Jonathan Williams
@mpic.de
Atmospheric Chemistry Department
Max Planck Institute for Chemistry
RESEARCH INTERESTS
Volatile Organic Compounds
Atmospheric Chemistry
Scopus Publications
Scholar Citations
Scholar h-index
Scholar i10-index
Scopus Publications
Efstratios Bourtsoukidis, Andrea Pozzer, Jonathan Williams, David Makowski, Josep Peñuelas, Vasileios N. Matthaios, Georgia Lazoglou, Ana Maria Yañez-Serrano, Jos Lelieveld, Philippe Ciais,et al.
Springer Science and Business Media LLC
AbstractTerrestrial vegetation emits vast amounts of monoterpenes into the atmosphere, influencing ecological interactions and atmospheric chemistry. Global emissions are simulated as a function of temperature with a fixed exponential relationship (β coefficient) across forest ecosystems and environmental conditions. We applied meta-analysis algorithms on 40 years of published monoterpene emission data and show that relationship between emissions and temperature is more sensitive and intricate than previously thought. Considering the entire dataset, a higher temperature sensitivity (β = 0.13 ± 0.01 °C−1) is derived but with a linear increase with the reported coefficients of determination (R2), indicating that co-occurring environmental factors modify the temperature sensitivity of the emissions that is primarily related to the specific plant functional type (PFT). Implementing a PFT-dependent β in a biogenic emission model, coupled with a chemistry – climate model, demonstrated that atmospheric processes are exceptionally dependent on monoterpene emissions which are subject to amplified variations under rising temperatures.
Sarka Langer, Charles J. Weschler, Gabriel Bekö, Glenn Morrison, Ann Sjöblom, Georgios Giovanoulis, Pawel Wargocki, Nijing Wang, Nora Zannoni, Shen Yang,et al.
American Chemical Society (ACS)
A major component of human skin oil is squalene, a highly unsaturated hydrocarbon that protects the skin from atmospheric oxidants. Skin oil, and thus squalene, is continuously replenished on the skin surface. Squalene is also quickly consumed through reactions with ozone and other oxidants. This study examined the extent of squalene depletion in the skin oils of the forearm of human volunteers after exposure to ozone in a climate chamber. Temperature, relative humidity (RH), skin coverage by clothing, and participants' age were varied in a controlled manner. Concentrations of squalene were determined in skin wipe samples collected before and after ozone exposure. Exposures to ozone resulted in statistically significant decreases in post-exposure squalene concentrations compared to pre-exposure squalene concentrations in the skin wipes when squalene concentrations were normalized by concentrations of co-occurring cholesterol but not by co-occurring pyroglutamic acid (PGA). The rate of squalene loss due to ozonolysis was lower than its replenishment on the skin surface. Within the ranges examined, temperature and RH did not significantly affect the difference between normalized squalene levels in post-samples versus pre-samples. Although not statistically significant, skin coverage and age of the volunteers (three young adults, three seniors, and three teenagers) did appear to impact squalene depletion on the skin surfaces.
Shen Yang, Tatjana Müller, Nijing Wang, Gabriel Bekö, Meixia Zhang, Marouane Merizak, Pawel Wargocki, Jonathan Williams, and Dusan Licina
American Chemical Society (ACS)
Ozone reaction with human surfaces is an important source of ultrafine particles indoors. However, 1–20 nm particles generated from ozone–human chemistry, which mark the first step of particle formation and growth, remain understudied. Ventilation and indoor air movement could have important implications for these processes. Therefore, in a controlled-climate chamber, we measured ultrafine particles initiated from ozone–human chemistry and their dependence on the air change rate (ACR, 0.5, 1.5, and 3 h–1) and operation of mixing fans (on and off). Concurrently, we measured volatile organic compounds (VOCs) and explored the correlation between particles and gas-phase products. At 25–30 ppb ozone levels, humans generated 0.2–7.7 × 1012 of 1–3 nm, 0–7.2 × 1012 of 3–10 nm, and 0–1.3 × 1012 of 10–20 nm particles per person per hour depending on the ACR and mixing fan operation. Size-dependent particle growth and formation rates increased with higher ACR. The operation of mixing fans suppressed the particle formation and growth, owing to enhanced surface deposition of the newly formed particles and their precursors. Correlation analyses revealed complex interactions between the particles and VOCs initiated by ozone–human chemistry. The results imply that ventilation and indoor air movement may have a more significant influence on particle dynamics and fate relative to indoor chemistry.
Shen Yang, Gabriel Bekö, Pawel Wargocki, Meixia Zhang, Marouane Merizak, Athanasios Nenes, Jonathan Williams, and Dusan Licina
American Chemical Society (ACS)
Humans are the primary sources of CO2 and NH3 indoors. Their emission rates may be influenced by human physiological and psychological status. This study investigated the impact of physiological and psychological engagements on the human emissions of CO2 and NH3. In a climate chamber, we measured CO2 and NH3 emissions from participants performing physical activities (walking and running at metabolic rates of 2.5 and 5 met, respectively) and psychological stimuli (meditation and cognitive tasks). Participants’ physiological responses were recorded, including the skin temperature, electrodermal activity (EDA), and heart rate, and then analyzed for their relationship with CO2 and NH3 emissions. The results showed that physiological engagement considerably elevated per-person CO2 emission rates from 19.6 (seated) to 46.9 (2.5 met) and 115.4 L/h (5 met) and NH3 emission rates from 2.7 to 5.1 and 8.3 mg/h, respectively. CO2 emissions reduced when participants stopped running, whereas NH3 emissions continued to increase owing to their distinct emission mechanisms. Psychological engagement did not significantly alter participants’ emissions of CO2 and NH3. Regression analysis revealed that CO2 emissions were predominantly correlated with heart rate, whereas NH3 emissions were mainly associated with skin temperature and EDA. These findings contribute to a deeper understanding of human metabolic emissions of CO2 and NH3.
Giovanni Pugliese, Johannes Ingrisch, Laura K. Meredith, Eva Y. Pfannerstill, Thomas Klüpfel, Kathiravan Meeran, Joseph Byron, Gemma Purser, Juliana Gil-Loaiza, Joost van Haren,et al.
Springer Science and Business Media LLC
A. Ringsdorf, A. Edtbauer, J. Vilà-Guerau de Arellano, E. Y. Pfannerstill, S. Gromov, V. Kumar, A. Pozzer, S. Wolff, A. Tsokankunku, M. Soergel,et al.
Springer Science and Business Media LLC
AbstractThe atmospheric oxidation of biogenic volatile organic compounds (BVOC) by OH radicals over tropical rainforests impacts local particle production and the lifetime of globally distributed chemically and radiatively active gases. For the pristine Amazon rainforest during the dry season, we empirically determined the diurnal OH radical variability at the forest-atmosphere interface region between 80 and 325 m from 07:00 to 15:00 LT using BVOC measurements. A dynamic time warping approach was applied showing that median averaged mixing times between 80 to 325 m decrease from 105 to 15 min over this time period. The inferred OH concentrations show evidence for an early morning OH peak (07:00–08:00 LT) and an OH maximum (14:00 LT) reaching 2.2 (0.2, 3.8) × 106 molecules cm−3 controlled by the coupling between BVOC emission fluxes, nocturnal NOx accumulation, convective turbulence, air chemistry and photolysis rates. The results were evaluated with a turbulence resolving transport (DALES), a regional scale (WRF-Chem) and a global (EMAC) atmospheric chemistry model.
Giovanni Pugliese, Johannes Ingrisch, Laura K. Meredith, Eva Y. Pfannerstill, Thomas Klüpfel, Kathiravan Meeran, Joseph Byron, Gemma Purser, Juliana Gil-Loaiza, Joost van Haren,et al.
Springer Science and Business Media LLC
AbstractDrought can affect the capacity of soils to emit and consume biogenic volatile organic compounds (VOCs). Here we show the impact of prolonged drought followed by rewetting and recovery on soil VOC fluxes in an experimental rainforest. Under wet conditions the rainforest soil acts as a net VOC sink, in particular for isoprenoids, carbonyls and alcohols. The sink capacity progressively decreases during drought, and at soil moistures below ~19%, the soil becomes a source of several VOCs. Position specific 13C-pyruvate labeling experiments reveal that soil microbes are responsible for the emissions and that the VOC production is higher during drought. Soil rewetting induces a rapid and short abiotic emission peak of carbonyl compounds, and a slow and long biotic emission peak of sulfur-containing compounds. Results show that, the extended drought periods predicted for tropical rainforest regions will strongly affect soil VOC fluxes thereby impacting atmospheric chemistry and climate.
Susanna Strada, Andrea Pozzer, Graziano Giuliani, Erika Coppola, Fabien Solmon, Xiaoyan Jiang, Alex Guenther, Efstratios Bourtsoukidis, Dominique Serça, Jonathan Williams,et al.
Copernicus GmbH
Abstract. Plants emit biogenic volatile organic compounds (BVOCs) in response to changes in environmental conditions (e.g. temperature, radiation, soil moisture). In the large family of BVOCs, isoprene is by far the strongest emitted compound and plays an important role in ozone chemistry, thus affecting both air quality and climate. In turn, climate change may alter isoprene emissions by increasing temperature as well as the occurrence and intensity of severe water stresses that alter plant functioning. The Model of Emissions of Gases and Aerosols from Nature (MEGAN) provides different parameterizations to account for the impact of water stress on isoprene emissions, which essentially reduces emissions in response to the effect of soil moisture deficit on plant productivity. By applying the regional climate–chemistry model RegCM4chem coupled to the Community Land Model CLM4.5 and MEGAN2.1, we thus performed sensitivity simulations to assess the effects of water stress on isoprene emissions and near-surface ozone levels over the Euro-Mediterranean region and across the drier and wetter summers over the 1992–2016 period using two different parameterizations of the impact of water stress implemented in the MEGAN model. Over the Euro-Mediterranean region and across the simulated summers, water stress reduces isoprene emissions on average by nearly 6 %. However, during the warmest and driest selected summers (e.g. 2003, 2010, 2015) and over large isoprene-source areas (e.g. the Balkans), decreases in isoprene emissions range from −20 % to −60 % and co-occur with negative anomalies in precipitation, soil moisture and plant productivity. Sustained decreases in isoprene emissions also occur after prolonged or repeated dry anomalies, as observed for the summers of 2010 and 2012. Although the decrease in isoprene emissions due to water stress may be important, it only reduces near-surface ozone levels by a few percent due to a dominant VOC-limited regime over southern Europe and the Mediterranean Basin. Overall, over the selected analysis region, compared to the old MEGAN parameterization, the new one leads to localized and 25 %–50 % smaller decreases in isoprene emissions and 3 %–8 % smaller reductions in near-surface ozone levels.
Einar Karu, Mengze Li, Lisa Ernle, Carl A. M. Brenninkmeijer, Jos Lelieveld, and Jonathan Williams
American Geophysical Union (AGU)
AbstractCarbonyl sulfide (OCS or COS) is a ubiquitous trace gas and plays a role in forming stratospheric sulfate aerosol particles, thereby influencing climate. In this study, whole‐air samples containing OCS were collected onboard a passenger aircraft (IAGOS‐CARIBIC) from the upper troposphere/lowermost stratosphere (UT/LMS, 10–12 km) region and analyzed with CryoTrap–GC–AED system in the laboratory. Global OCS mixing ratios are presented and by using the OCS measurements in conjunction with other trace gases, an atmospheric OCS lifetime of 2.1 ± 1.3 years, and lowermost stratospheric OCS lifetime of 47 ± 16 years were determined. A total flux of 137 GgS a−1 of OCS from the troposphere into the stratosphere was estimated, and the stratospheric sink estimate yielded 55 ± 23 GgS a−1 of OCS. The 60% smaller sink can be interpreted as 82 GgS a−1 OCS which is transported back from the stratosphere into the troposphere.
Linnea K. Honeker, Giovanni Pugliese, Johannes Ingrisch, Jane Fudyma, Juliana Gil-Loaiza, Elizabeth Carpenter, Esther Singer, Gina Hildebrand, Lingling Shi, David W. Hoyt,et al.
Springer Science and Business Media LLC
AbstractDrought impacts on microbial activity can alter soil carbon fate and lead to the loss of stored carbon to the atmosphere as CO2 and volatile organic compounds (VOCs). Here we examined drought impacts on carbon allocation by soil microbes in the Biosphere 2 artificial tropical rainforest by tracking 13C from position-specific 13C-pyruvate into CO2 and VOCs in parallel with multi-omics. During drought, efflux of 13C-enriched acetate, acetone and C4H6O2 (diacetyl) increased. These changes represent increased production and buildup of intermediate metabolites driven by decreased carbon cycling efficiency. Simultaneously,13C-CO2 efflux decreased, driven by a decrease in microbial activity. However, the microbial carbon allocation to energy gain relative to biosynthesis was unchanged, signifying maintained energy demand for biosynthesis of VOCs and other drought-stress-induced pathways. Overall, while carbon loss to the atmosphere via CO2 decreased during drought, carbon loss via efflux of VOCs increased, indicating microbially induced shifts in soil carbon fate.
Lisa Ernle, Nijing Wang, Gabriel Bekö, Glenn Morrison, Pawel Wargocki, Charles J. Weschler, and Jonathan Williams
Royal Society of Chemistry (RSC)
PTR m/z 69.07 commonly attributed to isoprene suffers interference from C5–C10 aldehydes indoors, especially when ozone is present. The contribution of nonanal could be quantified by using the protonated molecular ion, unlike the other aldehydes.
Akila Muthalagu, Helene Niculita-Hirzel, Shen Yang, Marouane Merizak, Michael Pikridas, Asif Qureshi, Pawel Wargocki, Gabriel Bekö, Jonathan Williams, Martin Täubel,et al.
Elsevier BV
Toni Krause, Piera Wiesinger, Diego González-Cabanelas, Nathalie Lackus, Tobias G Köllner, Thomas Klüpfel, Jonathan Williams, Johann Rohwer, Jonathan Gershenzon, and Axel Schmidt
Oxford University Press (OUP)
Abstract Dimethylallyl diphosphate (DMADP) and isopentenyl diphosphate (IDP) serves as the universal C5 precursors of isoprenoid biosynthesis in plants. These compounds are formed by the last step of the 2-C-methyl-D-erythritol 4-phosphate (MEP) pathway, catalyzed by (E)-4-hydroxy-3-methylbut-2-en-1-yl diphosphate reductase (HDR). In this study, we investigated the major HDR isoforms of two woody plant species, Norway spruce (Picea abies) and gray poplar (Populus × canescens), to determine how they regulate isoprenoid formation. Since each of these species has a distinct profile of isoprenoid compounds, they may require different proportions of DMADP and IDP with proportionally more IDP being needed to make larger isoprenoids. Norway spruce contained two major HDR isoforms differing in their occurrence and biochemical characteristics. PaHDR1 produced relatively more IDP than PaHDR2 and it encoding gene was expressed constitutively in leaves, likely serving to form substrate for production of carotenoids, chlorophylls, and other primary isoprenoids derived from a C20 precursor. On the other hand, Norway spruce PaHDR2 produced relatively more DMADP than PaHDR1 and its encoding gene was expressed in leaves, stems, and roots, both constitutively and after induction with the defense hormone methyl jasmonate. This second HDR enzyme likely forms a substrate for the specialized monoterpene (C10), sesquiterpene (C15), and diterpene (C20) metabolites of spruce oleoresin. Gray poplar contained only one dominant isoform (named PcHDR2) that produced relatively more DMADP and the gene of which was expressed in all organs. In leaves, where the requirement for IDP is high to make the major carotenoid and chlorophyll isoprenoids derived from C20 precursors, excess DMADP may accumulate, which could explain the high rate of isoprene (C5) emission. Our results provide new insights into the biosynthesis of isoprenoids in woody plants under conditions of differentially regulated biosynthesis of the precursors IDP and DMADP.
Lisa Ernle, Monika Akima Ringsdorf, and Jonathan Williams
Copernicus GmbH
Abstract. The measurement of volatile organic compounds (VOCs) can be influenced by ozone (O3), resulting in sampling artefacts that corrupt the data obtained. Published literature reports both positive (false enhancements of signal) and negative (loss of signal) interference in VOC data due to ozonolysis occurring in the sample gas. To assure good data quality it is essential to be aware of such interfering processes, to characterize them and to try to minimize the impact with a suitable sampling setup. Here we present results from experiments with a sodium thiosulfate ozone scrubber (Na2S2O3), which is a cost-effective and easily applied option for O3 scavenging during gas-phase sampling. Simultaneous measurement of selected organic trace gases using gas chromatography–mass spectrometry and proton transfer reaction–mass spectrometry was performed at different ozone levels (0–1 ppm) and different relative humidities (0 %–80 %). In this way both tropospheric and stratospheric conditions were examined. The measured data show that several carbonyl compounds including acetaldehyde, acetone and propanal show artificial signal enhancement when ozone is present at higher concentrations (> 150 ppb) in dry air, while analytes with double bonds like isoprene (measured with GC-MS) and terpenes show lower signals due to reaction with ozone. Both effects can be eliminated or in the case of sesquiterpenes substantially reduced by using Na2S2O3 impregnated quartz filters in the inlet line. With the chosen scrubbing material, relative humidity (RH) substantially improves the scrubbing efficiency. Under surface conditions between 50 %–80 % RH, the filter allows for accurate measurement of all species examined.
Gisèle Krysztofiak, Valéry Catoire, Thierry Dudok de Wit, Douglas E. Kinnison, A. R. Ravishankara, Vanessa Brocchi, Elliot Atlas, Heiko Bozem, Róisín Commane, Francesco D’Amato,et al.
MDPI AG
Nitrous oxide (N2O) is the fourth most important greenhouse gas in the atmosphere and is considered the most important current source gas emission for global stratospheric ozone depletion (O3). It has natural and anthropogenic sources, mainly as an unintended by-product of food production activities. This work examines the identification and quantification of trends in the N2O concentration from the middle troposphere to the middle stratosphere (MTMS) by in situ and remote sensing observations. The temporal variability of N2O is addressed using a comprehensive dataset of in situ and remote sensing N2O concentrations based on aircraft and balloon measurements in the MTMS from 1987 to 2018. We determine N2O trends in the MTMS, based on observations. This consistent dataset was also used to study the N2O seasonal cycle to investigate the relationship between abundances and its emission sources through zonal means. The results show a long-term increase in global N2O concentration in the MTMS with an average of 0.89 ± 0.07 ppb/yr in the troposphere and 0.96 ± 0.15 ppb/yr in the stratosphere, consistent with 0.80 ppb/yr derived from ground-based measurements and 0.799 ± 0.024 ppb/yr ACE-FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) satellite measurements.
Denis Leppla, Nora Zannoni, Leslie Kremper, Jonathan Williams, Christopher Pöhlker, Marta Sá, Maria Christina Solci, and Thorsten Hoffmann
Copernicus GmbH
Abstract. Chiral chemodiversity plays a crucial role in biochemical processes such as insect and plant communication. However, the vast majority of organic aerosol studies do not distinguish between enantiomeric compounds in the particle phase. Here we report chirally specified measurements of secondary organic aerosol (SOA) at the Amazon Tall Tower Observatory (ATTO) at different altitudes during three measurement campaigns at different seasons. Analysis of filter samples by liquid chromatography coupled to mass spectrometry (LC-MS) has shown that the chiral ratio of pinic acid (C9H14O4) varies with increasing height above the canopy. A similar trend was recently observed for the gas-phase precursor α-pinene but more pronounced. Nevertheless, the measurements indicate that neither the oxidation of (+/−)-α-pinene nor the incorporation of the products into the particulate phase proceeds with stereo preference and that the chiral information of the precursor molecule is merely transferred to the low-volatility product. The observation of the weaker height gradient of the present enantiomers in the particle phase at the observation site can be explained by the significant differences in the atmospheric lifetimes of reactant and product. Therefore, it is suggested that the chiral ratio of pinic acid is mainly determined by large-scale emission processes of the two precursors, while meteorological, chemical, or physicochemical processes do not play a particular role. Characteristic emissions of the chiral aerosol precursors from different forest ecosystems, in some cases even with contributions from forest-related fauna, could thus provide large-scale information on the different contributions to biogenic secondary aerosols via the analytics of the chiral particle-bound degradation products.
Linnea K. Honeker, Giovanni Pugliese, Johannes Ingrisch, Jane Fudyma, Juliana Gil-Loaiza, Elizabeth Carpenter, Esther Singer, Gina Hildebrand, Lingling Shi, David W. Hoyt,et al.
Springer Science and Business Media LLC
Sergey Osipov, Sourangsu Chowdhury, John N. Crowley, Ivan Tadic, Frank Drewnick, Stephan Borrmann, Philipp Eger, Friederike Fachinger, Horst Fischer, Evgeniya Predybaylo,et al.
Springer Science and Business Media LLC
AbstractIn the Middle East, desert dust is assumed to dominate air pollution, being in permanent violation of public health guidelines. Here we present ship-borne measurements from around the Arabian Peninsula and modeling results to show that hazardous fine particulate matter is to a large extent of anthropogenic origin (>90%), and distinct from the less harmful, coarse desert dust particles. Conventionally, it was understood that desert dust dominates both the fine and coarse aerosol size fractions, which obscures the anthropogenic signal. We find that the annual excess mortality from the exposure to air pollution is 745 (514-1097) per 100,000 per year, similar to that of other leading health risk factors, like high cholesterol and tobacco smoking. Furthermore, anthropogenic pollution particles account for a major part (~53%) of the visible aerosol optical depth. Therefore, in the Middle East anthropogenic air pollution is a leading health risk and an important climatic factor.
N. Wang, G. Pugliese, M. Carrito, C. Moura, P. Vasconcelos, N. Cera, M. Li, P. Nobre, J. R. Georgiadis, J. K. Schubert,et al.
Springer Science and Business Media LLC
Abstract The chemical composition of exhaled breath was examined for volatile organic compound (VOC) indicators of sexual arousal in human beings. Participants (12-male, 12-female) were shown a randomized series of three emotion-inducing 10-min film clips interspersed with 3-min neutral film clips. The films caused different arousals: sports film (positive-nonsexual); horror film (negative-nonsexual); and erotic (sexual) that were monitored with physiological measurements including genital response and temperature. Simultaneously the breath was monitored for VOC and CO2. While some breath compounds (methanol and acetone) changed uniformly irrespective of the film order, several compounds did show significant arousal associated changes. For both genders CO2 and isoprene decreased in the sex clip. Some male individuals showed particularly strong increases of indole, phenol and cresol coincident with sexual arousal that decreased rapidly afterwards. These VOCs are degradation products of tyrosine and tryptophan, precursors for dopamine, noradrenalin, and serotonin, and therefore represent potential breath markers of sexual arousal.
Pascale S. J. Lakey, Andreas Zuend, Glenn C. Morrison, Thomas Berkemeier, Jake Wilson, Caleb Arata, Allen H. Goldstein, Kevin R. Wilson, Nijing Wang, Jonathan Williams,et al.
Royal Society of Chemistry (RSC)
Models were developed to treat Criegee chemistry and estimate gas-phase squalene ozonolysis products under different conditions. Relative humidity can significantly impact human exposure to these products.
Mengze Li, Andrea Pozzer, Jos Lelieveld, and Jonathan Williams
Copernicus GmbH
Abstract. Methane, ethane, and propane are among the most abundant hydrocarbons in the atmosphere. These compounds have many emission sources in common and are all primarily removed through OH oxidation. Their mixing ratios and long-term trends in the upper troposphere and stratosphere are rarely reported due to the paucity of measurements. In this study, we present long-term (2006–2016) northern hemispheric ethane, propane, and methane data from airborne observation in the upper troposphere-lower stratosphere (UTLS) region from the IAGOS-CARIBIC project. The methane and propane observations provide additional information for understanding northern hemispheric ethane trends, which is the major focus of this study. The linear trends, moving averages, nonlinear trends and monthly variations of ethane, methane and propane in 2006–2016 are presented for the upper troposphere and lower stratosphere over 5 regions (whole Northern Hemisphere, Europe, North America, Asia and the rest of the world). The growth rates of ethane, methane, and propane in the upper troposphere are −2.24 % yr−1, 0.33 % yr−1, and −0.78 % yr−1, respectively, and in the lower stratosphere they are −3.27 % yr−1, 0.26 % yr−1, and −4.91 % yr−1, respectively, in 2006–2016. This dataset is of value to future global ethane budget estimates and the optimization of current ethane inventories. The data are publicly accessible at https://doi.org/10.5281/zenodo.6536109 (Li et al., 2022a).
Therese S. Carter, Colette L. Heald, Jesse H. Kroll, Eric C. Apel, Donald Blake, Matthew Coggon, Achim Edtbauer, Georgios Gkatzelis, Rebecca S. Hornbrook, Jeff Peischl,et al.
Copernicus GmbH
Abstract. Fires emit a substantial amount of non-methane organic gases (NMOGs), the atmospheric oxidation of which can contribute to ozone and secondary particulate matter formation. However, the abundance and reactivity of these fire NMOGs are uncertain and historically not well constrained. In this work, we expand the representation of fire NMOGs in a global chemical transport model, GEOS-Chem. We update emission factors to Andreae (2019) and the chemical mechanism to include recent aromatic and ethene and ethyne model improvements (Bates et al., 2021; Kwon et al., 2021). We expand the representation of NMOGs by adding lumped furans to the model (including their fire emission and oxidation chemistry) and by adding fire emissions of nine species already included in the model, prioritized for their reactivity using data from the Fire Influence on Regional to Global Environments (FIREX) laboratory studies. Based on quantified emissions factors, we estimate that our improved representation captures 72 % of emitted, identified NMOG carbon mass and 49 % of OH reactivity from savanna and temperate forest fires, a substantial increase from the standard model (49 % of mass, 28 % of OH reactivity). We evaluate fire NMOGs in our model with observations from the Amazon Tall Tower Observatory (ATTO) in Brazil, Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) and DC3 in the US, and Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) in boreal Canada. We show that NMOGs, including furan, are well simulated in the eastern US with some underestimates in the western US and that adding fire emissions improves our ability to simulate ethene in boreal Canada. We estimate that fires provide 15 % of annual mean simulated surface OH reactivity globally, as well as more than 75 % over fire source regions. Over continental regions about half of this simulated fire reactivity comes from NMOG species. We find that furans and ethene are important globally for reactivity, while phenol is more important at a local level in the boreal regions. This is the first global estimate of the impact of fire on atmospheric reactivity.
Joseph Byron, Juergen Kreuzwieser, Gemma Purser, Joost van Haren, S. Nemiah Ladd, Laura K. Meredith, Christiane Werner, and Jonathan Williams
Springer Science and Business Media LLC
AbstractMonoterpenes (C10H16) are emitted in large quantities by vegetation to the atmosphere (>100 TgC year−1), where they readily react with hydroxyl radicals and ozone to form new particles and, hence, clouds, affecting the Earth’s radiative budget and, thereby, climate change1–3. Although most monoterpenes exist in two chiral mirror-image forms termed enantiomers, these (+) and (−) forms are rarely distinguished in measurement or modelling studies4–6. Therefore, the individual formation pathways of monoterpene enantiomers in plants and their ecological functions are poorly understood. Here we present enantiomerically separated atmospheric monoterpene and isoprene data from an enclosed tropical rainforest ecosystem in the absence of ultraviolet light and atmospheric oxidation chemistry, during a four-month controlled drought and rewetting experiment7. Surprisingly, the emitted enantiomers showed distinct diel emission peaks, which responded differently to progressive drying. Isotopic labelling established that vegetation emitted mainly de novo-synthesized (−)-α-pinene, whereas (+)-α-pinene was emitted from storage pools. As drought progressed, the source of (−)-α-pinene emissions shifted to storage pools, favouring cloud formation. Pre-drought mixing ratios of both α-pinene enantiomers correlated better with other monoterpenes than with each other, indicating different enzymatic controls. These results show that enantiomeric distribution is key to understanding the underlying processes driving monoterpene emissions from forest ecosystems and predicting atmospheric feedbacks in response to climate change.
Nora Zannoni, Pascale S. J. Lakey, Youngbo Won, Manabu Shiraiwa, Donghyun Rim, Charles J. Weschler, Nijing Wang, Lisa Ernle, Mengze Li, Gabriel Bekö,et al.
American Association for the Advancement of Science (AAAS)
Hydroxyl (OH) radicals are highly reactive species that can oxidize most pollutant gases. In this study, high concentrations of OH radicals were found when people were exposed to ozone in a climate-controlled chamber. OH concentrations calculated by two methods using measurements of total OH reactivity, speciated alkenes, and oxidation products were consistent with those obtained from a chemically explicit model. Key to establishing this human-induced oxidation field is 6-methyl-5-hepten-2-one (6-MHO), which forms when ozone reacts with the skin-oil squalene and subsequently generates OH efficiently through gas-phase reaction with ozone. A dynamic model was used to show the spatial extent of the human-generated OH oxidation field and its dependency on ozone influx through ventilation. This finding has implications for the oxidation, lifetime, and perception of chemicals indoors and, ultimately, human health.