A Future Multi-Platform Atmospheric Chemistry Measurement Campaign to Study Oxidation in Mixed Anthropogenic-Biogenic Air Masses

Author(s):  
Christopher Cantrell ◽  
Vincent Michoud ◽  
Paola Formenti ◽  
Jean-Francois Doussin ◽  
Stephanie Alhajj Moussa ◽  
...  

<p>It is well known that the high population density of urban regions leads to significant degradation of the quality of the air because of the emissions of pollutants that are by-products of energy production, transportation, and industry. The composition and chemistry of urban air has been studied for many decades and these studies have led to detailed understanding of the factors controlling, for example, the formation of ozone, peroxyacetyl nitrate and other secondary species. In the last 20 to 30 years, significant progress has been made in reducing emissions of volatile organic compounds (VOCs) and oxides of nitrogen (NO<sub>x</sub>) in urban atmospheres. Substantial reductions in the abundance of secondary compounds, though, have been more elusive.</p><p>Research has continued to reveal more and more details of the complex processes involved in the atmospheric degradation of wide varieties of volatile organic compounds (VOCs) of anthropogenic and biospheric (BVOCs) origins. BVOCs include isoprene, monoterpenes and sesquiterpenes, and oxygenated VOCs (OVOCs, such as small alcohols). Emissions of BVOCs depend on several factors such as plant or tree species, temperature, and photosynthetically active radiation. They consist almost exclusively of unsaturated compounds with chemistry somewhat different from those of typical urban organic compound emissions. Oxidation of VOCs can lead to molecules of low volatility that are prone to uptake into the aerosol phase.</p><p>Recent studies conducted in megacities such as Paris, Mexico City, Los Angeles and those in China have led to significant advances in our understanding of the chemical evolution of urban plumes. However, important scientific questions remain on how mixing of anthropogenic and biogenic air masses modifies the composition of urban plumes and hence their impacts. Indeed, the proximity of cites to areas of strong biogenic emissions is not unusual. Many major cities at mid-latitudes are surrounded by forested areas.</p><p>ACROSS (Atmospheric ChemistRy Of the Suburban foreSt) is an integrative, innovative, multi-scale project awarded under the “Make Our Planet Great Again” (MOPGA) framework that seeks to definitively improve understanding of the impacts of mixing urban and biogenic air masses on the oxidation of atmospheric VOCs. The ACROSS working hypothesis is that this leads to changes in the production of oxygenated VOCs whose properties (e.g. vapor pressures) alter their importance in incorporation into SOA and their roles in production of ozone and other secondary species. Changes are also expected in the efficiency of radical recycling affecting the atmospheric oxidative capacity. Particularly important is NO<sub>x</sub> transport to suburban biogenic environments and the resulting modification of key chemical processes.</p><p>A key highlight of ACROSS is an intensive, multi-platform measurement campaign in the summer of 2022. It will use instruments staged on an airborne platform, a tower in the Rambouillet Forest near Paris, and other ground sites. The data collected from this campaign will be analyzed and studied to extract information about tropospheric oxidation chemistry generally, but also changes observed in the situation of mixed urban and biogenic air masses.</p><p>This presentation will summarize plans for the ACROSS campaign.</p>

2012 ◽  
Vol 117 (D21) ◽  
pp. n/a-n/a ◽  
Author(s):  
Carsten Warneke ◽  
Joost A. de Gouw ◽  
John S. Holloway ◽  
Jeff Peischl ◽  
Thomas B. Ryerson ◽  
...  

2009 ◽  
Vol 6 (1) ◽  
pp. 70 ◽  
Author(s):  
Aurélie Colomb ◽  
Valérie Gros ◽  
Séverine Alvain ◽  
Roland Sarda-Esteve ◽  
Bernard Bonsang ◽  
...  

Environmental context. Oceans represent 70% of the blue planet, and surprisingly, ocean emission in term of volatile organic compounds is poorly understood. The potential climate impacts on a global scale of various trace organic gases have been established, and the terrestrial inputs are well studied, but little is known about which of these can be emitted from oceanic sources. In the present study, atmospheric samples were taken over the Southern Indian Ocean, while crossing some oceanic fronts and different phytoplankton species. Such a study should aid in understanding oceanic emission, especially from phytoplankton, and will help modellers to determine concentrations of organic traces in the remote marine troposphere. Abstract. Considering its size and potential importance, the ocean is poorly characterised in terms of volatile organic compounds (VOC) that play important roles in global atmospheric chemistry. In order to better understand their potential sources and sinks over the Southern Indian Austral Ocean, shipborne measurements of selected species were made during the MANCHOT campaign during December 2004, on board the research vessel Marion Dufresne. Along the transect La Réunion to Kerguelen Island, air measurements of selected VOC (including dimethylsulfide (DMS) isoprene, carbonyls and organohalogens), carbon monoxide and ozone were performed, crossing subtropical, temperate and sub-Antarctic waters as well as pronounced subtropical and sub-Antarctic oceanic fronts. The remote marine boundary layer was characterised at latitudes 45–50°S. Oceanic fronts were associated with enhanced chlorophyll and biological activity in the seawater and elevated DMS and organohalogens in the atmosphere. These were compared with a satellite-derived phytoplankton distribution (PHYSAT). Diurnal variation for isoprene, terpenes, acetone and acetaldehyde was observed, analogously to recent results observed in mesocosm experiments.


2019 ◽  
Vol 19 (4) ◽  
pp. 2209-2232 ◽  
Author(s):  
Guo Li ◽  
Yafang Cheng ◽  
Uwe Kuhn ◽  
Rongjuan Xu ◽  
Yudong Yang ◽  
...  

Abstract. Volatile organic compounds (VOCs) play a key role in atmospheric chemistry. Emission and deposition on soil have been suggested as important sources and sinks of atmospheric trace gases. The exchange characteristics and heterogeneous chemistry of VOCs on soil, however, are not well understood. We used a newly designed differential coated-wall flow tube system to investigate the long-term variability of bidirectional air–soil exchange of 13 VOCs under ambient air conditions of an urban background site in Beijing. Sterilized soil was investigated to address physicochemical processes and heterogeneous/multiphase reactions independently from biological activity. Most VOCs revealed net deposition with average uptake coefficients (γ) in the range of 10−7–10−6 (referring to the geometric soil surface area), corresponding to deposition velocities (Vd) of 0.0013–0.01 cm s−1 and soil surface resistances (Rc) of 98–745 s cm−1, respectively. Formic acid, however, was emitted at a long-term average rate of ∼6×10-3 nmol m−2 s−1, suggesting that it was formed and released upon heterogeneous oxidation of other VOCs. The soil–atmosphere exchange of one individual VOC species can be affected by both its surface degradation/depletion caused by surface reactions and by competitive uptake or heterogeneous formation/accommodation of other VOC species. Overall, the results show that physicochemical processing and heterogeneous oxidation on soil and soil-derived dust can act as a sink or as a source of atmospheric VOCs, depending on molecular properties and environmental conditions.


2016 ◽  
Author(s):  
N. L. Ng ◽  
S. S. Brown ◽  
A. T. Archibald ◽  
E. Atlas ◽  
R. C. Cohen ◽  
...  

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.


2010 ◽  
Vol 10 (17) ◽  
pp. 8391-8412 ◽  
Author(s):  
B. Langford ◽  
P. K. Misztal ◽  
E. Nemitz ◽  
B. Davison ◽  
C. Helfter ◽  
...  

Abstract. As part of the OP3 field study of rainforest atmospheric chemistry, above-canopy fluxes of isoprene, monoterpenes and oxygenated volatile organic compounds were made by virtual disjunct eddy covariance from a South-East Asian tropical rainforest in Malaysia. Approximately 500 hours of flux data were collected over 48 days in April–May and June–July 2008. Isoprene was the dominant non-methane hydrocarbon emitted from the forest, accounting for 80% (as carbon) of the measured emission of reactive carbon fluxes. Total monoterpene emissions accounted for 18% of the measured reactive carbon flux. There was no evidence for nocturnal monoterpene emissions and during the day their flux rate was dependent on both light and temperature. The oxygenated compounds, including methanol, acetone and acetaldehyde, contributed less than 2% of the total measured reactive carbon flux. The sum of the VOC fluxes measured represents a 0.4% loss of daytime assimilated carbon by the canopy, but atmospheric chemistry box modelling suggests that most (90%) of this reactive carbon is returned back to the canopy by wet and dry deposition following chemical transformation. The emission rates of isoprene and monoterpenes, normalised to 30 °C and 1000 μmol m−2 s−1 PAR, were 1.6 mg m−2 h−1 and 0.46mg m−2 h−1 respectively, which was 4 and 1.8 times lower respectively than the default value for tropical forests in the widely-used MEGAN model of biogenic VOC emissions. This highlights the need for more direct canopy-scale flux measurements of VOCs from the world's tropical forests.


2017 ◽  
Vol 17 (15) ◽  
pp. 9547-9566 ◽  
Author(s):  
Bettina Derstroff ◽  
Imke Hüser ◽  
Efstratios Bourtsoukidis ◽  
John N. Crowley ◽  
Horst Fischer ◽  
...  

Abstract. During the summertime CYPHEX campaign (CYprus PHotochemical EXperiment 2014) in the eastern Mediterranean, multiple volatile organic compounds (VOCs) were measured from a 650 m hilltop site in western Cyprus (34° 57′ N/32° 23′ E). Periodic shifts in the northerly Etesian winds resulted in the site being alternately impacted by photochemically processed emissions from western (Spain, France, Italy) and eastern (Turkey, Greece) Europe. Furthermore, the site was situated within the residual layer/free troposphere during some nights which were characterized by high ozone and low relative humidity levels. In this study we examine the temporal variation of VOCs at the site. The sparse Mediterranean scrub vegetation generated diel cycles in the reactive biogenic hydrocarbon isoprene, from very low values at night to a diurnal median level of 80–100 pptv. In contrast, the oxygenated volatile organic compounds (OVOCs) methanol and acetone exhibited weak diel cycles and were approximately an order of magnitude higher in mixing ratio (ca. 2.5–3 ppbv median level by day, range: ca. 1–8 ppbv) than the locally emitted isoprene and aromatic compounds such as benzene and toluene. Acetic acid was present at mixing ratios between 0.05 and 4 ppbv with a median level of ca. 1.2 ppbv during the daytime. When data points directly affected by the residual layer/free troposphere were excluded, the acid followed a pronounced diel cycle, which was influenced by various local effects including photochemical production and loss, direct emission, dry deposition and scavenging from advecting air in fog banks. The Lagrangian model FLEXPART was used to determine transport patterns and photochemical processing times (between 12 h and several days) of air masses originating from eastern and western Europe. Ozone and many OVOC levels were  ∼  20 and  ∼  30–60 % higher, respectively, in air arriving from the east. Using the FLEXPART calculated transport time, the contribution of photochemical processing, sea surface contact and dilution was estimated. Methanol and acetone decreased with residence time in the marine boundary layer (MBL) with loss rate constants of 0.74 and 0.53 day−1 from eastern Europe and 0.70 and 0.34 day−1 from western Europe, respectively. Simulations using the EMAC model underestimate these loss rates. The missing sink in the calculation is most probably an oceanic uptake enhanced by microbial consumption of methanol and acetone, although the temporal and spatial variability in the source strength on the continents might play a role as well. Correlations between acetone and methanol were weaker in western air masses (r2  =  0.68), but were stronger in air masses measured after the shorter transport time from the east (r2  =  0.73).


2010 ◽  
Vol 10 (21) ◽  
pp. 10321-10334 ◽  
Author(s):  
J. Bechara ◽  
A. Borbon ◽  
C. Jambert ◽  
A. Colomb ◽  
P. E. Perros

Abstract. A large dataset of reactive trace gases was collected for the first time over West Africa during the African Monsoon Multidisciplinary Analysis (AMMA) field experiment in August 2006. Volatile Organic Compounds (VOC from C5–C9) were measured onboard the two French aircrafts the ATR-42 and the Falcon-20 by a new instrument AMOVOC (Airborne Measurement Of Volatile Organic Compounds). The goal of this study is (i) to characterize VOC distribution in the tropical region of West Africa (ii) to determine the impact of deep convection on VOC distribution and chemistry in the tropical upper troposphere (UT) and (iii) to characterize its spatial and temporal extensions. Experimental strategy consisted in sampling at altitudes between 0 and 12 km downwind of Mesoscale Convective Systems (MCS) and at cloud base. Biogenic and anthropogenic VOC distribution in West Africa is clearly affected by North to South emission gradient. Isoprene, the most abundant VOC, is at maximum level over the forest (1.26 ppb) while benzene reaches its maximum over the urban areas (0.11 ppb). First, a multiple physical and chemical tracers approach using CO, O3 and relative humidity was implemented to distinguish between convective and non-convective air masses. Then, additional tools based on VOC observations (tracer ratios, proxy of emissions and photochemical clocks) were adapted to characterize deep convection on a chemical, spatial and temporal basis. VOC vertical profiles show a "C-shaped" trend indicating that VOC-rich air masses are transported from the surface to the UT by deep convective systems. VOC mixing ratios in convective outflow are up to two times higher than background levels even for reactive and short-lived VOC (e.g. isoprene up to 0.19 ppb at 12 km-altitude) and are dependent on surface emission type. As a consequence, UT air mass reactivity increases from 0.52 s−1 in non-convective conditions to 0.95 s−1 in convective conditions. Fractions of boundary layer air contained in convective outflow are estimated to be 40 ± 15%. Vertical transport timescale is calculated to be 25 ± 10 min between 0 to 12 km altitude. These results characterize deep convection occurring over West Africa and provide relevant information for tropical convection parameterization in regional/global models.


2013 ◽  
Vol 13 (11) ◽  
pp. 30187-30232 ◽  
Author(s):  
E. Bourtsoukidis ◽  
J. Williams ◽  
J. Kesselmeier ◽  
S. Jacobi ◽  
B. Bonn

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.


2021 ◽  
Vol 2 (1) ◽  
Author(s):  
Achim Edtbauer ◽  
Eva Y. Pfannerstill ◽  
Ana Paula Pires Florentino ◽  
Cybelli G. G. Barbosa ◽  
Emilio Rodriguez-Caballero ◽  
...  

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.


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