Concentrations Of Biogenic Volatile Organic Compounds Research Articles

Urban–Rural Comparisons of Biogenic Volatile Organic Compounds and Ground-Level Ozone in Beijing

Ground-level ozone (O3) pollution has been a severe environmental and health problem for decades. The importance of biogenic volatile organic compounds (BVOCs) in the formation of tropospheric photochemistry O3 has been highlighted, especially in areas of rapid urbanization. We conducted simultaneous measurements of trace gases, including NO, NOX, O3, and BVOCs (i.e., isoprene and α-pinene), in the urban and rural forest areas of Beijing to determine the relationships between them. The results highlight the differences between the urban and rural forest areas of Beijing in terms of ambient air concentrations of BVOCs and O3, and the interrelationships between BVOCs, NOX, and ozone were quantified. Moreover, the isoprene concentration was found to be higher in the atmosphere of the urban site than of the rural site, which had higher α-pinene concentrations and higher O3 concentrations. The NOX concentration was higher at the urban site than at the rural site, and there was a significant exponential relationship between NOX and O3 at the urban site, indicating that the impact of NOx on O3 at the urban site was greater than that at the rural site. The O3 concentration increased with rising isoprene and α-pinene in both sites. In the case of substantially increased BVOC concentrations, declining NOX concentrations strongly promote the formation of O3. Consideration should be given to planting tree species with low-BVOC emissions, as they are crucial for mitigating O3 pollution in urban areas. Additionally, the relationships between BVOCs, NOX, and O3 should be considered in policymaking related to O3 control.

Determination of BVOCs based on high time-resolved measurements in urban and forest areas in Japan

Biogenic volatile organic compounds (BVOCs) with high photochemical activity and short atmospheric lifetimes are major contributors to tropospheric ozone and other photochemical air pollution. Although several studies have been conducted on BVOC emissions in Japan, no comprehensive observations have been made to determine the actual state of BVOCs in the atmosphere. Therefore, we conducted time-resolved measurements of atmospheric BVOCs in urban and forested areas throughout the year. The concentrations of BVOCs were higher in summer than in the other seasons. Isoprene concentrations were higher during hours with higher temperatures and solar radiation. However, there were also months and times of the year when monoterpenes showed high concentrations, which indicates that the behavior of the BVOC components differed depending on the time of the year. The results of the propylene equivalent concentration indicated that BVOCs considerably contributed to tropospheric ozone production. The year-long observations of BVOCs in this study contribute to our understanding of the actual status of atmospheric BVOC concentrations and components and the uncertainty in the calculation results of chemical transport models.

Sequential Interaction of Biogenic Volatile Organic Compounds and SOAs in Urban Forests Revealed Using Toeplitz Inverse Covariance-Based Clustering and Causal Inference

Urban forests play a crucial role in both emitting and absorbing atmospheric pollutants. Understanding the ecological processes of biogenic volatile organic compounds (BVOCs) and secondary organic aerosols (SOAs) and their interactions in urban forests can help to assess how they influence air quality. Additionally, exploring the adaptation and feedback mechanisms between urban forests and their surrounding environments can identify new pollutants and potential risks in urban forests. However, the relationship between BVOC emissions and SOA formation is complex due to the influence of meteorological conditions, photochemical reactions, and other factors. This complexity makes it challenging to accurately describe this relationship. In this study, we used time-of-flight mass spectrometry and aerosol particle size spectrometry to monitor concentrations of BVOCs and particulate matter with a diameter less than 1 µm (PM1; representing SOAs) at a frequency of 10–12 times per min in an urban forest near Shanghai. We then analyzed the temporal changes in concentrations of BVOCs, SOAs, and other chemical pollutants in different periods of the day by using subsequence clustering and causal inference methods. The results showed that after using this method for diurnal segmentation, PM1 prediction accuracy was improved by 26.77%–47.51%, and the interaction rules of BVOCs and SOAs had sequential interaction characteristics. During the day, BVOCs are an important source of SOAs and have a negative feedback relationship with O3. From night to early morning, BVOCs have a positive, balanced relationship with O3, SOAs are affected by wind speed or deposition, BVOCs have no obvious relationship with O3, and SOAs are affected by temperature or humidity. This study is the first to apply Toeplitz inverse covariance-based clustering and causal inference methods for the high-frequency monitoring of BVOCs and SOAs, revealing the temporal effects and characteristics of BVOCs and SOAs and providing a scientific basis and new methods for understanding the dynamic effects of urban forest communities on the environment.

The potential impact of biogenic volatile organic compounds (BVOCs) from terrestrial vegetation on a Mediterranean area using two different emission models

Biogenic Volatile Organic Compounds (BVOCs) emitted from vegetation are precursors of ozone (O3), photochemical oxidants and secondary organic aerosols (SOA) in the lower troposphere. The interaction between urban polluted air plumes originated along the coasts of the Mediterranean basin with biogenic emission occurring inland contributes to the occurrence of exceedances of the air quality standards for O3 and fine suspended particles (PM10, PM2.5). This interaction is favoured by prevailing sea-land breeze circulation during persistent high-pressure conditions. The actual contribution of BVOC to photochemical pollution is still uncertain because the approaches used to assess the emissions from terrestrial vegetation are quite different. There is some evidence in literature that BVOC emissions from Mediterranean vegetation is not accurately estimated by models based on the plant functional types (PFT) approach. To investigate these issues, a Plant Specific Emission Model (PSEM) was developed and applied to the Campania region in Southern Italy, for which a detailed vegetation inventory has been built. BVOC emission maps estimated by PSEM were compared with those generated using a PFT methodology, evidencing significant differences. BVOC emissions from the two models were then used to predict the concentrations of precursors and products of photochemical smog pollution over the Gulf of Naples (Italy) using a chemical-transport model. Simulations were performed during a period characterised by high pressure conditions that favour an enhanced O3 production under a sea-breeze circulation regime. VOCs concentration profiles predicted by the two models were compared with field data collected over Mount Vesuvius using a tethered balloon coupled with a PTR-MS. The results proved the better capability of PSEM to predict the concentrations of many BVOCs, including isoprene and some of its primary oxidation products over the measuring site, and suggested the significant potential of BVOC emission to produce SOA over the gulf of Naples.

Biogenic volatile organic compound emission from tropical plants in relation to temperature changes

Climate change has resulted in many environmental changes which impact living organisms including plants. Biogenic volatile organic compounds (BVOC) are emitted from plants under stressful conditions as a defensive mechanism. This study aimed to evaluate the effects of temperature on the emission rate of the BVOC (isoprene and monoterpenes) from the tropical plants Syzygium cumini and Peltophorum pterocarpum. These species were reported as high BVOC emitting and abundant species in the urban green area. The temperatures focused in this study were low temperature (16–18 °C), three optimal temperatures (36–38 °C, 38–40 °C and 40–42 °C) and high temperature (48–50 °C). BVOC were measured using a VOCs analyser. The results showed that the BVOC emission rate increased with increasing temperature up to 38–40 °C and decreased after. The highest concentration of BVOC of S. cumini and P. pterocarpum were 44.04 and 13.12 µg/m2 h, respectively. S. cumini had higher emission than P. pterocarpum owing to the leaf morphology such as number and width of stomata. These results can be used to develop a model study of plant BVOC emissions in the urban green area, especially megacities where heat island effect is likely to occur.

A potential ozone defense in intercellular air space: Clues from intercellular BVOC concentrations and stomatal conductance

Ozone (O3) enters plants through the stomata, passes into the intercellular air space and is decomposed in cell walls. Two factors that affect the O3 level in the intercellular air space are the stomatal conductance and the concentration of biogenic volatile organic compounds (BVOCs). Stomatal conductance controls the O3 flux into the air space and the intercellular BVOCs react with the O3. Therefore, the intercellular air space serves as a place where O3 defense can occur, but it has received relatively little attention. This study aimed to explore potential plant-defense against O3 in the intercellular air space by measuring the stomatal conductance and intercellular BVOC concentrations of Scots pine (Pinus sylvestris) and Norway spruce (Picea abies). Seedlings of both species were exposed to two levels of O3, ambient (15 nmol mol−1) and 80 nmol mol−1 (dropping to an ambient level at night), in plant growth chambers for five days in both spring and summer. We found that O3 decreased stomatal conductance in both species and in both seasons, which can lower the O3 flux into the intercellular air space. Intercellular BVOC concentrations were decreased in spring while increased in summer for both species in response to O3. This suggests that the BVOC protection in the intercellular air space is only of consequence in summer. These results demonstrate the potential for BVOCs to provide intercellular O3 defense in both species, but with seasonal variation.

Vapor pressure deficit helps explain biogenic volatile organic compound fluxes from the forest floor and canopy of a temperate deciduous forest.

Biogenic volatile organic compounds (BVOCs) play critical roles in ecological and earth-system processes. Ecosystem BVOC models rarely include soil and litter fluxes and their accuracy is often challenged by BVOC dynamics during periods of rapid ecosystem change like spring leaf out. We measured BVOC concentrations within the air space of a mixed deciduous forest and used a hybrid Lagrangian/Eulerian canopy transport model to estimate BVOC flux from the forest floor, canopy, and whole ecosystem during spring. Canopy flux measurements were dominated by a large methanol source and small isoprene source during the leaf-out period, consistent with past measurements of leaf ontogeny and theory, and indicative of a BVOC flux situation rarely used in emissions model testing. The contribution of the forest floor to whole-ecosystem BVOC flux is conditional on the compound of interest and is often non-trivial. We created linear models of forest floor, canopy, and whole-ecosystem flux for each study compound and used information criteria-based model selection to find the simplest model with the best fit. Most published BVOC flux models do not include vapor pressure deficit (VPD), but it entered the best canopy, forest floor, and whole-ecosystem BVOC flux model more than any other study variable in the present study. Since VPD is predicted to increase in the future, future studies should investigate how it contributes to BVOC flux through biophysical mechanisms like evaporative demand, leaf temperature and stomatal function.

Seasonal Variation of Biogenic and Anthropogenic VOCs in a Semi-Urban Area Near Sydney, Australia

Volatile organic compounds (VOCs) play a key role in the formation of ozone and secondary organic aerosol, the two most important air pollutants in Sydney, Australia. Despite their importance, there are few available VOC measurements in the area. In this paper, we discuss continuous GC-MS measurements of 10 selected VOCs between February (summer in the southern hemisphere) and June (winter in the southern hemisphere) of 2019 in a semi-urban area between natural eucalypt forest and the Sydney metropolitan fringe. Combined, isoprene, methacrolein, methyl-vinyl-ketone, α-pinene, p-cymene, eucalyptol, benzene, toluene xylene and tri-methylbenzene provide a reasonable representation of variability in the total biogenic VOC (BVOC) and anthropogenic VOC (AVOC) loading in the area. Seasonal changes in environmental conditions were reflected in observed BVOC concentrations, with a summer peak of 8 ppb, dropping to approximately 0.1 ppb in winter. Isoprene, and its immediate oxidation products methacrolein (MACR) and methyl-vinyl-ketone (MVK), dominated BVOC concentrations during summer and early autumn, while monoterpenes comprised the larger fraction during winter. Temperature and solar radiation drive most of the seasonal variation observed in BVOCs. Observed levels of isoprene, MACR and MVK in the atmosphere are closely related with variations in temperature and photosynthetically active radiation (PAR), but chemistry and meteorology may play a more important role for the monoterpenes. Using a nonlinear model, temperature explains 51% and PAR 38% of the isoprene, MACR and MVK variation. Eucalyptol dominated the observed monoterpene fraction (contributing ~75%), with p-cymene (20%) and α-pinene (5%) also present. AVOCs maintain an average concentration of ~0.4 ppb, with a slight decrease during autumn–winter. The low AVOC concentrations observed indicate a relatively small anthropogenic influence, generally occurring when (rare) northerly winds transport Sydney emissions to the measurement site. The site is influenced by domestic, commercial and vehicle AVOC emissions. Our observed AVOC concentrations can be explained by the seasonal changes in meteorology and the emissions in the area as listed in the NSW emissions inventory and thereby act as an independent validation of this inventory. We conclude that the variations in atmospheric composition observed during the seasons are an important variable to consider when formulating air pollution control policies over Sydney given the influence of biogenic sources during summer, autumn and winter.

Increases in Biogenic Volatile Organic Compound Concentrations Observed after Rains at Six Forest Sites in Non-Summer Periods

Since biogenic volatile organic compounds (BVOCs) are important precursors of ozone, the monitoring of the BVOC concentration distributions is needed. In general, forest BVOC concentrations increase in summer as well as in other seasons. This study aims to detect temporally sporadic increases in BVOC concentrations in the non-summer months and to analyze the occurring climatic conditions. Using a uniform sampling system and shared gas chromatography–mass spectrometry, the concentrations of isoprene and monoterpenes in six Japanese forests were observed approximately once a month for 3 years. Using the observed data, the relations between the BVOC concentration increases and meteorological factors were evaluated. Twenty instances of temporal increases in BVOC concentrations were observed. These mainly occurred in spring for isoprene and in autumn for monoterpenes. Most of the increases in the non-summer months were observed after a rainfall event, when the daily temperature range was large, suggesting that wind, rain, and a rapid diurnal temperature rise could be factors in the non-summer months. Thus, the network monitoring of BVOC concentrations might be effective for understanding the effects of factors other than temperature, and the mechanisms and frequency of the temporal increases, on the BVOC concentrations in various forests.

Evaluation of OH and HO<sub>2</sub> concentrations and their budgets during photooxidation of 2-methyl-3-butene-2-ol (MBO) in the atmospheric simulation chamber SAPHIR

Abstract. Several previous field studies have reported unexpectedly large concentrations of hydroxyl and hydroperoxyl radicals (OH and HO2, respectively) in forested environments that could not be explained by the traditional oxidation mechanisms that largely underestimated the observations. These environments were characterized by large concentrations of biogenic volatile organic compounds (BVOC) and low nitrogen oxide concentration. In isoprene-dominated environments, models developed to simulate atmospheric photochemistry generally underestimated the observed OH radical concentrations. In contrast, HO2 radical concentration showed large discrepancies with model simulations mainly in non-isoprene-dominated forested environments. An abundant BVOC emitted by lodgepole and ponderosa pines is 2-methyl-3-butene-2-ol (MBO), observed in large concentrations for studies where the HO2 concentration was poorly described by model simulations. In this work, the photooxidation of MBO by OH was investigated for NO concentrations lower than 200 pptv in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich. Measurements of OH and HO2 radicals, OH reactivity (kOH), MBO, OH precursors, and organic products (acetone and formaldehyde) were used to test our current understanding of the OH-oxidation mechanisms for MBO by comparing measurements with model calculations. All the measured trace gases agreed well with the model results (within 15 %) indicating a well understood mechanism for the MBO oxidation by OH. Therefore, the oxidation of MBO cannot contribute to reconciling the unexplained high OH and HO2 radical concentrations found in previous field studies.

Measurements of a potential interference with laser-induced fluorescence measurements of ambient OH from the ozonolysis of biogenic alkenes

Abstract. Reactions of the hydroxyl radical (OH) play a central role in the chemistry of the atmosphere, and measurements of its concentration can provide a rigorous test of our understanding of atmospheric oxidation. Several recent studies have shown large discrepancies between measured and modeled OH concentrations in forested areas impacted by emissions of biogenic volatile organic compounds (BVOCs), where modeled concentrations were significantly lower than measurements. A potential reason for some of these discrepancies involves interferences associated with the measurement of OH using the laser-induced fluorescence–fluorescence assay by gas expansion (LIF-FAGE) technique in these environments. In this study, a turbulent flow reactor operating at atmospheric pressure was coupled to a LIF-FAGE cell and the OH signal produced from the ozonolysis of α-pinene, β-pinene, ocimene, isoprene, and 2-methyl-3-buten-2-ol (MBO) was measured. To distinguish between OH produced from the ozonolysis reactions and any OH artifact produced inside the LIF-FAGE cell, an external chemical scrubbing technique was used, allowing for the direct measurement of any interference. An interference under high ozone (between 2 × 1013 and 10 × 1013 cm−3) and BVOC concentrations (between approximately 0.1 × 1012 and 40 × 1012 cm−3) was observed that was not laser generated and was independent of the ozonolysis reaction time. For the ozonolysis of α- and β-pinene, the observed interference accounted for approximately 40 % of the total OH signal, while for the ozonolysis of ocimene the observed interference accounted for approximately 70 % of the total OH signal. Addition of acetic acid to the reactor eliminated the interference, suggesting that the source of the interference in these experiments involved the decomposition of stabilized Criegee intermediates (SCIs) inside the FAGE detection cell. Extrapolation of these measurements to ambient concentrations suggests that these interferences should be below the detection limit of the instrument.

Measurements of biogenic volatile organic compounds at a grazed savannah grassland agricultural landscape in South Africa

Abstract. Biogenic volatile organic compounds (BVOCs) play an important role in the chemistry of the troposphere, especially in the formation of tropospheric ozone (O3) and secondary organic aerosols (SOA). Ecosystems produce and emit a large number of BVOCs. It is estimated on a global scale that approximately 90 % of annual BVOC emissions are from terrestrial sources. In this study, measurements of BVOCs were conducted at the Welgegund measurement station (South Africa), which is considered to be a regionally representative background site situated in savannah grasslands. Very few BVOC measurements exist for savannah grasslands and results presented in this study are the most extensive for this type of landscape. Samples were collected twice a week for 2 h during the daytime and 2 h during the night-time through two long-term sampling campaigns from February 2011 to February 2012 and from December 2013 to February 2015, respectively. Individual BVOCs were identified and quantified using a thermal desorption instrument, which was connected to a gas chromatograph and a mass selective detector. The annual median concentrations of isoprene, 2-methyl-3-butene-2-ol (MBO), monoterpene and sesquiterpene (SQT) during the first campaign were 14, 7, 120 and 8 pptv, respectively, and 14, 4, 83 and 4 pptv, respectively, during the second campaign. The sum of the concentrations of the monoterpenes were at least an order of magnitude higher than the concentrations of other BVOC species during both sampling campaigns, with α-pinene being the most abundant species. The highest BVOC concentrations were observed during the wet season and elevated soil moisture was associated with increased BVOC concentrations. However, comparisons with measurements conducted at other landscapes in southern Africa and the rest of the world that have more woody vegetation indicated that BVOC concentrations were, in general, significantly lower for savannah grasslands. Furthermore, BVOC concentrations were an order of magnitude lower compared to total aromatic concentrations measured at Welgegund. An analysis of concentrations by wind direction indicated that isoprene concentrations were higher from the western sector that is considered to be a relatively clean regional background region with no large anthropogenic point sources, while wind direction did not indicate any significant differences in the concentrations of the other BVOC species. Statistical analysis indicated that soil moisture had the most significant impact on atmospheric levels of MBO, monoterpene and SQT concentrations, whereas temperature had the greatest influence on isoprene levels. The combined O3 formation potentials of all the BVOCs measured calculated with maximum incremental reactivity (MIR) coefficients during the first and second campaign were 1162 and 1022 pptv, respectively. α-Pinene and limonene had the highest reaction rates with O3, whereas isoprene exhibited relatively small contributions to O3 depletion. Limonene, α-pinene and terpinolene had the largest contributions to the OH reactivity of BVOCs measured at Welgegund for all of the months during both sampling campaigns.

Evidence of aqueous secondary organic aerosol formation from biogenic emissions in the North American Sonoran Desert

This study examines the role of aqueous secondary organic aerosol formation in the North American Sonoran Desert as a result of intense solar radiation, enhanced moisture, and biogenic volatile organic compounds (BVOCs). The ratio of water-soluble organic carbon (WSOC) to organic carbon (OC) nearly doubles during the monsoon season relative to other seasons of the year. When normalized by mixing height, the WSOC enhancement during monsoon months relative to preceding dry months (May-June) exceeds that of sulfate by nearly a factor of 10. WSOC:OC and WSOC are most strongly correlated with moisture parameters, temperature, and concentrations of O3 and BVOCs. No positive relationship was identified between WSOC or WSOC:OC and anthropogenic tracers such as CO over a full year. This study points at the need for further work to understand the effect of BVOCs and moisture in altering aerosol properties in understudied desert regions.

Enhanced SOA formation from mixed anthropogenic and biogenic emissions during the CARES campaign

Abstract. The CARES campaign was conducted during June, 2010 in the vicinity of Sacramento, California to study aerosol formation and aging in a region where anthropogenic and biogenic emissions regularly mix. Here, we describe measurements from an Aerodyne High Resolution Aerosol Mass Spectrometer (AMS), an Ionicon Proton Transfer Reaction Mass Spectrometer (PTR-MS), and trace gas detectors (CO, NO, NOx) deployed on the G-1 research aircraft to investigate ambient gas- and particle-phase chemical composition. AMS measurements showed that the particle phase is dominated by organic aerosol (OA) (85% on average) with smaller concentrations of sulfate (5%), nitrate (6%) and ammonium (3%) observed. PTR-MS data showed that isoprene dominated the biogenic volatile organic compound concentrations (BVOCs), with monoterpene concentrations generally below the detection limit. Using two different metrics, median OA concentrations and the slope of plots of OA vs. CO concentrations (i.e., ΔOA/ΔCO), we contrast organic aerosol evolution on flight days with different prevailing meteorological conditions to elucidate the role of anthropogenic and biogenic emissions on OA formation. Airmasses influenced predominantly by biogenic emissions had median OA concentrations of 2.2 μg m−3 and near zero ΔOA/ΔCO. Those influenced predominantly by anthropogenic emissions had median OA concentrations of 4.7 μg m−3 and ΔOA/ΔCO ratios of 35–44 μg m−3 ppmv. But, when biogenic and anthropogenic emissions mixed, OA levels were enhanced, with median OA concentrations of 11.4 μg m−3 and ΔOA/ΔCO ratios of 77–157 μg m−3 ppmv. Taken together, our observations show that production of OA was enhanced when anthropogenic emissions from Sacramento mixed with isoprene-rich air from the foothills. After considering several anthropogenic/biogenic interaction mechanisms, we conclude that NOx concentrations play a strong role in enhancing SOA formation from isoprene, though the chemical mechanism for the enhancement remains unclear. If these observations are found to be robust in other seasons and in areas outside of Sacramento, regional and global aerosol modules will need to incorporate more complex representations of NOx-dependent SOA mechanisms and yields into their algorithms. Ultimately, accurately predicting OA mass concentrations and their effect on radiation balance will require a mechanistically-based treatment of the interactions of biogenic and anthropogenic emissions.

Seasonal cycles of biogenic volatile organic compound fluxes and concentrations in a California citrus orchard

Abstract. Orange trees are widely cultivated in Mediterranean climatic regions where they are an important agricultural crop. Citrus have been characterized as emitters of volatile organic compounds (VOC) in chamber studies under controlled environmental conditions, but an extensive characterization at field scale has never been performed using modern measurement methods, and is particularly needed considering the complex interactions between the orchards and the polluted atmosphere in which Citrus is often cultivated. For one year, in a Valencia orange orchard in Exeter, California, we measured fluxes using PTRMS (Proton Transfer Reaction Mass Spectrometer) and eddy covariance for the most abundant VOC typically emitted from citrus vegetation: methanol, acetone, and isoprenoids. Concentration gradients of additional oxygenated and aromatic compounds from the ground level to above the canopy were also measured. In order to characterize concentrations of speciated biogenic VOC (BVOC) in leaves, we analyzed leaf content by GC-MS (Gas Chromatography – Mass Spectrometery) regularly throughout the year. We also characterized in more detail concentrations of speciated BVOC in the air above the orchard by in-situ GC-MS during a few weeks in spring flowering and summer periods. Here we report concentrations and fluxes of the main VOC species emitted by the orchard, discuss how fluxes measured in the field relate to previous studies made with plant enclosures, and describe how VOC content in leaves and emissions change during the year in response to phenological and environmental parameters. The orchard was a source of monoterpenes and oxygenated VOC. The highest emissions were observed during the springtime flowering period, with mid-day fluxes above 2 nmol m−2 s−1 for methanol and up to 1 nmol m−2 s−1 for acetone and monoterpenes. During hot summer days emissions were not as high as we expected considering the known dependence of biogenic emissions on temperature. We provide evidence that thickening of leaf cuticle wax content limited gaseous emissions during the summer.

In-canopy gas-phase chemistry during CABINEX 2009: sensitivity of a 1-D canopy model to vertical mixing and isoprene chemistry

Abstract. Vegetation emits large quantities of biogenic volatile organic compounds (BVOC). At remote sites, these compounds are the dominant precursors to ozone and secondary organic aerosol (SOA) production, yet current field studies show that atmospheric models have difficulty in capturing the observed HOx cycle and concentrations of BVOC oxidation products. In this manuscript, we simulate BVOC chemistry within a forest canopy using a one-dimensional canopy-chemistry model (Canopy Atmospheric CHemistry Emission model; CACHE) for a mixed deciduous forest in northern Michigan during the CABINEX 2009 campaign. We find that the base-case model, using fully-parameterized mixing and the simplified biogenic chemistry of the Regional Atmospheric Chemistry Model (RACM), underestimates daytime in-canopy vertical mixing by 50–70% and by an order of magnitude at night, leading to discrepancies in the diurnal evolution of HOx, BVOC, and BVOC oxidation products. Implementing observed micrometeorological data from above and within the canopy substantially improves the diurnal cycle of modeled BVOC, particularly at the end of the day, and also improves the observation-model agreement for some BVOC oxidation products and OH reactivity. We compare the RACM mechanism to a version that includes the Mainz isoprene mechanism (RACM-MIM) to test the model sensitivity to enhanced isoprene degradation. RACM-MIM simulates higher concentrations of both primary BVOC (isoprene and monoterpenes) and oxidation products (HCHO, MACR+MVK) compared with RACM simulations. Additionally, the revised mechanism alters the OH concentrations and increases HO2. These changes generally improve agreement with HOx observations yet overestimate BVOC oxidation products, indicating that this isoprene mechanism does not improve the representation of local chemistry at the site. Overall, the revised mechanism yields smaller changes in BVOC and BVOC oxidation product concentrations and gradients than improving the parameterization of vertical mixing with observations, suggesting that uncertainties in vertical mixing parameterizations are an important component in understanding observed BVOC chemistry.

Impacts of herbaceous bioenergy crops on atmospheric volatile organic composition and potential consequences for global climate change

AbstractThe introduction of new crops to agroecosystems can change the chemical composition of the atmosphere by altering the amount and type of plant‐derived biogenic volatile organic compounds (BVOCs). BVOCs are produced by plants to aid in defense, pollination, and communication. Once released into the atmosphere, they have the ability to influence its chemical and physical properties. In this study, we compared BVOC emissions from three potential bioenergy crops and estimated their theoretical impacts on bioenergy agroecosystems. The crops chosen were miscanthus (Miscanthus × giganteus), switchgrass (Panicum virgatum), and an assemblage of prairie species (mix of ~28 species). The concentration of BVOCs was different within and above plant canopies. All crops produced higher levels of emissions at the upper canopy level. Miscanthus produced lower amounts of volatiles compared with other grasses. The chemical composition of volatiles differed significantly among plant communities. BVOCs from miscanthus were depleted in terpenoids relative to the other vegetation types. The carbon flux via BVOC emissions, calculated using the flux‐gradient method, was significantly higher in the prairie assemblage compared with miscanthus and switchgrass. The BVOC carbon flux was approximately three orders of magnitude lower than the net fluxes of carbon measured over the same fields using eddy covariance systems. Extrapolation of our findings to the landscape scale leads us to suggest that the widespread adoption of bioenergy crops could potentially alter the composition of BVOCs in the atmosphere, thereby influencing its warming potential, the formation of atmospheric particulates, and interactions between plants and arthropods. Our data and projections indicate that, among at least these three potential options for bioenergy production, miscanthus is likely to have lower impacts on atmospheric chemistry and biotic interactions mediated by these volatiles when miscanthus is planted on the landscape scale.

The atmospheric potential of biogenic volatile organic compounds from needles of white pine (<i>Pinus strobus</i>) in Northern Michigan

Abstract. The key role that biogenic volatile organic compounds (BVOC) play in atmospheric chemistry requires a detailed understanding of how BVOC concentrations will be affected by environmental change. Large-scale screening of BVOC emissions from whole forest ecosystems is difficult with enclosure methods. Leaf composition of BVOC, as a surrogate for direct emissions, can more easily reflect the distribution of BVOC compounds in a forest. In this study, BVOC composition in needles of 92 white pine trees (Pinus strobus), which are becoming a large part of Midwest forests, are tracked for three summers at the University of Michigan Biological Station (UMBS). α-Pinene, the dominant terpene in all samples, accounts for 30–50% of all terpenes on a mole basis. The most abundant sesquiterpenoid was a C15 alcohol identified as germacrene D-4-ol. The relationship between limonene and total other monoterpenes shows two distinct trends in the population of these forests. About 14% (n = 13) of the trees showed high levels of limonene (up to 36% of the total BVOC) in the same trees every year. Assuming that needle concentrations scale with emission rate, we estimate that hydroxyl radical reactivity due to reaction with monoterpenes from white pine increases approximately 6% at UMBS when these elevated concentrations are included. We suggest that chemotypic variation within forests has the potential to affect atmospheric chemistry and that large-scale screening of BVOC can be used to study the importance of BVOC variation.

Characterization of biogenic volatile organic compounds (BVOCs) in cleaning reagents and air fresheners in Hong Kong

Abstract Biogenic volatile organic compounds (BVOCs) emitted from cleaning products and air fresheners indoors are prone to oxidation resulting in the formation of secondary pollutants that can pose health risks on residents. In this study, a solid phase microextraction (SPME) coupled with gas chromatography/mass spectrometry (SPME-GC/MS) method was applied for the determination of BVOCs compositions in three categories of cleaning products including floor cleaners (FC), kitchen cleaners (KC) and dishwashing detergents (DD), and also air fresheners (AF). The analysis results demonstrated that chemical composition and concentration of individual BVOC varied broadly with household products in the view of their different functions and scents as indicated on the labels. The concentration of total BVOCs for sample FC1 was the highest up to 4146.0 μg g−1, followed by FC2 of 264.6 μg g−1, FC4 of 249.3 μg g−1 and FC3 of 139.2 μg g−1. d -limonene was the most abundant detected BVOCs in KC samples with the chemical composition varying from 19.6 ± 1.0 to 1513.0 ± 37.1 μg g−1. For dishwashing detergents, only d -limonene was detected and quantified. The BVOCs compositions of air freshener samples are much more complicated. It was estimated that the consumption of floor cleaners contributed 51% of the total BVOCs amount indoors in Hong Kong, followed by air fresheners 42%, kitchen cleaners 5% and dishwashing detergents 2%.

Emission of biogenic volatile organic compounds involved in eruptive fire: implications for the safety of firefighters

Forest fires are can be fatal for firefighters owing to the phenomenon of eruptive fire. The hypothesis of this study is that biogenic volatile organic compounds (BVOCs) accumulate in the vicinity of the fire front. One of the factors required for an eruptive fire to take place is that BVOC concentrations must be between their lower flammable limit and upper flammable limit. When this accumulation of BVOCs is exacerbated by specific geographical zones (e.g. small valleys, thalwegs, canyons), the combination of these two factors can lead to situations with a very high flammability potential, representing a considerable risk for firefighters. In France, 16 firefighters have been fatally injured over the last 15 years. This work was carried out on three species of the Mediterranean basin: Pinus laricio Poir., Pinus pinaster Ait. and Cistus monspeliensis L. The maximum BVOCs emitted as a function of temperature (50–200°C) by these species were 147.9, 11.6 and 56.0 g m–3 respectively. The quantities of BOVCs emitted by P. laricio and C. monspeliensis were sufficiently high for eruptive fires to occur.