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The functional reasons for isoprene emission are still a matter of hot debate. It was hypothesized that isoprene biosynthesis evolved as an ancestral mechanism in plants adapted to high water availability, to cope with transient and recurrent oxidative stresses during their water-to-land transition. There is a tight association between isoprene emission and species hygrophily, suggesting that isoprene emission may be a favorable trait to cope with occasional exposure to stresses in mesic environments. The suite of morpho-anatomical traits does not allow a conservative water use in hygrophilic mesophytes challenged by the environmental pressures imposed or exacerbated by drought and heat stress. There is evidence that in stressed plants the biosynthesis of isoprene is uncoupled from photosynthesis. Because the biosynthesis of isoprene is costly, the great investment of carbon and energy into isoprene must have relevant functional reasons. Isoprene is effective in preserving the integrity of thylakoid membranes, not only through direct interaction with their lipid acyl chains, but also by up-regulating proteins associated with photosynthetic complexes and enhancing the biosynthesis of relevant membrane components, such as mono- and di-galactosyl-diacyl glycerols and unsaturated fatty acids. Isoprene may additionally protect photosynthetic membranes by scavenging reactive oxygen species. Here we explore the mode of actions and the potential significance of isoprene in the response of hygrophilic plants when challenged by severe stress conditions associated to rapid climate change in temperate climates, with special emphasis to the concomitant effect of drought and heat. We suggest that isoprene emission may be not a good estimate for its biosynthesis and concentration in severely droughted leaves, being the internal concentration of isoprene the important trait for stress protection.

US surface O3 responds to varying global-to-regional precursor emissions, climate, and extreme weather, with implications for designing effective air quality control policies. We examine these conjoined processes with observations and global chemistry-climate model (GFDL-AM3) hindcasts over 1980–2014. The model captures the salient features of observed trends in daily maximum 8 h average O3: (1) increases over East Asia (up to 2 ppb yr−1), (2) springtime increases at western US (WUS) rural sites (0.2–0.5 ppb yr−1) with a baseline sampling approach, and (3) summertime decreases, largest at the 95th percentile, and wintertime increases in the 50th to 5th percentiles over the eastern US (EUS). Asian NOx emissions have tripled since 1990, contributing as much as 65 % to modeled springtime background O3 increases (0.3–0.5 ppb yr−1) over the WUS, outpacing O3 decreases attained via 50 % US NOx emission controls. Methane increases over this period contribute only 15 % of the WUS background O3 increase. Springtime O3 observed in Denver has increased at a rate similar to remote rural sites. During summer, increasing Asian emissions approximately offset the benefits of US emission reductions, leading to weak or insignificant observed O3 trends at WUS rural sites. Mean springtime WUS O3 is projected to increase by  ∼  10 ppb from 2010 to 2030 under the RCP8.5 global change scenario. While historical wildfire emissions can enhance summertime monthly mean O3 at individual sites by 2–8 ppb, high temperatures and the associated buildup of O3 produced from regional anthropogenic emissions contribute most to elevating observed summertime O3 throughout the USA. GFDL-AM3 captures the observed interannual variability of summertime EUS O3. However, O3 deposition sink to vegetation must be reduced by 35 % for the model to accurately simulate observed high-O3 anomalies during the severe drought of 1988. Regional NOx reductions alleviated the O3 buildup during the recent heat waves of 2011 and 2012 relative to earlier heat waves (e.g., 1988, 1999). The O3 decreases driven by NOx controls were more pronounced in the southeastern US, where the seasonal onset of biogenic isoprene emissions and NOx-sensitive O3 production occurs earlier than in the northeast. Without emission controls, the 95th percentile summertime O3 in the EUS would have increased by 0.2–0.4 ppb yr−1 over 1988–2014 due to more frequent hot extremes and rising biogenic isoprene emissions.

Isoprene was recently shown to act as an electron acceptor for a homoacetogenic bacterium. The focus of this study is the molecular basis for isoprene reduction. Recent discoveries of isoprene-metabolizing microorganisms suggest they might play an important role in the global isoprene budget. Under anoxic conditions, isoprene can be used as an electron acceptor and is reduced to methylbutene. This study describes the proteogenomic profiling of an isoprene-reducing bacterial culture to identify organisms and genes responsible for the isoprene hydrogenation reaction. A metagenome-assembled genome (MAG) of the most abundant (89% relative abundance) lineage in the enrichment, Acetobacterium wieringae , was obtained. Comparative proteogenomics and reverse transcription-PCR (RT-PCR) identified a putative five-gene operon from the A. wieringae MAG upregulated during isoprene reduction. The operon encodes a putative oxidoreductase, three pleiotropic nickel chaperones (2 × HypA, HypB), and one 4Fe-4S ferredoxin. The oxidoreductase is proposed as the putative isoprene reductase with a binding site for NADH, flavin adenine dinucleotide (FAD), two pairs of canonical [4Fe-4S] clusters, and a putative iron-sulfur cluster site in a Cys 6 -bonding environment. Well-studied Acetobacterium strains, such as A. woodii DSM 1030, A. wieringae DSM 1911, or A. malicum DSM 4132, do not encode the isoprene-regulated operon but encode, like many other bacteria, a homolog of the putative isoprene reductase (~47 to 49% amino acid sequence identity). Uncharacterized homologs of the putative isoprene reductase are observed across the Firmicutes , Spirochaetes , Tenericutes , Actinobacteria , Chloroflexi , Bacteroidetes , and Proteobacteria , suggesting the ability of biohydrogenation of unfunctionalized conjugated doubled bonds in other unsaturated hydrocarbons. IMPORTANCE Isoprene was recently shown to act as an electron acceptor for a homoacetogenic bacterium. The focus of this study is the molecular basis for isoprene reduction. By comparing a genome from our isoprene-reducing enrichment culture, dominated by Acetobacterium wieringae , with genomes of other Acetobacterium lineages that do not reduce isoprene, we shortlisted candidate genes for isoprene reduction. Using comparative proteogenomics and reverse transcription-PCR we have identified a putative five-gene operon encoding an oxidoreductase referred to as putative isoprene reductase.

Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impact urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C5H8H+), acetaldehyde (m/z 45, CH3CHO+), and benzene (m/z 79, C6H6H+). Interferences from fragmentation are identified using gas chromatography (GC) pre-separation, and the impact of these interferences is quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher-carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to fragmentation and O2+ ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer-specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra.

Surface ozone is a secondary air pollutant produced during the atmospheric photochemical degradation of emitted volatile organic compounds (VOCs) in the presence of sunlight and nitrogen oxides (NOx). Temperature directly influences ozone production through speeding up the rates of chemical reactions and increasing the emissions of VOCs, such as isoprene, from vegetation. In this study, we used an idealised box model with different chemical mechanisms (Master Chemical Mechanism, MCMv3.2; Common Representative Intermediates, CRIv2; Model for OZone and Related Chemical Tracers, MOZART-4; Regional Acid Deposition Model, RADM2; Carbon Bond Mechanism, CB05) to examine the non-linear relationship between ozone, NOx and temperature, and we compared this to previous observational studies. Under high-NOx conditions, an increase in ozone from 20 to 40°C of up to 20ppbv was due to faster reaction rates, while increased isoprene emissions added up to a further 11ppbv of ozone. The largest inter-mechanism differences were obtained at high temperatures and high-NOx emissions. CB05 and RADM2 simulated more NOx-sensitive chemistry than MCMv3.2, CRIv2 and MOZART-4, which could lead to different mitigation strategies being proposed depending on the chemical mechanism. The increased oxidation rate of emitted VOC with temperature controlled the rate of Ox production; the net influence of peroxy nitrates increased net Ox production per molecule of emitted VOC oxidised. The rate of increase in ozone mixing ratios with temperature from our box model simulations was about half the rate of increase in ozone with temperature observed over central Europe or simulated by a regional chemistry transport model. Modifying the box model set-up to approximate stagnant meteorological conditions increased the rate of increase of ozone with temperature as the accumulation of oxidants enhanced ozone production through the increased production of peroxy radicals from the secondary degradation of emitted VOCs. The box model simulations approximating stagnant conditions and the maximal ozone production chemical regime reproduced the 2ppbv increase in ozone per degree Celsius from the observational and regional model data over central Europe. The simulated ozone-temperature relationship was more sensitive to mixing than the choice of chemical mechanism. Our analysis suggests that reductions in NOx emissions would be required to offset the additional ozone production due to an increase in temperature in the future.

The chemical link between isoprene and formaldehyde (HCHO) is a strong, nonlinear function of NOx (i.e., NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall photochemical mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the southeast US, we quantify HCHO production across the urban–rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a “prompt” yield of HCHO (molecules of HCHO produced per molecule of freshly emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1–2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv-1), while background HCHO increases by a factor of 2 (from 1.6 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D steady-state box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models underestimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or underestimated hydroxyl radical concentrations. Detailed process rates from the box model simulation demonstrate a 3-fold increase in HCHO production across the range of observed NOx values, driven by a 100 % increase in OH and a 40 % increase in branching of organic peroxy radical reactions to produce HCHO.

Biogenic volatile organic compounds (BVOCs) are important precursors to ozone and secondary organic aerosols in the atmosphere, affecting air quality, clouds, and climate. However, the trend in BVOC emissions and driving factors for the emission changes in different geographic regions over the past 2 decades has remained unclear. Here, regional to global changes in BVOC emissions during 2001–2020 are simulated using the latest Model of Emission of Gases and Aerosols from Nature (MEGANv3.2) with the input of time-varying satellite-retrieved vegetation and reanalysis meteorology data. Comparison of model simulations with the site observations shows that the model can reasonably reproduce the magnitude of isoprene and monoterpene emission fluxes. The spatial distribution of the modeled isoprene emissions is generally comparable to the satellite retrievals. The estimated annual average global BVOC emissions are 835.4 Tg yr−1 with the emissions from isoprene, monoterpenes, sesquiterpenes, and other BVOC comprised of 347.7, 184.8, 23.3, and 279.6 Tg yr−1, respectively. We find that the decrease in global isoprene emissions (−0.07 % per year) caused by the increase in CO2 concentrations (−0.20 % per year) is stronger than that caused by changes in vegetation (−0.03 % per year) and meteorological factors (0.15 % per year). However, regional disparities are large. Isoprene emissions increase significantly in Europe, East Asia, and South Asia (0.37 % per year–0.66 % per year). Half of the increasing trend is contributed by increased leaf area index (LAI) (maximum over 0.02 m2 m−2 yr−1) and tree cover. Changes in meteorological factors contribute to another half, with elevated temperature dominating in Europe and increased soil moisture dominating in East and South Asia. In contrast, in South America and Southeast Asia, shifts in vegetation type associated with the BVOC emission capacity, which partly results from the deforestation and agricultural expansion, decrease the BVOC emission and offset nearly half of the emission increase caused by changes in meteorological factors. Overall, isoprene emission increases by 0.35 % per year and 0.25 % per year in South America and Southeast Asia, respectively. In Central Africa, a decrease in temperature dominates the negative emission trend (−0.74 % per year). Global monoterpene emissions show a significantly increasing trend (0.34 % per year, 0.6 Tg yr−1) compared to that of isoprene (−0.07 % per year, −0.2 Tg yr−1), especially in strong greening hotspots. This is mainly because the monoterpene emissions are more sensitive to changes in LAI and are not subject to the inhibition effect of CO2. The findings highlight the important roles of vegetation cover and biomass, temperature, and soil moisture in modulating the temporal variations of global BVOC emissions in the past 2 decades.

Isoprene is the dominant non-methane organic compound emitted to the atmosphere 1 – 3 . It drives ozone and aerosol production, modulates atmospheric oxidation and interacts with the global nitrogen cycle 4 – 8 . Isoprene emissions are highly uncertain 1 , 9 , as is the nonlinear chemistry coupling isoprene and the hydroxyl radical, OH—its primary sink 10 – 13 . Here we present global isoprene measurements taken from space using the Cross-track Infrared Sounder. Together with observations of formaldehyde, an isoprene oxidation product, these measurements provide constraints on isoprene emissions and atmospheric oxidation. We find that the isoprene–formaldehyde relationships measured from space are broadly consistent with the current understanding of isoprene–OH chemistry, with no indication of missing OH recycling at low nitrogen oxide concentrations. We analyse these datasets over four global isoprene hotspots in relation to model predictions, and present a quantification of isoprene emissions based directly on satellite measurements of isoprene itself. A major discrepancy emerges over Amazonia, where current underestimates of natural nitrogen oxide emissions bias modelled OH and hence isoprene. Over southern Africa, we find that a prominent isoprene hotspot is missing from bottom-up predictions. A multi-year analysis sheds light on interannual isoprene variability, and suggests the influence of the El Niño/Southern Oscillation. Direct satellite measurements of atmospheric isoprene are compared with model predictions, showing broad agreement but highlighting spatial and temporal biases in modelled isoprene and nitrogen oxide emissions.

Ozone (O3) pollution is a severe air quality issue in China, posing a threat to human health and ecosystems. The climate change will affect O3 levels by directly changing physical and chemical processes of O3 and indirectly changing natural emissions of O3 precursors. In this study, near‐surface O3 concentrations in China in 2030 and 2060 are predicted using the process‐based interpretable Extreme Gradient Boosting (XGBoost) model integrated with multi‐source data. The results show that the climate‐driven O3 levels over eastern China are projected to decrease by more than 0.4 ppb in 2060 under the carbon neutral scenario (SSP1‐1.9) compared with the high emission scenario (SSP5‐8.5). Among this reduction, 80% is attributed to the changes in physical and chemical processes of O3 related to a cooler climate, while the remaining 20% is attributed to the reduced biogenic isoprene emissions. Plain Language Summary O3 pollution is a severe air quality issue in China that threatens human health and ecosystem. Under the background of climate change, O3 pollution will continue to evolve in the future. Here, we predict near‐surface O3 concentrations in China in 2030 and 2060 based on an interpretable machine learning method, integrated with physical and chemical processes of O3, natural emissions of O3 precursors, and other multi‐source data. The direct (via changing physical and chemical processes of O3) and indirect (via changing natural emissions of O3 precursors) impacts of future climate change on O3 concentrations are quantitatively analyzed. It demonstrates that the climate‐driven O3 levels are projected to decrease by more than 0.4 ppb in 2060 over eastern China under a carbon neutral scenario relative to a high emission scenario. The changes in physical and chemical processes under climate change play a more important role in regulating O3 concentrations in the future than the changes in natural emissions. Key Points Climate change influences O3 pollution in China through changing physical and chemical processes and natural precursor emissions of O3 Physical and chemical processes play a dominant role in regulating future near‐surface O3 concentrations over eastern China Carbon neutral scenario is an ideal pathway for China to mitigate both climate change and O3 pollution in 2060