. Tropospheric VOCs originate to 90 % from biogenic sources on a global scale, mainly from forests. Crops are also a potentially large yet poorly characterized source of VOCs (30 % of the VOC emissions in Europe, mostly oxygenated). In this study, we investigated VOC fluxes over a winter wheat field by eddy covariance using a PTR-Qi-TOF-MS with high sensitivity and mass resolution. The study took place near Paris over a 5-week period and included flowering, crop maturity and senescence. We found a total of 123 VOCs with fluxes 3 times above the detection limit. Methanol was the most emitted compound with an average flux of 63 µg m−2 h−1, representing about 52 % of summed VOC emissions on a molar basis (36 % on a mass basis). We also identified ethanol, acetone, acetaldehyde and dimethyl sulfide among the six most emitted compounds. The third most emitted VOC corresponded to the ion m/z 93.033. It was tentatively identified as furan (C6H4O), a compound not previously reported to be strongly emitted by crops. The average summed VOC emissions were about 173 ± 6 µg m2 h−1, while the average VOC depositions were about 109 ± 2 µg m−2 h−1 and hence 63 % of the VOC emissions on a mass basis. The net ecosystem flux of VOCs was an emission of 64 ± 6 µg m−2 h−1 (0.5 ± 0.05 nmol m−2 s−1). The most deposited VOCs were identified as hydroxyacetone, acetic acid and fragments of oxidized VOCs. Overall, our results reveal that wheat fields represent a non-negligible source and sink of VOCs to be considered in regional VOC budgets and underline the usefulness and limitations of eddy covariance measurements with a PTR-Qi-TOF-MS.

Leaf Fluxes of Carbon Dioxide, Methane and Biogenic Volatile Organic Compounds of the Urban Trees Platanus × acerifolia and Schinus molle in Santiago, Chile

This study assessed leaf fluxes of CO2, CH4 and biogenic volatile organic compounds (BVOC) for two common urban tree species, Platanus × acerifolia (exotic) and Schinus molle (native), widely distributed in Santiago, Chile. The emission factors (EF) and the Photochemical Ozone Creation Index (POCI) for S. molle and P. × acerifolia were estimated. The global EF was 6.4 times higher for P. × acerifolia compared with S. molle, with similar rates of photosynthesis for both species. Isoprene represented more than 86% of the total BVOCs leaf fluxes being 7.6 times greater for P. × acerifolia than S. molle. For P. × acerifolia, BVOCs represented 2% of total carbon fixation while representing 0.24% for S. molle. These results may suggest that plant species growing outside their ecological range may exhibit greater BVOCs leaf fluxes, proportional to photosynthesis, compared to well-adapted ones. The results found may contribute to better urban forest planning.