Isoprene Production Research Articles

Solvent-Induced Selectivity of Isoprene From Bio-Derived Prenol.

In this work we demonstrate the selective catalytic conversion of prenol, which is an allylic alcohol that can be prepared from renewable resources to isoprene. The catalyst is an inexpensive molybdenum complex (Molyvan L) designed and used as an additive for lubricants. Isoprene is generated under relatively mild reaction parameters at 130–150°C, for 2 h, under vapor pressure conditions that do not exceed 50 psi. Two cases were studied: one in which Molyvan L was dissolved in a base oil at 1% concentration (weight/weight) and then mixed with a solvent and prenol and the other in which neat Molyvan L was introduced in the reaction and the base oil was replaced with the solvent and prenol. We investigated the selectivity of the reaction using the following solvents in both cases: dodecane, dodecanol, isododecane, octane, blendstock for oxygenate blending (BOB3), a fuel surrogate, a polyalphaolefin (PAO4), and methoxy polyethylene glycol (methoxy PEG350). Although conversion of prenol was above 94% in all experiments, isoprene was formed with various degrees of efficiency alongside a prenol isomeric alcohol, diprenyl ether and mixed ether via intramolecular and intermolecular dehydration reactions. Dodecane appeared to have the highest level of selectivity initially in base oil so we studied the effect of various dodecane-like solvents on isoprene yield and product profile. Surprisingly, octane (similar to dodecane) and isododecane (branched alkane) generated insignificant amounts of byproducts, essentially providing the highly desired isoprene with a very high selectivity. Branching of the solvent does not appear to have an effect on selectivity. Another advantage of this catalyst is the low loadings required to effect the transformation; that is, 0.25% (weight/volume) in the cases using neat Molyvan L and 0.5% (weight/volume) in the cases using Molyvan L dissolved in the base oil. Provided that prenol can be produced in large scale from bioresources, this work would enable the sustainable production of isoprene, in good yield, and with very high selectivity.

Diurnal Variations of Isoprene, Monoterpenes, and Toluene Oxidation Products in Aerosols at a Rural Site of Guanzhong Plain, Northwest China

In this study, the characteristics and formation mechanism of summertime isoprene, monoterpene, and toluene-derived secondary organic aerosols (SOAs) were investigated in a rural area of Guanzhong Plain, Northwest China. The variations in key indicators of primary sources indicated a significant influence of biomass burning on PM2.5 during the observation period. The concentrations of total measured SOA tracers from isoprene, monoterpene, and toluene were 40.85 ± 17.31, 24.27 ± 7.50, and 10.61 ± 0.33 ng/m3, respectively. The average ratio of cis-pinonic and pinic acids to 3-Methyl-1,2,3-butanetricarboxylic acid (MBTCA)(P/M) were 0.45 and 0.85 by day and by night, respectively. The low ratio in the daytime was mainly due to the stronger photo-degradation and particle-to-gas distribution of semi-volatile cis-pinonic and pinic acids. The monoterpene SOA tracers were significantly correlated with levoglucosan at night (R2 = 0.51, p < 0.01), as were toluene SOA tracers and levoglucosan (R2 > 0.67, p < 0.01), indicating the significant contribution of biomass combustion to these SOAs. The mass concentration of isoprene-, monoterpenes-, and toluene-derived SOC was estimated by using the tracer yield method. The total calculated SOCs by day and by night were 0.25–0.71 (average: 0.46) and 0.26–0.78 (average: 0.42) µgC/m3, accounting for 3.35–10.58% and 3.87–13.51% of OC by day and by night, respectively.

Isoprene production by Rhodobacter sphaeroides and its antimicrobial activity

Extensive studies on the antimicrobial activity of terpene-based substances, which are the main components of essential oils, are continuously underway. And some hydrocarbons constituting antimicrobial substances have been reported to exhibit the antimicrobial activity. This study confirmed the production of isoprene, the most basic constituent hydrocarbon of terpene, by Rhodobacter sphaeroides, and investigated the antimicrobial activity of isoprene and its mechanism. We developed an air-sharing culture system in which different bacterial cultures aseptically shared the same atmosphere, to evaluate the effect of volatile isoprene. Effects were tested on two Gram-negative bacteria, and on two Gram-positive bacteria. As a result, the isoprene released from R. sphaeroides showed the antimicrobial activity against all evaluated strains, especially against Gram-positive bacteria than Gram-negative bacteria. In addition, the microstructure of the bacteria was evaluated via FE-SEM. The FE-SEM images showed that isoprene has the antimicrobial activity mechanism that causes cell death by acting on the cell wall or the extracellular membrane.

Water binding to the atmospheric oxidation product methyl vinyl ketone

Methyl vinyl ketone is one of the major oxidation products of isoprene, and therefore, an important precursor of secondary organic aerosol. Understanding its interactions with water is relevant to gain insight into aerosol formation and improve the predictive power of atmospheric chemistry models. The molecular complex formed between methyl vinyl ketone and water has been generated in a supersonic jet and characterized using high-resolution microwave spectroscopy in combination with quantum chemistry calculations. In this study, we show that methyl vinyl ketone interacts with water forming four 1:1 isomers connected by O − H···O and C − H···O hydrogen bond interactions. Water has been found to preferentially bind to the antiperiplanar conformation of methyl vinyl ketone. Evidence of a large amplitude motion arising from the methyl internal rotation has been found in the rotational spectra of the dimer. The threefold methyl internal rotation barrier heights have been further determined and discussed for all the species.

Isoprene production in the water column and sediment in Funka Bay, Hokkaido, Japan

Isoprene production in the water column and sediment in Funka Bay, Hokkaido, Japan

Isoprene measurements to assess plant hydrocarbon emissions and the methylerythritol pathway.

Isoprene is the most abundant non-methane hydrocarbon emitted to the atmosphere and a target of biotechnology as a source of biofuels or chemical feedstock. Measurements of the amount of isoprene or the rate of production of isoprene are important for atmospheric chemistry, evaluating biotechnology processes, and can provide information on the capacity and regulation of the methyl erythritol 4-phosphate pathway found in plants and bacteria. In this chapter we discuss techniques, and their strengths and weaknesses, of methods in common use for measuring isoprene. There are many sources of isoprene for measurements including emissions from leaves and head space analysis of reactions involving recombinant enzymes or bacterial/fungal cultures. Similarly, there are a variety of detection methods including several mass spectrometer methods that are useful for examining rates of labeling of isoprene when carbon isotopes are used.

Isoprene emission characteristics of tall and dwarf bamboos

Considerable isoprene emissions from several bamboo species have been reported. However, bamboos are highly diverse in taxonomy and have different niches or habitats among species, and the present investigation might be insufficient to conclude a representative isoprene emission trait for bamboos. In this study, isoprene flux, leaf mass per area (LMA), photosynthetic rate, and electron transport rate (ETR) observations were conducted for 18 species within five genera of bamboo species, which include different growth types (tall and dwarf) and climates of the region of origin (temperate, warm-temperate, and subtropical). As a result, we observed that dwarf bamboos exhibited very low or no emission; in contrast, tall bamboos demonstrated considerable isoprene emission fluxes mainly in August and September 2019 at temperatures greater than 30 °C. For tall bamboos, isoprene emission fluxes, photosynthetic rate, and ETR in area-based units were correlated with LMA. To exclude the systematic correlation among isoprene emission flux, photosynthetic rate, and ETR, correlations among the observations of mass-based units were also tested, and the results demonstrated significant positive correlations. The distinction in isoprene emission traits between tall and dwarf bamboos was independent of LMA, photosynthetic rate, and ETR, as there was no difference between them. This implies that the distinction in isoprene emission was caused by genetic differences. The low emission of isoprene from the dwarf species is reasonable because dwarf bamboos usually grow in areas with relatively low heat stress and low light where the production of isoprene could be futile due to carbon loss. This study suggests separating the two bamboo types into different functional types of isoprene emissions. • Isoprene emission flux from leaves of 18 bamboo species were observed. • Dwarf bamboos exhibited almost no isoprene emission. • Tall bamboos exhibited remarkably large isoprene flux in summer. • Dependences on LMA and ETR were observed across the tall bamboos.

Co-Production of Isoprene and Lactate by Engineered Escherichia coli in Microaerobic Conditions.

Lactate and isoprene are two common monomers for the industrial production of polyesters and synthetic rubbers. The present study tested the co-production of D-lactate and isoprene by engineered Escherichia coli in microaerobic conditions. The deletion of alcohol dehydrogenase (adhE) and acetate kinase (ackA) genes, along with the supplementation with betaine, improved the co-production of lactate and isoprene from the substrates of glucose and mevalonate. In fed-batch studies, microaerobic fermentation significantly improved the isoprene concentration in fermentation outlet gas (average 0.021 g/L), compared with fermentation under aerobic conditions (average 0.0009 g/L). The final production of D-lactate and isoprene can reach 44.0 g/L and 3.2 g/L, respectively, through fed-batch microaerobic fermentation. Our study demonstrated a dual-phase production strategy in the co-production of isoprene (gas phase) and lactate (liquid phase). The increased concentration of gas-phase isoprene could benefit the downstream process and decrease the production cost to collect and purify the bio-isoprene from the fermentation outlet gas. The proposed microaerobic process can potentially be applied in the production of other volatile bioproducts to benefit the downstream purification process.

Application of the Metabolic Modeling Pipeline in KBase to Categorize Reactions, Predict Essential Genes, and Predict Pathways in an Isolate Genome.

The DOE Systems Biology Knowledgebase (KBase) platform offers a range of powerful tools for the reconstruction, refinement, and analysis of genome-scale metabolic models built from microbial isolate genomes. In this chapter, we describe and demonstrate these tools in action with an analysis of isoprene production in the Bacillus subtilis DSM genome. Two different methods are applied to build initial metabolic models for the DSM genome, then the models are gapfilled in three different growth conditions. Next, flux balance analysis (FBA) and flux variability analysis (FVA) techniques are applied to both study the growth of these models in minimal media and classify reactions within each model based on essentiality and functionality. The models are applied with the FBA method to predict essential genes, which are then compared to an updated list of essential genes obtained for B. subtilis 168, a very similar strain to the DSM isolate. The models are also applied to simulate Biolog growth conditions, and these results are compared with Biolog data collected for B. subtilis 168. Finally, the DSM metabolic models are applied to explore the pathways and genes responsible for producing isoprene in this strain. These studies demonstrate the accuracy and utility of models generated from the KBase pipelines, as well as exploring the tools available for analyzing these models.

Drought affects carbon partitioning into volatile organic compound biosynthesis in Scots pine needles.

The effect of drought on the interplay of processes controlling carbon partitioning into plant primary and secondary metabolisms, such as respiratory CO2 release and volatile organic compound (VOC) biosynthesis, is not fully understood. To elucidate the effect of drought on the fate of cellular C sources into VOCs vs CO2 , we conducted tracer experiments with 13 CO2 and position-specific 13 C-labelled pyruvate, a key metabolite between primary and secondary metabolisms, in Scots pine seedlings. We determined the stable carbon isotope composition of leaf exchanged CO2 and VOC. Drought reduced the emission of the sesquiterpenes α-farnesene and β-farnesene but did not affect 13 C-incorporation from 13 C-pyruvate. The labelling patterns suggest that farnesene biosynthesis partially depends on isopentenyl diphosphate crosstalk between chloroplasts and cytosol, and that drought inhibits this process. Contrary to sesquiterpenes, drought did not affect emission of isoprene, monoterpenes and some oxygenated compounds. During the day, pyruvate was used in the TCA cycle to a minor degree but was mainly consumed in pathways of secondary metabolism. Drought partly inhibited such pathways, while allocation into the TCA cycle increased. Drought caused a re-direction of pyruvate consuming pathways, which contributed to maintenance of isoprene and monoterpene production despite strongly inhibited photosynthesis. This underlines the importance of these volatiles for stress tolerance.

Metabolic engineering of Yarrowia lipolytica for the production of isoprene

Yarrowia lipolytica has recently emerged as a prominent microbial host for production of terpenoids. Its robust metabolism and growth in wide range of substrates offer several advantages at industrial scale. In the present study, we investigate the metabolic potential of Y. lipolytica to produce isoprene. Sustainable production of isoprene has been attempted through engineering several microbial hosts; however, the engineering studies performed so far are challenged with low titers. Engineering of Y. lipolytica, which have inherent high acetyl-CoA flux could fuel precursors into the biosynthesis of isoprene and thus is an approach that would offer sustainable production opportunities. The present work, therefore, explores this opportunity wherein a codon-optimized IspS gene (single copy) of Pueraria montana was integrated into the Y. lipolytica genome. With no detectable isoprene level during the growth or stationary phase of modified strain, attempts were made to overexpress enzymes from MVA pathway. GC-FID analyses of gas collected during stationary phase revealed that engineered strains were able to produce detectable isoprene only after overexpressing HMGR (or tHMGR). The significant role of HMGR (tHMGR) in diverting the pathway flux toward DMAPP is thus highlighted in our study. Nevertheless, the final recombinant strains overexpressing HMGR (tHMGR) along with Erg13 and IDI showed isoprene titers of ~500 μg/L and yields of ~80 μg/g. Further characterization of the recombinant strains revealed high lipid and squalene content compared to the unmodified strain. Overall, the preliminary results of our laboratory-scale studies represent Y. lipolytica as a promising host for fermentative production of isoprene.

Secondary Ion Chemistry Mediated by Ozone and Acidic Organic Molecules in Iodide-Adduct Chemical Ionization Mass Spectrometry

Iodide-adduct chemical ionization mass spectrometry (I-CIMS) is a widely used technique in the atmospheric chemistry community to detect oxygenated volatile organic compounds (OVOCs) in real time. In this work, we report the occurrence of secondary ion chemistry from interactions between a strong oxygen donor (such as O3 and peracids) and acidic OVOCs (such as carboxylic acids and organic hydroperoxides) in the ion-molecule reaction (IMR) region of I-CIMS. Such interactions can lead to acidic organic molecules (HA or HB) clustering with [IO]- (e.g., [HA + IO]-) and dimer adducts ([A + B + I]-), in addition to the well-known iodide clusters ([HA + I]-). This ion chemistry was probed using common chemical standards as well as the gas-phase oxidation products of α-pinene and isoprene in a flowtube reactor. The results show that secondary ion chemistry can lead to misinterpretations of molecular compositions and distributions of the gas-phase products and an overestimation of the elemental O/C ratio overall. Nevertheless, the varying degrees of signal change in response to the secondary ion chemistry might be a clue to inform OVOCs' functionalities. Specifically, in the α-pinene ozonolysis system, the extents of ion signal reduction in the presence of additional acids in the IMR suggest that C9H14O4 produced in the gas phase is a peracid, rather than the often-assumed pinic acid. Thus, we suggest that the potential application of the secondary ion chemistry to inform organic functionalities is promising, which could help better understand the molecular compositions of gas-phase OVOCs and the reaction mechanisms therein.

Impairing photorespiration increases photosynthetic conversion of CO2 to isoprene in engineered cyanobacteria

Photorespiration consumes fixed carbon and energy generated from photosynthesis to recycle glycolate and dissipate excess energy. The aim of this study was to investigate whether we can use the energy that is otherwise consumed by photorespiration to improve the production of chemicals which requires energy input. To this end, we designed and introduced an isoprene synthetic pathway, which requires ATP and NADPH input, into the cyanobacterium Synechocystis sp. 6803. We then deleted the glcD1 and glcD2 genes which encode glycolate dehydrogenase to impair photorespiration in isoprene-producing strain of Synechocystis. Production of isoprene in glcD1/glcD2 disrupted strain doubled, and stoichiometric analysis indicated that the energy saved from the impaired photorespiration was redirected to increase production of isoprene. Thus, we demonstrate we can use the energy consumed by photorespiration of cyanobacteria to increase the energy-dependent production of chemicals from CO2.

Isoprene Production from Municipal Wastewater Biosolids by Engineered Archaeon Methanosarcina acetivorans

Wastewater biosolids are a promising feedstock for production of value-added renewable chemicals. Methane-producing archaea (methanogens) are already used to produce renewable biogas via the anaerobic treatment of wastewater. The ability of methanogens to efficiently convert dissolved organic carbon into methane makes them an appealing potential platform for biorefining using metabolic engineering. We have engineered a strain of the methanogen Methanosarcina acetivorans to produce the volatile hemiterpene isoprene in addition to methane. The engineered strain was adapted to grow in municipal wastewater through cultivation in a synthetic wastewater medium. When introduced to municipal wastewater the engineered methanogens were able to compete with the indigenous microorganisms and produce 0.97 mM of isoprene (65.9 ± 21.3 g per m3 of effluent). The production of isoprene in wastewater appears to be dependent on the quantity of available methanogenic substrate produced during upstream digestion by heterotrophic fermenters. This shows that with minimal adaptation it is possible to drop-in engineered methanogens to existing wastewater environments and attain value-added products in addition to the processing of wastewater. This shows the potential for utilizing methanogens as a platform for low-cost production of renewable materials without expensive feedstocks or the need to build or adapt existing facilities.

Assessment of Isoprene as a Possible Biosignature Gas in Exoplanets with Anoxic Atmospheres.

The search for possible biosignature gases in habitable exoplanet atmospheres is accelerating, although actual observations are likely years away. This work adds isoprene, C5H8, to the roster of biosignature gases. We found that isoprene geochemical formation is highly thermodynamically disfavored and has no known abiotic false positives. The isoprene production rate on Earth rivals that of methane (CH4; ∼500 Tg/year). Unlike methane, on Earth isoprene is rapidly destroyed by oxygen-containing radicals. Although isoprene is predominantly produced by deciduous trees, isoprene production is ubiquitous to a diverse array of evolutionary distant organisms, from bacteria to plants and animals-few, if any, volatile secondary metabolites have a larger evolutionary reach. Although non-photochemical sinks of isoprene may exist, such as degradation of isoprene by life or other high deposition rates, destruction of isoprene in an anoxic atmosphere is mainly driven by photochemistry. Motivated by the concept that isoprene might accumulate in anoxic environments, we model the photochemistry and spectroscopic detection of isoprene in habitable temperature, rocky exoplanet anoxic atmospheres with a variety of atmosphere compositions under different host star ultraviolet fluxes. Limited by an assumed 10 ppm instrument noise floor, habitable atmosphere characterization when using James Webb Space Telescope (JWST) is only achievable with a transit signal similar or larger than that for a super-Earth-sized exoplanet transiting an M dwarf star with an H2-dominated atmosphere. Unfortunately, isoprene cannot accumulate to detectable abundance without entering a run-away phase, which occurs at a very high production rate, ∼100 times the Earth's production rate. In this run-away scenario, isoprene will accumulate to >100 ppm, and its spectral features are detectable with ∼20 JWST transits. One caveat is that some isoprene spectral features are hard to distinguish from those of methane and also from other hydrocarbons containing the isoprene substructure. Despite these challenges, isoprene is worth adding to the menu of potential biosignature gases.

C/N Ratio and Specific Growth Rate Plays Important Role on Enhancing Isoprene Production in Recombinant Escherichia coli.

Effect of fermentation parameters such as C/N ratio, specific growth rate, phosphate limitation, and plasmid instability on enhancing isoprene production is the focus of the current study. Isoprene productivity in the recombinant Escherichia coli K12_MVA strain showed a bell-shaped relationship with specific growth rate in bioreactor studies with isoprene volumetric productivity peaking at 0.35/h. This behavior was depicted by a production inhibition kinetic model which envisaged a serious competition between the cellular growth, acetic acid production, and isoprene biosynthesis. The model equation derived showed a reasonable fit with the experimental values. Judicious control of the growth rates and acetate accumulation by optimizing C/N ratio, phosphate concentration, and intermittent feeding strategy resulted in maximizing the carbon flux towards isoprene. Plasmid instability caused by metabolic burden posed by the presence of dual plasmids on the bacteria was simulated using first-order degradation kinetics. The experimental plasmid loss trend was in accordance with the model simulated trend, where higher plasmid loss correlated with higher specific growth rates. Modulating the growth rate, acetate accumulation, and plasmid instability resulted in achieving maximum isoprene volumetric productivity of 1.125 g/l/h with 46.67% of carbon flux towards isoprene and a isoprene titre of 18 g/l in 16 h fermentation run.

Study on the isoprene-producing co-culture system of Synechococcus elongates\u2013Escherichia coli through omics analysis

BackgroundThe majority of microbial fermentations are currently performed in the batch or fed-batch manner with the high process complexity and huge water consumption. The continuous microbial production can contribute to the green sustainable development of the fermentation industry. The co-culture systems of photo-autotrophic and heterotrophic species can play important roles in establishing the continuous fermentation mode for the bio-based chemicals production.ResultsIn the present paper, the co-culture system of Synechococcus elongates–Escherichia coli was established and put into operation stably for isoprene production. Compared with the axenic culture, the fermentation period of time was extended from 100 to 400 h in the co-culture and the isoprene production was increased to eightfold. For in depth understanding this novel system, the differential omics profiles were analyzed. The responses of BL21(DE3) to S. elongatus PCC 7942 were triggered by the oxidative pressure through the Fenton reaction and all these changes were linked with one another at different spatial and temporal scales. The oxidative stress mitigation pathways might contribute to the long-lasting fermentation process. The performance of this co-culture system can be further improved according to the fundamental rules discovered by the omics analysis.ConclusionsThe isoprene-producing co-culture system of S. elongates–E. coli was established and then analyzed by the omics methods. This study on the co-culture system of the model S. elongates–E. coli is of significance to reveal the common interactions between photo-autotrophic and heterotrophic species without natural symbiotic relation, which could provide the scientific basis for rational design of microbial community.

Edge Growth Form of European Buckthorn Increases Isoprene Emissions From Urban Forests

Urban trees provide numerous benefits, such as cooling from transpiration, carbon sequestration, and street aesthetics. But volatile organic compound emissions from trees can combine with anthropogenic nitrogen oxide emissions to form ozone, a harmful air pollutant. The most commonly-emitted of these compounds, isoprene, negatively impacts air quality and hence is detrimental to human health. In addition to environmental controls such as light and temperature, the quantity of isoprene emitted from a leaf is a genus-specific trait. Leaf isoprene emission is enzymatically controlled, and species are typically classified as emitters or non-emitters (near-zero emission rates). Therefore, the species composition of urban forests affects whole-system isoprene production. The process of plant invasion alters species composition, and invasive tree species can be either emitters or non-emitters. If an invasive, isoprene-emitting tree species displaces native, non-emitting species, then isoprene emission rates from urban forests will increase, with a concomitant deterioration of air quality. We tested a hypothesis that invasive species have higher isoprene emission rates than native species. Using existing tree species inventory data for the Chicago region, leaf-level isoprene emission rates of the six most common invasive and native tree species were measured and compared. The difference was not statistically significant, but this could be due to the variability associated with making a sufficient number of measurements to quantify species isoprene emission rates. The most common invasive species European buckthorn (Rhamnus cathartica, L.) was an emitter. Because European buckthorn often invades the disturbed edges common in urban forests, we tested a second hypothesis that edge-effect isoprene emissions would significantly increase whole-system modeled isoprene emissions. Using Google Earth satellite imagery to estimate forested area and edge length in the LaBagh Woods Forest Preserve of Cook County (Chicago, IL, USA), edge isoprene emission contributed 8.1% compared to conventionally modeled forest emissions. Our results show that the invasion of European buckthorn has increased isoprene emissions from urban forests. This implies that ecological restoration efforts to remove European buckthorn have the additional benefit of improving air quality.

Low molecular weight dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls as ozonolysis products of isoprene: Implication for the gaseous-phase formation of secondary organic aerosols

Oxidation of isoprene, a major biogenic volatile organic compound emitted from forest canopies, is a potential source of oxalic acid; the dominant species in organic aerosols. We evaluated here ozonolysis of isoprene in dry darkness as a source of oxalic (C2), malonic (C3) and succinic (C4) acids. We found that oxalic acid and methylglyoxal are dominant products within 10 min of reaction followed by glyoxylic, malonic or succinic acids. Interestingly, molecular distributions of oxidation products from early reactions (9–29 min) were characterized by the predominance of methylglyoxal followed by C2, which became dominant after 30 min. The isoprene-derived secondary organic aerosols (SOAs) showed chemical evolution with reaction time towards the molecular characteristics of dicarboxylic acids similar to those of ambient aerosols (C2>C3≥C4). The carbon-based relative abundances of methylglyoxal decreased steadily (40%→30%), while those of C2 increased with reaction time (15%→25%), but no such variations persisted for glyoxal (6–10%). This finding means that methylglyoxal is more important intermediate of oxalic acid than glyoxal. In contrast, smaller variability and lower concentrations of pyruvic and glyoxylic acids than other intermediates indicate that oxalic acid formation under dry conditions follows a different pathway than in aqueous-phase heterogeneous chemistry usually invoked for cloud/fog/atmospheric waters. Here, we propose new reaction schemes for high levels of methylglyoxal and oxalic acid via gas-phase chemical reactions with ozone and OH radicals to better interpret the ambient SOA composition. Furthermore, the relative abundances of C2 exhibit small variability from 1 to 8 h, suggesting its stable character towards the oxidation by hydroxyl radicals.

The microbiology of isoprene cycling in aquatic ecosystems

Isoprene (2-methyl-1,3-butadiene) is emitted in vast quantities (>500 Tg C yr-1). Most isoprene is emitted by trees, but there is still incomplete understanding of the diversity of isoprene sources. The reactivity of isoprene in the atmosphere has potential implications for both global warming and global cooling, with human health implications also arising from isoprene-induced ozone formation in urban areas. Isoprene emissions from terrestrial environments have been studied for many years, but our understanding of aquatic isoprene emissions is less complete. Several abundant phytoplankton taxa produced isoprene in the laboratory, and the relationship between chlorophyll a and isoprene production has been used to estimate emissions from marine environments. The aims of this review are to highlight the role of aquatic environments in the biological cycling of isoprene and to stimulate further study of isoprene metabolism in marine and freshwater environments. From a microbial ecology perspective, the isoprene metabolic gene cluster, first identified in Rhodococcus sp. AD45 (isoGHIJABCDEF) and subsequently found in every genome-sequenced isoprene-degrader, provides the ideal basis for molecular studies on the distribution and diversity of isoprene-degrading communities. Further investigations of isoprene-emitting microbes, such as the influence of environmental factors and geographical location, must also be considered when attempting to constrain estimates of the flux of isoprene in aquatic ecosystems. We also report isoprene emission by the scleractinian coral Acropora horrida and the degradation of isoprene by the same coral holobiont, which highlights the importance of better understanding the cycling of isoprene in marine environments.