scholarly journals Seasonal and diurnal variations in biogenic volatile organic compounds in highland and lowland ecosystems in southern Kenya

2021 ◽  
Vol 21 (19) ◽  
pp. 14761-14787
Author(s):  
Yang Liu ◽  
Simon Schallhart ◽  
Ditte Taipale ◽  
Toni Tykkä ◽  
Matti Räsänen ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Daily Maximum ◽  
Mixing Ratio ◽  
Biogenic Volatile Organic Compounds ◽  
Mixing Ratios ◽  
Seasonal And Diurnal Variations ◽  
Volatile Organic ◽  
Dry Seasons

Abstract. The East African lowland and highland areas consist of water-limited and humid ecosystems. The magnitude and seasonality of biogenic volatile organic compounds (BVOCs) emissions and concentrations from these functionally contrasting ecosystems are limited due to a scarcity of direct observations. We measured mixing ratios of BVOCs from two contrasting ecosystems, humid highlands with agroforestry and dry lowlands with bushland, grassland, and agriculture mosaics, during both the rainy and dry seasons of 2019 in southern Kenya. We present the diurnal and seasonal characteristics of BVOC mixing ratios and their reactivity and estimated emission factors (EFs) for certain BVOCs from the African lowland ecosystem based on field measurements. The most abundant BVOCs were isoprene and monoterpenoids (MTs), with isoprene contributing > 70 % of the total BVOC mixing ratio during daytime, while MTs accounted for > 50 % of the total BVOC mixing ratio during nighttime at both sites. The contributions of BVOCs to the local atmospheric chemistry were estimated by calculating the reactivity towards the hydroxyl radical (OH), ozone (O3), and the nitrate radical (NO3). Isoprene and MTs contributed the most to the reactivity of OH and NO3, while sesquiterpenes dominated the contribution of organic compounds to the reactivity of O3. The mixing ratio of isoprene measured in this study was lower than that measured in the relevant ecosystems in western and southern Africa, while that of monoterpenoids was similar. Isoprene mixing ratios peaked daily between 16:00 and 20:00 (all times are given as East Africa Time, UTC+3),​​​​​​​ with a maximum mixing ratio of 809 pptv (parts per trillion by volume) and 156 pptv in the highlands and 115 and 25 pptv in the lowlands during the rainy and dry seasons, respectively. MT mixing ratios reached their daily maximum between midnight and early morning (usually 04:00 to 08:00), with mixing ratios of 254 and 56 pptv in the highlands and 89 and 7 pptv in the lowlands in the rainy and dry seasons, respectively. The dominant species within the MT group were limonene, α-pinene, and β-pinene. EFs for isoprene, MTs, and 2-Methyl-3-buten-2-ol (MBO) were estimated using an inverse modeling approach. The estimated EFs for isoprene and β-pinene agreed very well with what is currently assumed in the world's most extensively used biogenic emissions model, the Model of Emissions of Gases and Aerosols from Nature (MEGAN), for warm C4 grass, but the estimated EFs for MBO, α-pinene, and especially limonene were significantly higher than that assumed in MEGAN for the relevant plant functional type. Additionally, our results indicate that the EF for limonene might be seasonally dependent in savanna ecosystems.

scholarly journals Seasonal and diurnal variations of biogenic volatile organic compounds in highland and lowland ecosystems in southern Kenya

2021 ◽  
Author(s):  
Yang Liu ◽  
Simon Schallhart ◽  
Ditte Taipale ◽  
Toni Tykkä ◽  
Matti Räsänen ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Daily Maximum ◽  
Mixing Ratio ◽  
Biogenic Volatile Organic Compounds ◽  
Mixing Ratios ◽  
Seasonal And Diurnal Variations ◽  
Volatile Organic ◽  
Dry Seasons

Abstract. The East African lowland and highland areas consist of water-limited and humid ecosystems. The magnitude and seasonality of biogenic volatile organic compounds (BVOCs) emissions from these functionally contrasting ecosystems are limited due to a scarcity of direct observations. We measured mixing ratios of BVOCs from two contrasting ecosystems, humid highlands with agroforestry and dry lowlands with bushland, grassland, and agriculture mosaics, during both the rainy and dry seasons of 2019 in southern Kenya. We present the diurnal and seasonal characteristics of BVOC mixing ratios and their reactivity, and estimated emission factors (EFs) for certain BVOCs from the African lowland ecosystem based on field measurements. The most abundant BVOCs were isoprene and monoterpenoids (MTs), with isoprene contributing > 70 % of the total BVOC mixing ratio during daytime, while MTs accounted for > 50 % of the total BVOC mixing ratio during nighttime at both sites. The contributions of BVOCs to the local atmospheric chemistry were estimated by calculating the reactivity towards the hydroxyl radical (OH), ozone (O3), and the nitrate radical (NO3). Isoprene and MTs contributed the most to the reactivity of OH and NO3, while sesquiterpenes dominated the contribution of organic compounds to the reactivity of O3. The mixing ratio of isoprene measured in this study was lower to that measured in the relevant ecosystems in west and south Africa, while that of monoterpenoids was similar. Isoprene mixing ratios peaked daily between 16:00 and 20:00 with a maximum mixing ratio of 809 parts per trillion by volume (pptv) and 156 pptv in the highlands, and 115 pptv and 25 pptv in the lowlands, during the rainy and dry seasons, respectively. MT mixing ratios reached their daily maximum between midnight and early morning (usually 04:00 to 08:00) with mixing ratios of 254 pptv and 56 pptv in the highlands, and 89 pptv and 7 pptv in the lowlands, in the rainy and dry seasons, respectively. The dominant species within the MT group were limonene, α-pinene, and β-pinene. EFs for isoprene, MTs, and 2-methyl-3-buten-2-ol (MBO) were estimated using an inverse modeling approach. The estimated EFs for isoprene and β-pinene agreed very well with what is currently assumed in the world’s most extensively used biogenic emissions model, the Model of Emissions of Gases and Aerosols from Nature (MEGAN), for warm C4 grass, but the estimated EFs for MBO, α-pinene, and especially limonene, were significantly higher than that assumed in MEGAN for the relevant plant functional type. Additionally, our results indicate that the EF for limonene might be seasonally dependent in savanna ecosystems.

scholarly journals Measurement report: Variability in the composition of biogenic volatile organic compounds in a Southeastern US forest and their role in atmospheric reactivity

2021 ◽  
Vol 21 (20) ◽  
pp. 15755-15770
Author(s):  
Deborah F. McGlynn ◽  
Laura E. R. Barry ◽  
Manuel T. Lerdau ◽  
Sally E. Pusede ◽  
Gabriel Isaacman-VanWertz
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Growing Season ◽  
Mixing Ratio ◽  
Biogenic Volatile Organic Compounds ◽  
Mixing Ratios ◽  
Southeastern Us ◽  
Atmospheric Reactivity ◽  
Volatile Organic ◽  
The Impact

Abstract. Despite the significant contribution of biogenic volatile organic compounds (BVOCs) to organic aerosol formation and ozone production and loss, there are few long-term, year-round, ongoing measurements of their volume mixing ratios and quantification of their impacts on atmospheric reactivity. To address this gap, we present 1 year of hourly measurements of chemically resolved BVOCs between 15 September 2019 and 15 September 2020, collected at a research tower in Central Virginia in a mixed forest representative of ecosystems in the Southeastern US. Mixing ratios of isoprene, isoprene oxidation products, monoterpenes, and sesquiterpenes are described and examined for their impact on the hydroxy radical (OH), ozone, and nitrate reactivity. Mixing ratios of isoprene range from negligible in the winter to typical summertime 24 h averages of 4–6 ppb, while monoterpenes have more stable mixing ratios in the range of tenths of a part per billion up to ∼2 ppb year-round. Sesquiterpenes are typically observed at mixing ratios of <10 ppt, but this represents a lower bound in their abundance. In the growing season, isoprene dominates OH reactivity but is less important for ozone and nitrate reactivity. Monoterpenes are the most important BVOCs for ozone and nitrate reactivity throughout the year and for OH reactivity outside of the growing season. To better understand the impact of this compound class on OH, ozone, and nitrate reactivity, the role of individual monoterpenes is examined. Despite the dominant contribution of α-pinene to total monoterpene mass, the average reaction rate of the monoterpene mixture with atmospheric oxidants is between 25 % and 30 % faster than α-pinene due to the contribution of more reactive but less abundant compounds. A majority of reactivity comes from α-pinene and limonene (the most significant low-mixing-ratio, high-reactivity isomer), highlighting the importance of both mixing ratio and structure in assessing atmospheric impacts of emissions.

scholarly journals Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms and organic aerosol

2016 ◽  
Author(s):  
N. L. Ng ◽  
S. S. Brown ◽  
A. T. Archibald ◽  
E. Atlas ◽  
R. C. Cohen ◽  
...  
Keyword(s):  
Air Quality ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Climate Models ◽  
Large Body ◽  
Organic Aerosol ◽  
Organic Nitrate ◽  
Biogenic Volatile Organic Compounds ◽  
Volatile Organic

Abstract. Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than three decades, during which time a large body of research has emerged from laboratory, field and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first section summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

scholarly journals Diel and seasonal changes of biogenic volatile organic compounds within and above an Amazonian rainforest

2015 ◽  
Vol 15 (6) ◽  
pp. 3359-3378 ◽  
Author(s):  
A. M. Yáñez-Serrano ◽  
A. C. Nölscher ◽  
J. Williams ◽  
S. Wolff ◽  
E. Alves ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Ambient Air ◽  
Dry Season ◽  
Solar Irradiation ◽  
Biogenic Volatile Organic Compounds ◽  
Wet Season ◽  
Mixing Ratios ◽  
Volatile Organic ◽  
Amazonian Rainforest

Abstract. The Amazonian rainforest is a large tropical ecosystem, which is one of the last pristine continental terrains. This ecosystem is ideally located for the study of diel and seasonal behaviour of biogenic volatile organic compounds (BVOCs) in the absence of local human interference. In this study, we report the first atmospheric BVOC measurements at the Amazonian Tall Tower Observatory (ATTO) site, located in central Amazonia. A quadrupole proton-transfer-reaction mass spectrometer (PTR-MS), with seven ambient air inlets, positioned from near ground to about 80 m (0.05, 0.5, 4, 24, 38, 53 and 79 m above the forest floor), was deployed for BVOC monitoring. We report diel and seasonal (February–March 2013 as wet season and September 2013 as dry season) ambient mixing ratios for isoprene, monoterpenes, isoprene oxidation products, acetaldehyde, acetone, methyl ethyl ketone (MEK), methanol and acetonitrile. Clear diel and seasonal patterns were observed for all compounds. In general, lower mixing ratios were observed during night, while maximum mixing ratios were observed during the wet season (February–March 2013), with the peak in solar irradiation at 12:00 LT (local time) and during the dry season (September 2013) with the peak in temperature at 16:00 LT. Isoprene and monoterpene mixing ratios were the highest within the canopy with a median of 7.6 and 1 ppb, respectively (interquartile range (IQR) of 6.1 and 0.38 ppb) during the dry season (at 24 m, from 12:00 to 15:00 LT). The increased contribution of oxygenated volatile organic compounds (OVOCs) above the canopy indicated a transition from dominating forest emissions during the wet season (when mixing ratios were higher than within the canopy), to a blend of biogenic emission, photochemical production and advection during the dry season when mixing ratios were higher above the canopy. Our observations suggest strong seasonal interactions between environmental (insolation, temperature) and biological (phenology) drivers of leaf BVOC emissions and atmospheric chemistry. Considerable differences in the magnitude of BVOC mixing ratios, as compared to other reports of Amazonian BVOC, demonstrate the need for long-term observations at different sites and more standardized measurement procedures, in order to better characterize the natural exchange of BVOCs between the Amazonian rainforest and the atmosphere.

scholarly journals From emissions to ambient mixing ratios: on-line seasonal field measurements of volatile organic compounds over a Norway spruce dominated forest in central Germany

2013 ◽  
Vol 13 (11) ◽  
pp. 30187-30232 ◽  
Author(s):  
E. Bourtsoukidis ◽  
J. Williams ◽  
J. Kesselmeier ◽  
S. Jacobi ◽  
B. Bonn
Keyword(s):  
Volatile Organic Compounds ◽  
Norway Spruce ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Temperature Dependency ◽  
Emission Rates ◽  
Temperature Dependent ◽  
Central Germany ◽  
Mixing Ratios ◽  
Volatile Organic

Abstract. Biogenic volatile organic compounds (BVOC) are substantial contributors to atmospheric chemistry and physics and demonstrate the close relationship between biosphere and atmosphere. Their emission rates are highly sensitive to meteorological and environmental changes with concomitant impacts on atmospheric chemistry. We have investigated seasonal isoprenoid and oxygenated VOC (oxVOC) fluxes from a Norway spruce (Picea abies) tree in Central Germany and explored the emission responses under various atmospheric conditions. Emission rates were quantified by using dynamic branch enclosure and Proton Transfer Reaction–Mass Spectrometry (PTR-MS) techniques. Additionally, ambient mixing ratios were derived through application of a new box model treatment on the dynamic chamber measurements. These are compared in terms of abundance and origin with the corresponding emissions. Isoprenoids govern the BVOC emissions from Norway spruce, with monoterpenes and sesquiterpenes accounting for 50.8 ± 7.2% and 19.8 ± 8.1% respectively of the total emissions. Normalizing the VOC emission rates, we have observed a trend of reduction of carbon containing emissions from April to November, with an enhancement of oxVOC. Highest emission rates were observed in June for all measured species, with the exception of sesquiterpenes that were emitted most strongly in April. We exploit the wide range of conditions experienced at the site to filter the dataset with a combination of temperature, ozone and absolute humidity values in order to derive the emission potential and temperature dependency development for the major chemical species investigated. A profound reduction of monoterpene emission potential (E30) and temperature dependency (β) was found under low temperature regimes, combined with low ozone levels (E30MT, LTLO3=56 ± 9.1 ng g(dw)−1 h−1, βMT,LTLO3=0.03±0.01 K−1) while a combination of both stresses was found to alter their emissions responses with respect to temperature substantially (E30MT,HTHO3=1420.1 ± 191.4 ng g(dw)−1 h−1, βMT,HTHO3=0.15 ± 0.02 K−1). Moreover, we have explored compound relationships under different atmospheric condition sets, addressing possible co-occurrence of emissions under specific conditions. Finally, we evaluate the temperature dependent algorithm that seems to describe the temperature dependent emissions. Highest emission deviations were observed for monoterpenes and these emission fluctuations were attributed to a fraction which is triggered by an additional light dependency.

scholarly journals Simulations of atmospheric OH, O<sub>3</sub> and NO<sub>3</sub> reactivities within and above the boreal forest

2015 ◽  
Vol 15 (7) ◽  
pp. 3909-3932 ◽  
Author(s):  
D. Mogensen ◽  
R. Gierens ◽  
J. N. Crowley ◽  
P. Keronen ◽  
S. Smolander ◽  
...  
Keyword(s):  
Steady State ◽  
Volatile Organic Compounds ◽  
Boreal Forest ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Inorganic Compounds ◽  
Spectral Irradiance ◽  
Biogenic Volatile Organic Compounds ◽  
Short Period ◽  
Volatile Organic

Abstract. Using the 1-D atmospheric chemistry transport model SOSAA, we have investigated the atmospheric reactivity of a boreal forest ecosystem during the HUMPPA-COPEC-10 campaign (summer 2010, at SMEAR~II in southern Finland). For the very first time, we present vertically resolved model simulations of the NO3 and O3 reactivity (R) together with the modelled and measured reactivity of OH. We find that OH is the most reactive oxidant (R ∼ 3 s-1) followed by NO3 (R ∼ 0.07 s-1) and O3 (R ∼ 2 × 10-5s-1). The missing OH reactivity was found to be large in accordance with measurements (∼ 65%) as would be expected from the chemical subset described in the model. The accounted OH radical sinks were inorganic compounds (∼ 41%, mainly due to reaction with CO), emitted monoterpenes (∼ 14%) and oxidised biogenic volatile organic compounds (∼ 44%). The missing reactivity is expected to be due to unknown biogenic volatile organic compounds and their photoproducts, indicating that the true main sink of OH is not expected to be inorganic compounds. The NO3 radical was found to react mainly with primary emitted monoterpenes (∼ 60%) and inorganic compounds (∼ 37%, including NO2). NO2 is, however, only a temporary sink of NO3 under the conditions of the campaign (with typical temperatures of 20–25 °C) and does not affect the NO3 concentration. We discuss the difference between instantaneous and steady-state reactivity and present the first boreal forest steady-state lifetime of NO3 (113 s). O3 almost exclusively reacts with inorganic compounds (∼ 91%, mainly NO, but also NO2 during night) and less with primary emitted sesquiterpenes (∼ 6%) and monoterpenes (∼ 3%). When considering the concentration of the oxidants investigated, we find that OH is the oxidant that is capable of removing organic compounds at a faster rate during daytime, whereas NO3 can remove organic molecules at a faster rate during night-time. O3 competes with OH and NO3 during a short period of time in the early morning (around 5 a.m. local time) and in the evening (around 7–8 p.m.). As part of this study, we developed a simple empirical parameterisation for conversion of measured spectral irradiance into actinic flux. Further, the meteorological conditions were evaluated using radiosonde observations and ground-based measurements. The overall vertical structure of the boundary layer is discussed, together with validation of the surface energy balance and turbulent fluxes. The sensible heat and momentum fluxes above the canopy were on average overestimated, while the latent heat flux was underestimated.

scholarly journals Quantifying the uncertainty in simulating global tropospheric composition due to the variability in global emission estimates of Biogenic Volatile Organic Compounds

2013 ◽  
Vol 13 (5) ◽  
pp. 2857-2891 ◽  
Author(s):  
J. E. Williams ◽  
P. F. J. van Velthoven ◽  
C. A. M. Brenninkmeijer
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Global Distribution ◽  
Chemical Mechanism ◽  
Biogenic Volatile Organic Compounds ◽  
Atmospheric Measurements ◽  
Large Variability ◽  
Mixing Ratios ◽  
Volatile Organic ◽  
Tropospheric O3

Abstract. The emission of organic compounds from biogenic processes acts as an important source of trace gases in remote regions away from urban conurbations, and is likely to become more important in future decades due to the further mitigation of anthropogenic emissions that affect air quality and climate forcing. In this study we examine the contribution of biogenic volatile organic compounds (BVOCs) towards global tropospheric composition using the global 3-D chemistry transport model TM5 and the recently developed modified CB05 chemical mechanism. By comparing regional BVOC emission estimates we show that biogenic processes act as dominant sources for many regions and exhibit a large variability in the annually and seasonally integrated emission fluxes. By performing sensitivity studies we find that the contribution of BVOC species containing between 1 to 3 carbon atoms has an impact on the resident mixing ratios of tropospheric O3 and CO, accounting for ~2.5% and ~10.8% of the simulated global distribution, respectively. This is approximately a third of the cumulative effect introduced by isoprene and the monoterpenes. By examining an ensemble of 3-D global chemistry transport simulations which adopt different global BVOC emission inventories we determine the associated uncertainty introduced towards simulating the composition of the troposphere for the year 2000. By comparing the model ensemble values against a composite of atmospheric measurements we show that the effects on tropospheric O3 are limited to the lower troposphere (with an uncertainty between −2% to 10%), whereas that for tropospheric CO extends up to the upper troposphere (with an uncertainty of between 10 to 45%). Comparing the mixing ratios for low molecular weight alkenes in TM5 against surface measurements taken in Europe implies that the cumulative emission estimates are too low, regardless of the chosen BVOC inventory. This variability in the global distribution of CO due to BVOC emissions introduces an associated uncertainty in the tropospheric CO burden of 11.4%, which impacts strongly on the oxidative capacity of the troposphere, introducing an uncertainty in the atmospheric lifetime of the greenhouse gas CH4 of ~3.3%. This study thus identifies the necessity of placing further constraints on non-CH4 global biogenic emission estimates in large-scale global atmospheric chemistry models.

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

2012 ◽  
Vol 12 (4) ◽  
pp. 2245-2252 ◽  
Author(s):  
S. Toma ◽  
S. Bertman
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Large Scale ◽  
Pinus Strobus ◽  
Biogenic Volatile Organic Compounds ◽  
White Pine ◽  
Volatile Organic ◽  
Pine Trees ◽  
Large Scale Screening

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.

scholarly journals Diel and seasonal changes of Biogenic Volatile Organic Compounds within and above an Amazonian rainforest site

2014 ◽  
Vol 14 (21) ◽  
pp. 29159-29208 ◽  
Author(s):  
A. M. Yañez-Serrano ◽  
A. C. Nölscher ◽  
J. Williams ◽  
S. Wolff ◽  
E. Alves ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Ambient Air ◽  
Dry Season ◽  
Solar Irradiation ◽  
Biogenic Volatile Organic Compounds ◽  
Wet Season ◽  
Mixing Ratios ◽  
Volatile Organic ◽  
Amazonian Rainforest

Abstract. The Amazonian rainforest is a large tropical ecosystem, and is one of the last pristine continental terrains. This ecosystem is ideally located for the study of diel and seasonal behaviour of Biogenic Volatile Organic Compounds (BVOC) in the absence of local human interference. In this study, we report the first atmospheric BVOC measurements at the Amazonian Tall Tower Observatory (ATTO) site, located in Central Amazonia. A quadrupole Proton Transfer Reaction Mass Spectrometer (PTR-MS) with 7 ambient air inlets, positioned from near the ground to about 80 m (0.05, 0.5, 4, 24, 38, 53 and 79 m above the forest floor), was deployed for BVOC monitoring. We report diel and seasonal (February/March 2013 and September 2013) ambient mixing ratios for isoprene, monoterpenes, methyl vinyl ketone (MVK) + methacrolein (MACR), acetaldehyde, acetone, methyl ethyl ketone (MEK), methanol and acetonitrile. Clear diel and seasonal patterns were observed for all compounds during the study. In general, lower mixing ratios were observed during night, while maximum mixing ratios were observed with the peak in solar irradiation at 12:00 LT during the wet season (February/March 2013), and with the peak in temperature at 16:00 LT during the dry season (September 2013). Isoprene mixing ratios were highest within the canopy with a median of 7.6 ppb and interquartile range (IQR) of 6.1 ppb (dry season at 24 m, from 12:00–15:00). Monoterpene mixing ratios were higher than previously reported for any Amazonian rainforest ecosystem (median 1 ppb, IQR 0.38 ppb during the dry season at 24 m from 15:00–18:00). Oxygenated Volatile Organic Compound (OVOC) patterns indicated a transition from dominating forest emissions during the wet season to a blend of biogenic emission, photochemical production, and advection during the dry season. This was inferred from the high mixing ratios found within the canopy, and those obtained above the canopy for the wet and dry season, respectively. Our observations reveal strong seasonal BVOC patterns and oxidation capacity, reflected in the different vertical profiles obtained between the dry and wet season, most likely driven by insolation, temperature and phenology. In addition, significant differences to other reports of Amazonian BVOC demonstrate the need for long-term observations and more standardized measurement procedures in order to better understand the natural exchange of BVOC between the Amazonian rainforest and the atmosphere.

scholarly journals The oxidation capacity of the boreal forest: first simulated reactivities of O<sub>3</sub> and NO<sub>3</sub>

2014 ◽  
Vol 14 (22) ◽  
pp. 30947-31007 ◽  
Author(s):  
D. Mogensen ◽  
R. Gierens ◽  
J. N. Crowley ◽  
P. Keronen ◽  
S. Smolander ◽  
...  
Keyword(s):  
Steady State ◽  
Volatile Organic Compounds ◽  
Boreal Forest ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Transport Model ◽  
Inorganic Compounds ◽  
Spectral Irradiance ◽  
Biogenic Volatile Organic Compounds ◽  
Volatile Organic

Abstract. Using the 1D atmospheric chemistry–transport model SOSAA, we have investigated the atmospheric reactivity of a boreal forest ecosystem during the HUMPPA-COPEC-10 campaign (summer 2010, at SMEAR II in Southern Finland). For the very first time, we present vertically resolved model simulations of the NO3- and O3-reactivity (R) together with the modelled and measured reactivity of OH. We find that OH is the most reactive oxidant (R~3 s−1) followed by NO3 (R~0.07 s−1) and O3 (R~2 × 10−5 s−1). The missing OH-reactivity was found to be large in accordance with measurements (~65%) as would be expected from the chemical subset described in the model. The accounted OH radical sinks were inorganic compounds (~41%, mainly due to reaction with CO), emitted monoterpenes (~14%) and oxidised biogenic volatile organic compounds (~44%). The missing reactivity is expected to be due to unknown biogenic volatile organic compounds and their photoproducts, indicating that the true main sink of OH is not expected to be inorganic compounds. The NO3 radical was found to react mainly with primary emitted monoterpenes (~60%) and inorganic compounds (~37%, including NO2). NO2 is, however, only a temporary sink of NO3 under the conditions of the campaign and does not affect the NO3 concentration. We discuss the difference between instantaneous and steady state reactivity and present the first boreal forest steady state lifetime of NO3 (113 s). O3 almost exclusively reacts with inorganic compounds (~91%, mainly NO, but also NO2 during night) and less with primary emitted sesquiterpenes (~6%) and monoterpenes (~3%). When considering the concentration of the oxidants investigated, we find that O3 is the oxidant that is capable of removing pollutants fastest. As part of this study, we developed a simple empirical parameterisation for conversion of measured spectral irradiance into actinic flux. Further, the meteorological conditions were evaluated using radiosonde observations and ground based measurements. The overall vertical structure of the boundary layer is discussed, together with validation of the surface energy balance and turbulent fluxes. The sensible heat and momentum fluxes above the canopy were on average overestimated, while the latent heat flux was underestimated.

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