scholarly journals Oxidation of Volatile Organic Compounds as the Major Source of Formic Acid in a Mixed Forest Canopy

2019 ◽  
Vol 46 (5) ◽  
pp. 2940-2948 ◽  
Author(s):  
Hariprasad D. Alwe ◽  
Dylan B. Millet ◽  
Xin Chen ◽  
Jonathan D. Raff ◽  
Zachary C. Payne ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Formic Acid ◽  
Organic Compounds ◽  
Forest Canopy ◽  
Mixed Forest ◽  
Volatile Organic

scholarly journals Emissions of isoprenoids and oxygenated biogenic volatile organic compounds from a New England mixed forest

2010 ◽  
Vol 10 (11) ◽  
pp. 28565-28633
Author(s):  
K. A. McKinney ◽  
B. H. Lee ◽  
A. Vasta ◽  
T. V. Pho ◽  
J. W. Munger
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Forest Canopy ◽  
Emission Rate ◽  
Mixed Forest ◽  
Emission Rates ◽  
Biogenic Volatile Organic Compounds ◽  
Methanol Production ◽  
Short Period ◽  
Volatile Organic

Abstract. Fluxes of biogenic volatile organic compounds, including isoprene, monoterpenes, and oxygenated VOCs measured above a mixed forest canopy in western Massachusetts during the 2005 and 2007 growing seasons are reported. Measurements were made using proton transfer reaction mass spectrometry (PTR-MS) and converted to fluxes using the disjunct eddy covariance technique. Isoprene was by far the predominant BVOC emitted at this site, with summer mid-day average fluxes of 5.3 and 4.4 mg m−2 h−1 in 2005 and 2007, respectively. In comparison, mid-day average fluxes of monoterpenes were 0.21 and 0.15 mg m−2 h−1 in each of these years. On short times scales (days), the diel pattern in emission rate compared well with a standard emission algorithm for isoprene. The general shape of the seasonal cycle and the observed decrease in isoprene emission rate in early September was, however, not well captured by the model. Monoterpene emission rates exhibited dependence on light as well as temperature, as determined from the improved fit to the observations obtained by including a light-dependent term in the model. The mid-day average flux of methanol from the canopy was 0.14 mg m−2 h−1 in 2005 and 0.19 mg m−2 h−1 in 2007, but the maximum flux was observed in spring (29 May 2007), when the flux reached 1.0 mg m−2 h−1. This observation is consistent with enhanced methanol production during leaf expansion. Summer mid-day fluxes of acetone were 0.15 mg m−2 h−1 during a short period in 2005, but only 0.03 mg m−2 h−1 averaged over 2007. Episodes of negative fluxes of oxygenated VOCs, particularly acetone, were observed periodically, especially in 2007. Thus, deposition within the canopy could help explain the low season-averaged flux of acetone in 2007. Fluxes of species of biogenic origin at mass-to-charge (m/z) ratios of 73 (0.05 mg m−2 h−1 in 2005; 0.03 mg m−2 h−1 in 2007) and 153 (5 μg m−2 h−1 in 2007), possibly corresponding to methyl ethyl ketone and an oxygenated terpene, respectively, were also observed.

scholarly journals Emissions of isoprenoids and oxygenated biogenic volatile organic compounds from a New England mixed forest

2011 ◽  
Vol 11 (10) ◽  
pp. 4807-4831 ◽  
Author(s):  
K. A. McKinney ◽  
B. H. Lee ◽  
A. Vasta ◽  
T. V. Pho ◽  
J. W. Munger
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Forest Canopy ◽  
Emission Rate ◽  
Mixed Forest ◽  
Emission Rates ◽  
Biogenic Volatile Organic Compounds ◽  
Methanol Production ◽  
Short Period ◽  
Volatile Organic

Abstract. Fluxes of biogenic volatile organic compounds, including isoprene, monoterpenes, and oxygenated VOCs measured above a mixed forest canopy in central Massachusetts during the 2005 and 2007 growing seasons are reported. Mixing ratios were measured using proton transfer reaction mass spectrometry (PTR-MS) and fluxes computed by the disjunct eddy covariance technique. Isoprene was by far the predominant BVOC emitted at this site, with summer mid-day average fluxes of 5.3 and 4.4 mg m−2 hr−1 in 2005 and 2007, respectively. In comparison, mid-day average fluxes of monoterpenes were 0.21 and 0.15 mg m−2 hr−1 in each of these years. On short times scales (days), the diel pattern in emission rate compared well with a standard emission algorithm for isoprene. The general shape of the seasonal cycle and the observed decrease in isoprene emission rate in early September was, however, not well captured by the model. Monoterpene emission rates exhibited dependence on light as well as temperature, as determined from the improved fit to the observations obtained by including a light-dependent term in the model. The mid-day average flux of methanol from the canopy was 0.14 mg m−2 hr−1 in 2005 and 0.19 mg m−2 hr−1 in 2007, but the maximum flux was observed in spring (29 May 2007), when the flux reached 1.0 mg m−2 hr−1. This observation is consistent with enhanced methanol production during leaf expansion. Summer mid-day fluxes of acetone were 0.15 mg m−2 hr−1 during a short period in 2005, but only 0.03 mg m−2 h−1 averaged over 2007. Episodes of negative fluxes of oxygenated VOCs, particularly acetone, were observed periodically, especially in 2007. Thus, deposition within the canopy could help explain the low season-averaged flux of acetone in 2007. Fluxes of species of biogenic origin at mass-to-charge ($m/z$) ratios of 73 (0.05 mg m−2 hr−1 in 2005; 0.03 mg m−2 hr−1 in 2007) and 153 (5 μg m−2 hr−1 in 2007), possibly corresponding to methyl ethyl ketone and an oxygenated terpene or methyl salicylate, respectively, were also observed.

scholarly journals Contributions to OH reactivity from unexplored volatile organic compounds measured by PTR-ToF-MS – A case study in a suburban forest of the Seoul Metropolitan Area during KORUS-AQ 2016

2020 ◽  
Author(s):  
Dianne Sanchez ◽  
Roger Seco ◽  
Dasa Gu ◽  
Alex Guenther ◽  
John Mak ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Mass Spectrometer ◽  
Metropolitan Area ◽  
Forest Canopy ◽  
Oxidation Products ◽  
Ionization Mass ◽  
Seoul Metropolitan Area ◽  
Volatile Organic ◽  
Tof Ms

Abstract. We report OH reactivity observations by a chemical ionization mass spectrometer – comparative reactivity method (CIMS-CRM) instrument in a suburban forest of the Seoul Metropolitan Area (SMA) during Korea US Air Quality Study (KORUS-AQ 2016) from mid-May to mid-June of 2016. A comprehensive observational suite was deployed to quantify reactive trace gases inside of the forest canopy including a high-resolution proton transfer reaction time of flight mass spectrometer (PTR-ToF-MS). An average OH reactivity of 30.7 ± 5.1 s−1 was observed, while the OH reactivity calculated from CO, NO + NO2 (NOx), ozone (O3), sulfur dioxide (SO2), and 14 volatile organic compounds (VOCs) was 11.8 ± 1.0 s−1. An analysis of 346 peaks from the PTR-ToF-MS accounted for an additional 6.0 ± 2.2 s−1 of the total measured OH reactivity, leaving 42.0 % missing OH reactivity. The missing OH reactivity most likely comes from VOC oxidation products of both biogenic and anthropogenic origin.

scholarly journals Turbulent exchange and segregation of HO<sub>x</sub> radicals and volatile organic compounds above a deciduous forest

2010 ◽  
Vol 10 (13) ◽  
pp. 6215-6235 ◽  
Author(s):  
R. Dlugi ◽  
M. Berger ◽  
M. Zelger ◽  
A. Hofzumahaus ◽  
M. Siese ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Forest Canopy ◽  
Deciduous Forest ◽  
Inorganic Compounds ◽  
Sonic Anemometer ◽  
Transport Processes ◽  
Biogenic Volatile Organic Compounds ◽  
Measuring Point ◽  
Volatile Organic

Abstract. The eddy covariance method was applied for the first time to estimate fluxes of OH and HO2 together with fluxes of isoprene, the sum of methyl vinyl ketone (MVK) and methacrolein (MACR) and the sum of monoterpenes above a mixed deciduous forest. Highly sensitive measurements of OH and HO2 were performed by laser induced fluorescence (LIF), and biogenic volatile organic compounds (BVOCs) were measured by Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) at a time resolution of 5 s, each. Wind speed was measured by a sonic anemometer at 10 Hz. The one-day feasibility study was conducted at a total height of 37 m, about 7 m above forest canopy, during the ECHO (Emission and CHemical transformation of biogenic volatile Organic compounds) intensive field study in July 2003. The daytime measurements yielded statistically significant OH fluxes directed downward into the direction of the canopy and HO2 fluxes mainly upward out of the canopy. This hints towards a significant local chemical sink of OH by reactions with BVOCs, other organic and inorganic compounds and conversion of OH to HO2 above the canopy. For OH the measured flux is locally balanced by chemical sources and sinks and direct transport of OH plays no important role for the local chemical OH budget at the measurement height, as expected from the short OH lifetime (<1 s). For HO2 the chemical lifetime (20 s) is in the range of the turbulent transport time for transfer between the top of the canopy and the measuring point. In this case, the radical balance is significantly influenced by both chemistry and transport processes. In addition, the highly time-resolved trace gas measurements were used to calculate the intensity of segregation of OH and BVOCs, demonstrating that the effective reaction rate of isoprene and OH was slowed down as much as 15% due to inhomogeneous mixing of the reactants. The paper describes the results, the applied methods and provides a detailed analysis of possible systematic errors of the covariance products.

scholarly journals Extension of a gaseous dry deposition algorithm to oxidized volatile organic compounds and hydrogen cyanide for application in chemistry transport models

2021 ◽  
Author(s):  
Zhiyong Wu ◽  
Leiming Zhang ◽  
John T. Walker ◽  
Paul A. Makar ◽  
Judith A. Perlinger ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Dry Deposition ◽  
Hydrogen Cyanide ◽  
Deposition Velocity ◽  
Mixed Forest ◽  
Chemical Species ◽  
Flux Divergence ◽  
Diel Cycles ◽  
Volatile Organic

Abstract. With increasing complexity of air quality models, additional chemical species have been included in model simulations for which dry deposition processes need to be parameterized. For this purpose, the gaseous dry deposition scheme of Zhang et al. (2003) is extended to include 12 oxidized volatile organic compounds (oVOCs) and hydrogen cyanide (HCN) based on their physicochemical properties, namely the effective Henry's law constants and oxidizing capacities. Modeled dry deposition velocity (Vd) values are compared against field flux measurements over a mixed forest in the southeastern U.S. during June 2013. The model captures the basic features of the diel cycles of the observed Vd. Modeled Vd values are comparable to the measurements for most of the oVOCs at night. However, modeled Vd values are mostly around 1 cm s−1 during daytime, which is much smaller than the observed daytime maxima of 2–5 cm s−1. Analysis of the individual resistance terms/uptake pathways suggests that flux divergence due to fast atmospheric chemical reactions near the canopy was likely the main cause of the large model-measurement discrepancies during daytime. The extended dry deposition scheme likely provides conservative Vd values for many oVOCs. While higher Vd values and bi-directional fluxes can be simulated by coupling key atmospheric chemical processes into the dry deposition scheme, we suggest that more experimental evidence of high oVOC Vd values at additional sites is required to confirm the broader applicability of the high values studied here. The underlying processes leading to high measured oVOC Vd values require further investigation.

scholarly journals Cryptogamic organisms are a substantial source and sink for volatile organic compounds in the Amazon region

2021 ◽  
Vol 2 (1) ◽  
Author(s):  
Achim Edtbauer ◽  
Eva Y. Pfannerstill ◽  
Ana Paula Pires Florentino ◽  
Cybelli G. G. Barbosa ◽  
Emilio Rodriguez-Caballero ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Atmospheric Chemistry ◽  
Forest Canopy ◽  
Oxidation Products ◽  
Atmospheric Oxidation ◽  
Tropical Rainforests ◽  
Volatile Organic ◽  
Flux Measurements ◽  
Made In

AbstractCryptogamic organisms such as bryophytes and lichens cover most surfaces within tropical forests, yet their impact on the emission of biogenic volatile organic compounds is unknown. These compounds can strongly influence atmospheric oxidant levels as well as secondary organic aerosol concentrations, and forest canopy leaves have been considered the dominant source of these emissions. Here we present cuvette flux measurements, made in the Amazon rainforest between 2016–2018, and show that common bryophytes emit large quantities of highly reactive sesquiterpenoids and that widespread lichens strongly uptake atmospheric oxidation products. A spatial upscaling approach revealed that cryptogamic organisms emit sesquiterpenoids in quantities comparable to current canopy attributed estimates, and take up atmospheric oxidation products at rates comparable to hydroxyl radical chemistry. We conclude that cryptogamic organisms play an important and hitherto overlooked role in atmospheric chemistry above and within tropical rainforests.

scholarly journals Emissions of biogenic volatile organic compounds and subsequent formation of secondary organic aerosols in a <I>Larix kaempferi</I> forest

2015 ◽  
Vol 15 (20) ◽  
pp. 12029-12041 ◽  
Author(s):  
T. Mochizuki ◽  
Y. Miyazaki ◽  
K. Ono ◽  
R. Wada ◽  
Y. Takahashi ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Forest Floor ◽  
Forest Canopy ◽  
Oxidation Products ◽  
Larix Kaempferi ◽  
Vertical Profiles ◽  
Biogenic Volatile Organic Compounds ◽  
Subsequent Formation ◽  
Volatile Organic

Abstract. We conducted simultaneous measurements of concentrations and above-canopy fluxes of isoprene and α-pinene, along with their oxidation products in aerosols in a Larix kaempferi (Japanese larch) forest in summer 2012. Vertical profiles of isoprene showed the maximum concentration near the forest floor with a peak around noon, whereas oxidation products of isoprene, i.e., methacrolein (MACR) and methyl vinyl ketone (MVK), showed higher concentrations near the canopy level of the forest. The vertical profile suggests large emissions of isoprene near the forest floor, likely due to Dryopteris crassirhizoma (a fern species), and the subsequent reaction within the canopy. The concentrations of α-pinene also showed highest values near the forest floor, with maximums in the early morning and late afternoon. The vertical profiles of α-pinene suggest its large emissions from soil and litter in addition to emissions from L. kaempferi leaves at the forest site. Isoprene and its oxidation products in aerosols exhibited similar diurnal variations within the forest canopy, providing evidence of secondary organic aerosol (SOA) formation via oxidation of isoprene most likely emitted from the forest floor. Although high abundance of α-pinene was observed in the morning, its oxidation products in aerosols showed peaks in daytime, due to a time lag between the emission and atmospheric reactions of α-pinene to form SOA. Positive matrix factorization (PMF) analysis indicated that anthropogenic influence is the most important factor contributing to the elevated concentrations of molecular oxidation products of isoprene- (> 64 %) and α-pinene-derived SOA (> 57 %). The combination of the measured fluxes and vertical profiles of biogenic volatile organic compounds (BVOCs) suggests that the inflow of anthropogenic precursors/aerosols likely enhanced the formation of both isoprene SOA and α-pinene SOA within the forest canopy even when the BVOC flux was relatively low. This study highlights the importance of intra-canopy processes that promote biogenic SOA formation in the presence of significant inflow of oxidants together with anthropogenic aerosols and their precursors.

scholarly journals Emissions of biogenic volatile organic compounds and subsequent formation of secondary organic aerosols in a <i>Larix kaempferi</i> forest

2015 ◽  
Vol 15 (7) ◽  
pp. 10739-10771 ◽  
Author(s):  
T. Mochizuki ◽  
Y. Miyazaki ◽  
K. Ono ◽  
R. Wada ◽  
Y. Takahashi ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Forest Floor ◽  
Forest Canopy ◽  
Oxidation Products ◽  
Larix Kaempferi ◽  
Vertical Profiles ◽  
Biogenic Volatile Organic Compounds ◽  
Subsequent Formation ◽  
Volatile Organic

Abstract. We conducted simultaneous measurements of concentrations and above-canopy fluxes of isoprene and α-pinene, along with their oxidation products in aerosols in a Larix kaempferi (Japanese larch) forest in summer 2012. Vertical profiles of isoprene showed the maximum concentration near the forest floor with a peak around noon, whereas oxidation products of isoprene, i.e., methacrolein (MACR) and methyl vinyl ketone (MVK), showed higher concentrations near the canopy level of the forest. The vertical profile suggests large emissions of isoprene near the forest floor, likely due to Dryopteris crassirhizoma (a fern species), and the subsequent reaction within the canopy. The concentrations of α-pinene also showed highest values near the forest floor with maximums in the early morning and late afternoon. The vertical profiles of α-pinene suggest its large emissions from soil and litter in addition to emissions from L. kaempferi leaves at the forest site. Isoprene and its oxidation products in aerosols exhibited similar diurnal variations within the forest canopy, providing evidence for secondary organic aerosol (SOA) formation via oxidation of isoprene most likely emitted from the forest floor. Although high abundance of α-pinene was observed in the morning, its oxidation products in aerosols showed peaks in daytime, due to a time lag between the emission and atmospheric reactions of α-pinene to form SOA. Positive matrix factorization (PMF) analysis indicated that anthropogenic influence is the most important factor contributing to the elevated concentrations of molecular oxidation products of isoprene- (> 64%) and α-pinene-derived SOA (> 57%). The combination of the measured fluxes and vertical profiles of biogenic volatile organic compounds (BVOCs) suggests that the inflow of anthropogenic precursors/aerosols likely enhanced the formation of both isoprene- and α-pinene-SOA within the forest canopy even when the BVOC flux was relatively low. This study highlights the importance of intra-canopy processes that promote biogenic SOA formation in the presence of significant inflow of anthropogenic aerosols and their precursors.

scholarly journals Different low-cost materials to prevent the alteration induced by formic acid on unstable glasses

2021 ◽  
Vol 9 (1) ◽  
Author(s):  
Rodrigo Arévalo ◽  
Jadra Mosa ◽  
Mario Aparicio ◽  
Teresa Palomar
Keyword(s):  
Activated Carbon ◽  
Volatile Organic Compounds ◽  
Formic Acid ◽  
Organic Compounds ◽  
Silica Gel ◽  
Low Cost ◽  
Glass Network ◽  
Steel Wool ◽  
Sorbent Material ◽  
Volatile Organic

AbstractThe most frequent cause of glass degradation is environmental moisture, which is adsorbed on its surface forming a hydration layer that induces the rupture of the glass network. This pathology is accelerated by the accumulation of volatile organic compounds (VOCs), like formic acid. Although there is extensive knowledge about their impact, concentrations inside display cases are difficult to reduce efficiently. This study presents the assessment of different materials to reduce the concentration of formic acid to mitigate the degradation produced in unstable glasses. With this objective, copper threads, steel wool, silica gel, and activated carbon were chosen as low-cost materials with good adsorption or reactivity to the VOCs, exposing them in desiccators to an environment of 100% RH and 10 ppm of formic acid. Given that silica gel obtained the best results, its optimization as a sorbent material was evaluated by maintaining, regenerating, or renewing it when exposed next to the same glass. The tests carried out concluded that the hygroscopic capacity of the glasses exposed with silica gel decreased and, therefore, a lower degradation is observed on its surface. In addition, regenerating and renewing weekly the silica gel improved the results.

scholarly journals Turbulent exchange and segregation of HO<sub>x</sub> radicals and volatile organic compounds above a deciduous forest

2009 ◽  
Vol 9 (6) ◽  
pp. 24423-24476 ◽  
Author(s):  
R. Dlugi ◽  
M. Berger ◽  
M. Zelger ◽  
A. Hofzumahaus ◽  
M. Siese ◽  
...  
Keyword(s):  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Forest Canopy ◽  
Deciduous Forest ◽  
Sonic Anemometer ◽  
Proton Transfer Reaction ◽  
Eddy Covariance Method ◽  
Time Resolved ◽  
Volatile Organic ◽  
Gas Measurements

Abstract. The eddy covariance method was applied for the first time to estimate fluxes of OH and HO2 together with fluxes of isoprene, the sum of methyl vinyl ketone (MVK) and methacrolein (MACR) and the sum of monoterpenes above a mixed deciduous forest. Highly sensitive measurements of OH and HO2 were performed by laser induced fluorescence (LIF), and biogenic volatile organic compounds (BVOCs) were measured by Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) at a time resolution of 5 s, each. Wind speed was measured by a sonic anemometer at 10 Hz. The one-day feasibility study was conducted at a total height of 37 m, about 7 m above forest canopy, during the ECHO 2003 intensive field study in July 2003. The daytime measurements yielded statistically significant OH fluxes that indicate downward transport of OH into the direction of the canopy and HO2 fluxes mainly upward out of the canopy. This hints towards a significant chemical sink of OH by reaction with BVOCs and conversion of OH to HO2 at the canopy. In addition, the highly time-resolved trace gas measurements were used to calculate the intensity of segregation of OH and BVOCs, demonstrating that the effective reaction rate of isoprene and OH was slowed down as much as 15% due to inhomogeneous mixing of the reactants. The paper describes the applied methods and provides a detailed analysis of possible systematic errors of the covariance products.

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