Biogenic Volatile Organic Carbon Research Articles

Possibility of condensation of nitric acid for cloud condensation nucleus in the summer at Mt. Fuji

We carried out measurements of size-segregated ionic and elemental components of aerosols at the Mt. Fuji, Japan, in the summers of 2013 and 2015. We studied aerosol chemistry in the free troposphere (FT). We investigated ratios of elements and the transformation of nitrate in long-range transported air pollution (LRTAP) mixed with domestic air pollution (DAP). We distinguished aerosols from LRTAP during daytime (D) and nighttime (N) and DAP (D) at a relative humidity of 80% based on CALIPSO satellite, back-trajectory analysis, volatile organic carbon (VOC) tracers, and elements. We identified the sources of LRTAP and DAP. DAP containing Zn and high concentrations of biogenic VOCs (BVOCs) was transported by valley winds from and forests near the foothill of the mountain. The contribution of BVOCs and secondary organic aerosols (SOAs) from the forest was high in FT. LRTAP containing high concentrations of VOCs and Pb was transported from China. The contribution of SOAs in LRTAP (N) was higher at Mt. Fuji than at a remote site in Okinawa. A comparison of chlorine loss in this study with the remote site revealed that HNO3 was absorbed in coarse particles in LRTAP (D) from urban sites when LRTAP (D) was mixed with DAP. When (NH4) 2 NO3 was degraded to NH3 and HNO3 during transport to Mt. Fuji, the high excess-HNO3 was absorbed in the aqueous phase without neutralization. This result indicates that nitrate can be enriched during cloud processes when LRTAP (D) is mixed with DAP.

Vapor-pressure pathways initiate but hydrolysis products dominate the aerosol estimated from organic nitrates.

Organic nitrates contribute significantly to the total organic aerosol burden. However, the formation and loss mechanisms of particulate organic nitrates (PONs) remain poorly understood. In this study, with the CMAQ modeling system, we implement a detailed biogenic volatile organic carbon gas phase oxidation mechanism and an explicit representation of multiphase organic nitrate formation and loss, including both aqueous-phase uptake and vapor-pressure driven partitioning into organic aerosol as well as condensed-phase reactions. We find vapor-pressure dependent partitioning is the leading mechanism for formation of PONs and hydrolysis is a major loss mechanism for PON resulting in substantial amounts of organic aerosol that originate as an organic nitrate. Partitioning and hydrolysis together can produce high concentrations (up to 5 μg/m3) of PON-derived aerosols over the southeast United States. The main source of PON-derived aerosols is monoterpene nitrates that have been chemically processed to lose their nitrate functionality through aqueous chemistry. In contrast, the major portion of aqueous aerosol and in-cloud PON, which retains its nitrate moiety, are soluble isoprene nitrates. We evaluate the model using the observations from the Southern Oxidant and Aerosol Study (SOAS) campaign in the Southeast US in summer 2013 and show implementing aerosol-phase pathways for organic nitrates dramatically improves the magnitude of total alkyl nitrates (ANs) in CMAQ. The contribution of PONs to the total ANs at the SOAS site is estimated to be ~20%, a value in the range of the measurements. The predicted AN composition is shifted from monoterpene to isoprene and anthropogenic organic nitrates.

The Green Ocean Amazon Experiment (GoAmazon2014/5) Observes Pollution Affecting Gases, Aerosols, Clouds, and Rainfall over the Rain Forest

AbstractThe Observations and Modeling of the Green Ocean Amazon 2014–2015 (GoAmazon2014/5) experiment took place around the urban region of Manaus in central Amazonia across 2 years. The urban pollution plume was used to study the susceptibility of gases, aerosols, clouds, and rainfall to human activities in a tropical environment. Many aspects of air quality, weather, terrestrial ecosystems, and climate work differently in the tropics than in the more thoroughly studied temperate regions of Earth. GoAmazon2014/5, a cooperative project of Brazil, Germany, and the United States, employed an unparalleled suite of measurements at nine ground sites and on board two aircraft to investigate the flow of background air into Manaus, the emissions into the air over the city, and the advection of the pollution downwind of the city. Herein, to visualize this train of processes and its effects, observations aboard a low-flying aircraft are presented. Comparative measurements within and adjacent to the plume followed the emissions of biogenic volatile organic carbon compounds (BVOCs) from the tropical forest, their transformations by the atmospheric oxidant cycle, alterations of this cycle by the influence of the pollutants, transformations of the chemical products into aerosol particles, the relationship of these particles to cloud condensation nuclei (CCN) activity, and the differences in cloud properties and rainfall for background compared to polluted conditions. The observations of the GoAmazon2014/5 experiment illustrate how the hydrologic cycle, radiation balance, and carbon recycling may be affected by present-day as well as future economic development and pollution over the Amazonian tropical forest.

Large contribution of natural aerosols to uncertainty in indirect forcing

The effect of anthropogenic aerosols on cloud droplet concentrations and radiative properties is the source of one of the largest uncertainties in the radiative forcing of climate over the industrial period. This uncertainty affects our ability to estimate how sensitive the climate is to greenhouse gas emissions. Here we perform a sensitivity analysis on a global model to quantify the uncertainty in cloud radiative forcing over the industrial period caused by uncertainties in aerosol emissions and processes. Our results show that 45 per cent of the variance of aerosol forcing since about 1750 arises from uncertainties in natural emissions of volcanic sulphur dioxide, marine dimethylsulphide, biogenic volatile organic carbon, biomass burning and sea spray. Only 34 per cent of the variance is associated with anthropogenic emissions. The results point to the importance of understanding pristine pre-industrial-like environments, with natural aerosols only, and suggest that improved measurements and evaluation of simulated aerosols in polluted present-day conditions will not necessarily result in commensurate reductions in the uncertainty of forcing estimates.

Characteristics of surface ozone at an urban site of Xi'an in Northwest China

Surface ozone concentrations in Xi'an, China were monitored from March 23, 2008 to January 12, 2009 using the Model ML/EC9810 ozone analyzer. The daily average O(3) ranged from <1 ppb to 64.2 ppbv with an annual average of 16.0 ppbv. The seasonal average of O(3) in summer (32.5 ppbv) was more than 10 times higher than that in winter (3.0 ppbv). A significant positive correlation was found between ozone concentration and ambient temperature, indicating that the intensity of solar radiation was one of the several major factors controlling surface ozone production. Using the NOAA HYSPLIT 4 trajectory model, the three longest O(3) pollution episodes were found to be associated with the high biogenic volatile organic carbon (BVOC) emissions from the vegetation of Qinling Mountains. No significant weekday and weekend difference in O(3) levels was detected due to the non-significant change in NO(x) emissions. O(3) depletion by NO emission directly emitted from vehicles, low oxygenated VOC concentrations, and low-level solar radiation caused by high aerosol loading all contributed to the low levels of O(3) found in Xi'an compared to other cities and rural areas.

In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007: implications for gas- and particle-phase chemistry

Abstract. We quantified ambient mixing ratios of 9 monoterpenes, 6 sesquiterpenes, methyl chavicol, the oxygenated terpene linalool, and nopinone using an in-situ gas chromatograph with a quadrupole mass spectrometer (GC-MS). These measurements were a part of the 2007 Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) at Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. To our knowledge, these observations represent the first direct in-situ ambient quantification of the sesquiterpenes α-bergamotene, longifolene, α-farnesene, and β-farnesene. From average diurnal mixing ratio profiles, we show that α-farnesene emissions are dependent mainly on temperature whereas α-bergamotene and β-farnesene emissions are temperature- and light-dependent. The amount of sesquiterpene mass quantified above the canopy was small (averaging a total of 3.3 ppt during the day), but nevertheless these compounds contributed 7.6% to the overall ozone-olefin loss rate above the canopy. Assuming that the monoterpene-to-sesquiterpene emission rate in the canopy is similar to that observed in branch enclosure studies at the site during comparable weather conditions, and the average yield of aerosol mass from these sesquiterpenes is 10–50%, the amount of sesquiterpene mass reacted within the Blodgett Forest canopy alone accounts for 6–32% of the total organic aerosol mass measured during BEARPEX. The oxygenated monoterpene linalool was also quantified for the first time at Blodgett Forest. The linalool mass contribution was small (9.9 ppt and 0.74 ppt within and above the canopy, respectively), but it contributed 1.1% to the total ozone-olefin loss rate above the canopy. Reactive and semi-volatile compounds, especially sesquiterpenes, significantly impact the gas- and particle-phase chemistry of the atmosphere at Blodgett Forest and should be included in both biogenic volatile organic carbon emission and atmospheric chemistry models.

Methyl chavicol: characterization of its biogenic emission rate, abundance, and oxidation products in the atmosphere

Abstract. We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS), a proton transfer reaction mass spectrometer (PTR-MS), and a thermal desorption aerosol GC-MS (TAG) – and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO), a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72–10.2 μgCg−1 h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

The effects of global changes upon regional ozone pollution in the United States

Abstract. A comprehensive numerical modeling framework was developed to estimate the effects of collective global changes upon ozone pollution in the US in 2050. The framework consists of the global climate and chemistry models, PCM (Parallel Climate Model) and MOZART-2 (Model for Ozone and Related Chemical Tracers v.2), coupled with regional meteorology and chemistry models, MM5 (Mesoscale Meteorological model) and CMAQ (Community Multi-scale Air Quality model). The modeling system was applied for two 10-year simulations: 1990–1999 as a present-day base case and 2045–2054 as a future case. For the current decade, the daily maximum 8-h moving average (DM8H) ozone mixing ratio distributions for spring, summer and fall showed good agreement with observations. The future case simulation followed the Intergovernmental Panel on Climate Change (IPCC) A2 scenario together with business-as-usual US emission projections and projected alterations in land use, land cover (LULC) due to urban expansion and changes in vegetation. For these projections, US anthropogenic NOx (NO+NO2) and VOC (volatile organic carbon) emissions increased by approximately 6% and 50%, respectively, while biogenic VOC emissions decreased, in spite of warmer temperatures, due to decreases in forested lands and expansion of croplands, grasslands and urban areas. A stochastic model for wildfire emissions was applied that projected 25% higher VOC emissions in the future. For the global and US emission projection used here, regional ozone pollution becomes worse in the 2045–2054 period for all months. Annually, the mean DM8H ozone was projected to increase by 9.6 ppbv (22%). The changes were higher in the spring and winter (25%) and smaller in the summer (17%). The area affected by elevated ozone within the US continent was projected to increase; areas with levels exceeding the 75 ppbv ozone standard at least once a year increased by 38%. In addition, the length of the ozone season was projected to increase with more pollution episodes in the spring and fall. For selected urban areas, the system projected a higher number of pollution events per year and these events had more consecutive days when DM8H ozone exceed 75 ppbv.

Sources of organic carbon in fine particulate matter in northern European urban air

Abstract. A major fraction of fine particle matter consists of organic carbon (OC) but its origin is still inadequately known. In this study the sources of OC were investigated in the northern European urban environment in Helsinki, Finland. Measurements were carried out over one year and they included both filter (PM1) and online methods. From the filter samples OC, elemental carbon (EC), water-soluble OC (WSOC), levoglucosan and major ions were analyzed. Filter data together with the concentrations of inorganic gases were analyzed by Positive matrix factorization (PMF) in order to find the sources of OC (and WSOC) on an annual as well as on a seasonal basis. In order to study the diurnal variation of sources, OC and EC were measured by a semicontinuous OC/EC analyzer and major ions were determined by a Particle-into-Liquid Sampler coupled to ion chromatographs. According to PMF, OC concentrations were impacted by four sources: biomass combustion, traffic, long-range transport and secondary production. On an annual basis the OC concentration was dominated by secondary organic aerosol (SOA). Its contribution to OC was as high as 64% in summer, which besides anthropogenic sources may also result from the large biogenic volatile organic carbon (VOC) emissions in the boreal region. In winter biomass combustion constituted the largest fraction in OC due to domestic wood combustion for heating purposes. Traffic contributed to OC from 15 to 27%. Regarding the diurnal variation, the contribution from traffic was higher from 08:00 to 18:00 on weekdays than on weekends. The contribution from long-range transport to OC was 24% on average. All four sources also influenced the WSOC concentrations, however, the contribution of SOA was significantly larger for WSOC than OC.

An investigation of the rate of biogenic volatile organic carbon emission from commercial crops and plantation species in the Mpumalanga Province

An investigation of the rate of biogenic volatile organic carbon emission from commercial crops and plantation species in the Mpumalanga Province

Past and present-day biogenic volatile organic compound emissions in East Asia

Biogenic volatile organic carbon (VOC) emissions from vegetation in East Asia are estimated for two contrasting land-cover scenarios: near present-day conditions derived from satellite data and pre-disturbed land-cover based on climatological parameters and plant functional type. Hourly fluxes of isoprene and monoterpenes are calculated on a grid of 60 km×60 km cells covering much of East Asia using meteorological conditions derived from a 12-month simulation of the region using regional climate model, monthly leaf area indexes, and the Guenther et al. (J. Geophys. Res. 101 (1995) 1345) ecosystem-dependent emission factors. Total present-day isoprene emissions are estimated at approximately 12 Tg C yr −1 and monoterpene emissions at 6 Tg C yr −1. These emissions are approximately 5.4 and 4 Tg C yr −1 lower than the estimated pre-disturbed emissions of isoprene and monoterpenes, respectively, largely due to the conversion of forested land to cropland. ORVOC emission estimates for the present-day scenario, obtained by assuming a constant ORVOC emission factor for all ecosystems, are slightly higher in magnitude than isoprene emissions. Present-day totals of combined biogenic and anthropogenic VOC emissions are generally larger than biogenic VOC emissions in the pre-disturbed scenario, indicating that human activities have led to a net increase in the atmospheric source of VOC in East Asia.

Seasonal and spatial variations in biogenic hydrocarbon emissions from southern African savannas and woodlands

Biogenic volatile organic carbon (BVOC) emissions are an important component of the global BVOC budget, contributing more than 90%. Emissions vary with species and vegetation type; therefore to produce accurate global budgets data is required from different vegetation types. This study investigates BVOC emissions from savannas, Kalahari woodlands, Kalahari open shrublands and Mopane woodlands in southern Africa. BVOC emission samples from individual species were collected using leaf cuvettes and the BVOC concentrations were determined by GC-FID/MS. Ten of the 14 woodland species measured were high isoprene emitters, while two showed high monoterpene emission capacities. Landscape average isoprene emission capacities were estimated to be as high as 9, 8 and 1 mg C m −2 h −1 for savannas, woodlands and shrub lands, respectively. The monoterpene emission capacity for Mopane woodlands were estimated at almost 3 mg C m −2 h −1, while for other landscapes it varied between 0.04 and 3 mg C m −2 h −1. Isoprene and monoterpene emissions at a savanna site in South Africa showed a seasonal variation, which is more pronounced for isoprene. During the winter (June–September) estimated emissions were <10 mg C m −2 d −1, with peak emissions (ranging between 20 and 80 mg C m −2 d −1) occurring during the summer months (December–March) when foliar density peaked. The total BVOC emission from southern African (south of the Equator) savannas was estimated to be in the range of 18–74 Tg C yr −1.

NET PRIMARY PRODUCTION IN TROPICAL FORESTS: AN EVALUATION AND SYNTHESIS OF EXISTING FIELD DATA

Information on net primary production in tropical forests is needed for the development of realistic global carbon budgets, for projecting how these ecosystems will be affected by climatic and atmospheric changes, and for evaluating eddy covariance mea- surements of tropical forest carbon flux. However, a review of the database commonly used to address these issues shows that it has serious flaws. In this paper we synthesize the data in the primary literature on NPP in old-growth tropical forests to produce a consistent data set on NPP for these forests. Studies in this biome have addressed only a few NPP com- ponents, all aboveground. Given the limited scope of the direct field measurements, we sought relationships in the existing data that allow estimation of unmeasured aspects of production from those that are more easily assessed. We found a predictive relationship between annual litterfall and aboveground biomass increment. For 39 diverse tropical forest sites, we then developed consistent, documented estimates of the upper and lower bounds around total NPP to serve as benchmarks for calibrating and validating biogeochemical models with respect to this biome. We developed these estimates based on existing field measurements, current understanding of aboveground consumption and biogenic volatile organic carbon emissions, and our judgment that belowground production is bounded by the range 0.2-1.2 3 ANPP (aboveground NPP). Across this broad spectrum of tropical forests (dry to wet, lowland to montane, nutrient-rich to nutrient-poor soils), our estimates of lower and upper bounds on total NPP range from 1.7 to 11.8 Mg C·ha 21 ·yr 21 (lower bounds) and from 3.1 to 21.7 Mg C·ha 21 ·yr 21 (upper bounds). We also showed that two relationships that have been used for estimating NPP (the Bray-Gorham relationship based on leaf litterfall and the Miami model based on temperature or precipitation) are not valid for the tropical forest biome.