scholarly journals Boreal forest BVOCs exchange: emissions versus in-canopy sinks

Author(s):  
Putian Zhou ◽  
Laurens Ganzeveld ◽  
Ditte Taipale ◽  
Üllar Rannik ◽  
Pekka Rantala ◽  
...  

Abstract. A multi-layer gas dry deposition model has been developed and implemented into a 1-dimensional chemical transport model SOSAA (a model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to calculate the dry deposition velocities for all the gas species included in the chemistry scheme. The new model was used to analyse in-canopy sources and sinks, including gas emissions, chemical production and loss, dry deposition and turbulent transport of 12 featured biogenic volatile organic compounds (BVOCs) or groups of BVOCs (e.g., monoterpenes, isoprene+2-methyl-3-buten-2-ol (MBO), sesquiterpenes and oxidation products of mono- and sesquiterpenes) in July, 2010 at the boreal forest site SMEAR II (Station to Measure Ecosystem-Atmosphere Relations II). According to the significance of modeled monthly averaged individual source and sink terms inside the canopy, the selected BVOCs were classified into five categories: (1) most of emitted gases are transported out of the canopy (monoterpenes, isoprene+MBO), (2) chemical reactions remove a significant portion of emitted gases (sesquiterpenes), (3) bidirectional fluxes occur since both emission and dry deposition are crucial for the in-canopy concentration tendency (acetaldehyde, methanol, acetone, formaldehyde), (4) gases removed by deposition inside the canopy are compensated by the gases transported from above the canopy (acetol, pinic acid, β-caryophyllene's oxidation product BCSOZOH), and finally (5) the chemical production is comparable to the sink by deposition (isoprene's oxidation products ISOP34OOH and ISOP34NO3). Most of the simulated sources and sinks were located above about 4 m for oxidation products and above about 8 m for emitted species except formaldehyde. In addition, soil deposition (including deposition onto understory vegetation) contributed 11–61 % to the overall in-canopy deposition. The emission sources peaked at about 14–16 m which was higher than 10 m where the maximum of dry deposition onto overstorey vegetation was located. This study provided a method to enable the quantification of the exchange between atmosphere and biosphere for numerous BVOCs, which could be applied in large-scale models in future. With this more explicit canopy exchange modeling system this study analysed both the temporal and spatial variations of individual in-caonpy sources and sinks, as well as their combined effects on driving BVOCs exchange. Twelve featured BVOCs or BVOC groups were analyzed in this study, more compounds could also be investigated similarly by being classified into the five categories.

2017 ◽  
Vol 17 (23) ◽  
pp. 14309-14332 ◽  
Author(s):  
Putian Zhou ◽  
Laurens Ganzeveld ◽  
Ditte Taipale ◽  
Üllar Rannik ◽  
Pekka Rantala ◽  
...  

Abstract. A multilayer gas dry deposition model has been developed and implemented into a one-dimensional chemical transport model SOSAA (model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to calculate the dry deposition velocities for all the gas species included in the chemistry scheme. The new model was used to analyse in-canopy sources and sinks, including gas emissions, chemical production and loss, dry deposition, and turbulent transport of 12 featured biogenic volatile organic compounds (BVOCs) or groups of BVOCs (e.g. monoterpenes, isoprene+2-methyl-3-buten-2-ol (MBO), sesquiterpenes, and oxidation products of mono- and sesquiterpenes) in July 2010 at the boreal forest site SMEAR II (Station for Measuring Ecosystem–Atmosphere Relations). According to the significance of modelled monthly-averaged individual source and sink terms inside the canopy, the selected BVOCs were classified into five categories: 1. Most of emitted gases are transported out of the canopy (monoterpenes, isoprene + MBO). 2. Chemical reactions remove a significant portion of emitted gases (sesquiterpenes). 3. Bidirectional fluxes occur since both emission and dry deposition are crucial for the in-canopy concentration tendency (acetaldehyde, methanol, acetone, formaldehyde). 4. Gases removed by deposition inside the canopy are compensated for by the gases transported from above the canopy (acetol, pinic acid, β-caryophyllene's oxidation product BCSOZOH). 5. The chemical production is comparable to the sink by deposition (isoprene's oxidation products ISOP34OOH and ISOP34NO3). Most of the simulated sources and sinks were located above about 0.2 hc (canopy height) for oxidation products and above about 0.4 hc for emitted species except formaldehyde. In addition, soil deposition (including deposition onto understorey vegetation) contributed 11–61 % to the overall in-canopy deposition. The emission sources peaked at about 0.8–0.9 hc, which was higher than 0.6 hc where the maximum of dry deposition onto overstorey vegetation was located. This study provided a method to enable the quantification of the exchange between atmosphere and biosphere for numerous BVOCs, which could be applied in large-scale models in future. With this more explicit canopy exchange modelling system, this study analysed both the temporal and spatial variations in individual in-canopy sources and sinks, as well as their combined effects on driving BVOC exchange. In this study 12 featured BVOCs or BVOC groups were analysed. Other compounds could also be investigated similarly by being classified into these five categories.


2019 ◽  
Vol 19 (23) ◽  
pp. 14431-14453 ◽  
Author(s):  
Arnaud P. Praplan ◽  
Toni Tykkä ◽  
Dean Chen ◽  
Michael Boy ◽  
Ditte Taipale ◽  
...  

Abstract. Total hydroxyl radical (OH) reactivity measurements were conducted at the second Station for Measuring Ecosystem–Atmosphere Relations (SMEAR II), a boreal forest site located in Hyytiälä, Finland, from April to July 2016. The measured values were compared with OH reactivity calculated from a combination of data from the routine trace gas measurements (station mast) as well as online and offline analysis with a gas chromatographer coupled to a mass spectrometer (GC–MS) and offline liquid chromatography. Up to 104 compounds, mostly volatile organic compounds (VOCs) and oxidized VOCs, but also inorganic compounds, were included in the analysis, even though the data availability for each compound varied with time. The monthly averaged experimental total OH reactivity was found to be higher in April and May (ca. 20 s−1) than in June and July (7.6 and 15.4 s−1, respectively). The measured values varied much more in spring with high reactivity peaks in late afternoon, with values higher than in the summer, in particular when the soil was thawing. Total OH reactivity values generally followed the pattern of mixing ratios due to change of the boundary layer height. The missing reactivity fraction (defined as the difference between measured and calculated OH reactivity) was found to be high. Several reasons that can explain the missing reactivity are discussed in detail such as (1) missing measurements due to technical issues, (2) not measuring oxidation compounds of detected biogenic VOCs, and (3) missing important reactive compounds or classes of compounds with the available measurements. In order to test the second hypothesis, a one-dimensional chemical transport model (SOSAA) has been used to estimate the amount of unmeasured oxidation products and their expected contribution to the reactivity for three different short periods in April, May, and July. However, only a small fraction (<4.5 %) of the missing reactivity can be explained by modelled secondary compounds (mostly oxidized VOCs). These findings indicate that compounds measured but not included in the model as well as unmeasured primary emissions contribute the missing reactivity. In the future, non-hydrocarbon compounds from sources other than vegetation (e.g. soil) should be included in OH reactivity studies.


2019 ◽  
Author(s):  
Arnaud P. Praplan ◽  
Toni Tykkä ◽  
Dean Chen ◽  
Michael Boy ◽  
Ditte Taipale ◽  
...  

Abstract. Total hydroxyl radical (OH) reactivity measurements were conducted at the second Station for Measuring Ecosystem-Atmosphere Relations (SMEAR II), a boreal forest site located in Hyytiälä, Finland, from April to July 2016. The measured values were compared with OH reactivity calculated from a combination of data from the routine trace gas measurements (station mast) as well as online and offline analysis with gas chromatography coupled to mass spectrometry (GC-MS) and offline liquid chromatography. Up to 104 compounds, mostly Volatile Organic Compounds (VOCs) and oxidised VOCs, but also inorganic compounds, were included in the analysis, even though the data availability for each compound varied with time. The averaged experimental total OH reactivity increased from April to June (from 5.3 to 11.3 s−1) and decreased in July (8.8 s−1) due to different environmental conditions during the measurement days. In general, the total OH reactivity increased in late-afternoon and is high at night. It decreases in the morning and is low during the day, following the pattern of mixing ratios due to change of the boundary layer height. The missing reactivity fraction (defined as the different between measured and calculated OH reactivity) was found to be high. Several reasons that can explain the missing reactivity are discussed in detail such as (1) missing measurements due to technical issues, (2) not measuring oxidation compounds of detected biogenic VOCs, (3) missing important reactive compounds or classes of compounds with the available measurements. In order to test the second hypothesis, a one-dimensional chemical transport model (SOSAA) has been used to estimate the amount of unmeasured oxidation products and their expected contribution to the reactivity for three different short periods in April, May, and July. However, only a small fraction (


2009 ◽  
Vol 9 (3) ◽  
pp. 13889-13916 ◽  
Author(s):  
A. Voulgarakis ◽  
O. Wild ◽  
N. H. Savage ◽  
G. D. Carver ◽  
J. A. Pyle

Abstract. We use a three-dimensional chemical transport model to examine the shortwave radiative effects of clouds on the tropospheric ozone budget. In addition to looking at changes in global concentrations as previous studies have done, we examine changes in ozone chemical production and loss caused by clouds and how these vary in different parts of the troposphere. On a global scale, we find that clouds have a modest effect on ozone chemistry, but on a regional scale their role is much more significant, with the size of the response dependent on the region. The largest averaged changes in chemical budgets (±10–14%) are found in the marine troposphere, where cloud optical depths are high. We demonstrate that cloud effects are small on average in the middle troposphere because this is a transition region between reduction and enhancement in photolysis rates. We show that increases in boundary layer ozone due to clouds are driven by large-scale changes in downward ozone transport from higher in the troposphere rather than by decreases in in-situ ozone chemical loss rates. Increases in upper tropospheric ozone are caused by higher production rates due to backscattering of radiation and consequent increases in photolysis rates, mainly J(NO2). The global radiative effect of clouds on isoprene is stronger than on ozone. Tropospheric isoprene lifetime increases by 7% when taking clouds into account. We compare the importance of clouds in contributing to uncertainties in the global ozone budget with the role of other radiatively-important factors. The budget is most sensitive to the overhead ozone column, while surface albedo and clouds have smaller effects. However, uncertainty in representing the spatial distribution of clouds may lead to a large sensitivity on regional scales.


2009 ◽  
Vol 9 (21) ◽  
pp. 8235-8246 ◽  
Author(s):  
A. Voulgarakis ◽  
O. Wild ◽  
N. H. Savage ◽  
G. D. Carver ◽  
J. A. Pyle

Abstract. We use a three-dimensional chemical transport model to examine the shortwave radiative effects of clouds on the tropospheric ozone budget. In addition to looking at changes in global concentrations as previous studies have done, we examine changes in ozone chemical production and loss caused by clouds and how these vary in different parts of the troposphere. On a global scale, we find that clouds have a modest effect on ozone chemistry, but on a regional scale their role is much more significant, with the size of the response dependent on the region. The largest averaged changes in chemical budgets (±10–14%) are found in the marine troposphere, where cloud optical depths are high. We demonstrate that cloud effects are small on average in the middle troposphere because this is a transition region between reduction and enhancement in photolysis rates. We show that increases in boundary layer ozone due to clouds are driven by large-scale changes in downward ozone transport from higher in the troposphere rather than by decreases in in-situ ozone chemical loss rates. Increases in upper tropospheric ozone are caused by higher production rates due to backscattering of radiation and consequent increases in photolysis rates, mainly J(NO2). The global radiative effect of clouds on isoprene, through decreases of OH in the lower troposphere, is stronger than on ozone. Tropospheric isoprene lifetime increases by 7% when taking clouds into account. We compare the importance of clouds in contributing to uncertainties in the global ozone budget with the role of other radiatively-important factors. The budget is most sensitive to the overhead ozone column, while surface albedo and clouds have smaller effects. However, uncertainty in representing the spatial distribution of clouds may lead to a large sensitivity of the ozone budget components on regional scales.


2016 ◽  
Author(s):  
Putian Zhou ◽  
Laurens Ganzeveld ◽  
Üllar Rannik ◽  
Luxi Zhou ◽  
Rosa Gierens ◽  
...  

Abstract. A multi-layer ozone (O3) dry deposition model has been implemented into SOSAA (a model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to improve the representation of O3 within and above the forest canopy in the planetary boundary layer where O3 is a key oxidant agent of biogenic volatile organic compounds (BVOCs) and thus affecting organic aerosol processes. We aim to predict the O3 uptake by a boreal forest canopy under varying environmental conditions and analyse the influence of different factors on total O3 uptake by the canopy as well as the vertical distribution of deposition sinks inside the canopy. We evaluated the newly implemented canopy deposition model by an extensive comparison of simulated and observed O3 fluxes and concentration profiles within and above the boreal forest canopy at SMEAR II (the Station to Measure Ecosystem-Atmosphere Relation II) in Hyytiälä, Finland, in August, 2010. The first half of August showed extremely warm and dry conditions which were probably representative for summer conditions prevailing at this site in future. The simulated O3 turbulent fluxes at the canopy top and the O3 concentration profiles inside the canopy agreed well with the measurement, which indicated that the turbulent transport and the O3 dry deposition onto the canopy and soil surface appeared to be properly represented in the model. In this model, the fraction of wet surface on vegetation leaves was parameterised according to the ambient relative humidity (RH). Model results showed that when RH was larger than 70 % the O3 uptake onto wet skin contributed 48.6 % to the total deposition during nighttime and 22.0 % during daytime. In addition, most of the O3 deposition occurred below 0.8 hc (canopy height) at this site. The contribution of sub-canopy deposition below 4.2 m was modelled to be about 40 % of the total O3 deposition during daytime which was similar to previous studies. Whereas for nighttime, the simulated sub-canopy deposition contributed 40–65 % to the total O3 deposition which was about two times as that in previous studies (25–30 %). The overall contribution of soil uptake was estimated as 36.5 %. These results indicated the importance of non-stomatal O3 uptake processes, especially the uptake on wet skin and soil surface. Furthermore, a qualitative evaluation of the chemical removal time scales indicated that the chemical removal rate within canopy was about 5 % of the total deposition flux at daytime and 16 % at nighttime under current knowledge of air chemistry. The evaluation of the O3 deposition processes provides improved understanding about the mechanisms involved in the removal of O3 for this boreal forest site which are also relevant to the removal of other reactive compounds such as the BVOCs and their oxidation products, which will be focus of a follow-up study.


2020 ◽  
Vol 4 (2) ◽  
pp. 321-327 ◽  
Author(s):  
Amit Sharma ◽  
Narendra Ojha ◽  
Tabish U. Ansari ◽  
Som K. Sharma ◽  
Andrea Pozzer ◽  
...  

2007 ◽  
Vol 7 (3) ◽  
pp. 9053-9092 ◽  
Author(s):  
C. R. Hoyle ◽  
T. Berntsen ◽  
G. Myhre ◽  
I. S. A. Isaksen

Abstract. The global chemical transport model Oslo CTM2 has been extended to include the formation, transport and deposition of secondary organic aerosol (SOA). Precursor hydrocarbons which are oxidised to form condensible species include both biogenic species such as terpenes and isoprene, as well as species emitted predominantly by anthropogenic activities (toluene, m-xylene, methylbenzene and other aromatics). A model simulation for 2004 gives an annual global SOA production of approximately 55 Tg. Of this total, 2.5 Tg is found to consist of the oxidation products of anthropogenically emitted hydrocarbons, and about 15 Tg is formed by the oxidation products of isoprene. The global production of SOA is increased to about 76 Tg yr−1 by allowing semi-volatile species to condense on ammonium sulphate aerosol. This brings modelled organic aerosol values closer to those observed, however observations in Europe remain significantly underestimated, raising the possibility of an unaccounted for SOA source. Allowing SOA to form on ammonium sulphate aerosol increases the contribution of anthropogenic SOA from about 4.5% to almost 9% of the total production. The importance of NO3 as an oxidant of SOA precursors is found to vary regionally, causing up to 50%–60% of the total amount of SOA near the surface in polluted regions and less than 25% in more remote areas. This study underscores the need for SOA to be represented in a more realistic way in global aerosol models in order to better reproduce observations of organic aerosol burdens in industrialised and biomass burning regions.


2009 ◽  
Vol 9 (5) ◽  
pp. 18511-18543 ◽  
Author(s):  
J. Aschmann ◽  
B. M. Sinnhuber ◽  
E. L. Atlas ◽  
S. M. Schauffler

Abstract. The transport of very short-lived substances into the tropical upper troposphere and lower stratosphere is investigated by a three-dimensional chemical transport model using archived convective updraft mass fluxes (or detrainment rates) from the European Centre for Medium-Range Weather Forecast's ERA-Interim reanalysis. Large-scale vertical velocities are calculated from diabatic heating rates. With this approach we explicitly model the large scale subsidence in the tropical troposphere with convection taking place in fast and isolated updraft events. The model calculations agree generally well with observations of bromoform and methyl iodide from aircraft campaigns and with ozone and water vapor from sonde and satellite observations. Using a simplified treatment of dehydration and bromine product gas washout we give a range of 1.6 to 3 ppt for the contribution of bromoform to stratospheric bromine, assuming a uniform source in the boundary layer of 1 ppt. We show that the most effective region for VSLS transport into the stratosphere is the West Pacific, accounting for about 55% of the bromine from bromoform transported into the stratosphere under the supposition of a uniformly distributed source.


2015 ◽  
Vol 15 (20) ◽  
pp. 11807-11833 ◽  
Author(s):  
W. W. Hu ◽  
P. Campuzano-Jost ◽  
B. B. Palm ◽  
D. A. Day ◽  
A. M. Ortega ◽  
...  

Abstract. Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.


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