Atmospheric Degradation of Ecologically Important Biogenic Volatiles: Investigating the Ozonolysis of (E)-ß-Ocimene, Isomers of α and ß-Farnesene, α-Terpinene and 6-Methyl-5-Hepten-2-One, and Their Gas-Phase Products.

Biogenic volatile organic compounds (bVOCs), synthesised by plants, are important mediators of ecological interactions that can also undergo a series of reactions in the atmosphere. Ground-level ozone is a secondary pollutant generated through sunlight-driven reactions between nitrogen oxides (NOx) and VOCs. Its levels have increased since the industrial revolution and reactions involving ozone drive many chemical processes in the troposphere. While ozone precursors often originate in urban areas, winds may carry these hundreds of kilometres, causing ozone formation to also occur in less populated rural regions. Under elevated ozone conditions, ozonolysis of bVOCs can result in quantitative and qualitative changes in the gas phase, reducing the concentrations of certain bVOCs and resulting in the formation of other compounds. Such changes can result in disruption of bVOC-mediated behavioural or ecological interactions. Through a series of gas-phase experiments using Gas Chromatography Mass Spectrometry (GC-MS) and Proton Transfer Reaction Mass Spectrometry (PTR-MS), we investigated the products and their yields from the ozonolysis of a range of ubiquitous bVOCs, which were selected because of their importance in mediating ecological interactions such as pollinator and natural enemy attraction and plant-to-plant communication, namely: (E)-ß-ocimene, isomers of α and ß-farnesene, α-terpinene and 6-methyl-5-hepten-2-one. New products from the ozonolysis of these compounds were identified, and the formation of these compounds is consistent with terpene-ozone oxidation mechanisms. We present the degradation mechanism of our model bVOCs and identify their reaction products. We discuss the potential ecological implications of the degradation of each bVOC and of the formation of reaction products.

Mapping the effects of ozone pollution and mixing on floral odour plumes and their impact on plant-pollinator interactions.

The critical ecological process of animal-mediated pollination is commonly facilitated by odour cues. These odours consist of volatile organic compounds (VOCs), often with short chemical lifetimes, which form the strong concentration gradients necessary for pollinating insects to locate a flower. Atmospheric oxidants, including ozone pollution, may react with and chemically alter these VOCs, impairing the ability of pollinators to locate a flower, and therefore the pollen and nectar on which they feed. However, there is limited mechanistic empirical evidence to explain these processes within an odour plume at temporal and spatial scales relevant to insect navigation and olfaction. We investigated the impact of ozone pollution and turbulent mixing on the fate of four model floral VOCs within odour plumes using a series of controlled experiments in a large wind tunnel. Average rates of chemical degradation of α-terpinene, ß-caryophyllene and 6-methyl-5-hepten-2-one were slightly faster than predicted by literature rate constants, but mostly within uncertainty bounds. Mixing reduced reaction rates by 8-10% in the first 2 m following release. Reaction rates also varied across the plumes, being fastest at plume edges where VOCs and ozone mixed most efficiently and slowest at plume centres. Honeybees were trained to learn a four VOC blend equivalent to the plume released at the wind tunnel source. When subsequently presented with an odour blend representative of that observed 6 m from the source at the centre of the plume, 52% of honeybees recognised the odour, decreasing to 38% at 12 m. When presented with the more degraded blend from the plume edge, recognition decreased to 32% and 10% at 6 and 12 m respectively. Our findings highlight a mechanism by which anthropogenic pollutants can disrupt the VOC cues used in plant-pollinator interactions, which likely impacts on other critical odour-mediated behaviours such as mate attraction.

Extreme Concentrations of Nitric Oxide Control Daytime Oxidation and Quench Nocturnal Oxidation Chemistry in Delhi during Highly Polluted Episodes.

Delhi, India, suffers from periods of very poor air quality, but little is known about the chemical production of secondary pollutants in this highly polluted environment. During the postmonsoon period in 2018, extremely high nighttime concentrations of NOx (NO and NO2) and volatile organic compounds (VOCs) were observed, with median NOx mixing ratios of ∼200 ppbV (maximum of ∼700 ppbV). A detailed chemical box model constrained to a comprehensive suite of speciated VOC and NOx measurements revealed very low nighttime concentrations of oxidants, NO3, O3, and OH, driven by high nighttime NO concentrations. This results in an atypical NO3 diel profile, not previously reported in other highly polluted urban environments, significantly perturbing nighttime radical oxidation chemistry. Low concentrations of oxidants and high nocturnal primary emissions coupled with a shallow boundary layer led to enhanced early morning photo-oxidation chemistry. This results in a temporal shift in peak O3 concentrations when compared to the premonsoon period (12:00 and 15:00 local time, respectively). This shift will likely have important implications on local air quality, and effective urban air quality management should consider the impacts of nighttime emission sources during the postmonsoon period.

Temperature driven variations in VOC emissions from plastic products and their fate indoors: A chamber experiment and modelling study.

Plastic products are ubiquitous in our homes, but we know very little about emissions from these products and their subsequent impact on indoor air quality. This is the first study to systematically determine temperature-dependent emissions of volatile organic compounds from commonly used plastic consumer products found in the home. The plastic types included high-density polyethylene (HDPE), polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS) and polyester rubber. Plastic samples were exposed to increasing temperatures (between 18 and 28 °C) in controlled environmental chambers, connected to a proton-transfer-reaction time-of-flight mass-spectrometer (PTR-ToF-MS), where real-time emissions were detected. Average emission rates were determined and used to initialise an indoor air chemistry model (INCHEM-Py) at the highest and lowest experimental temperatures, to explore the impact these product emissions have on the indoor air chemistry. The PS tubing plastic proved to be the highest emitting polymer per surface area. Almost all selected VOC emissions were found to have a linear relationship with temperature. Upon observing the impacts of primary VOC emissions from plastics in modelled simulations, the hydroxyl radical concentration decreased by an average of 1.6 and 10 % relative to the baseline (with no plastics included) at 18 °C and 28 °C respectively. On the other hand, formaldehyde concentrations increased by 29 and 31.6 % relative to the baseline conditions at 18 °C and 28 °C respectively. The presence of plastic products indoors, therefore, has the potential to impact the indoor air quality.

Passive breath monitoring of livestock: using factor analysis to deconvolve the cattle shed.

Respiratory and metabolic diseases in livestock cost the agriculture sector billions each year, with delayed diagnosis a key exacerbating factor. Previous studies have shown the potential for breath analysis to successfully identify incidence of disease in a range of livestock. However, these techniques typically involve animal handling, the use of nasal swabs or fixing a mask to individual animals to obtain a sample of breath. Using a cohort of 26 cattle as an example, we show how the breath of individual animals within a herd can be monitored using a passive sampling system, where no such handling is required. These benefits come at the cost of the desired breath samples unavoidably mixed with the complex cocktail of odours that are present within the cattle shed. Data were analysed using positive matrix factorisation (PMF) to identify and remove non-breath related sources of volatile organic compounds. In total three breath factors were identified (endogenous-, non-endogenous breath and rumen) and seven factors related to other sources within and around the cattle shed (e.g. cattle feed, traffic, urine and faeces). Simulation of a respiratory disease within the herd showed that the abnormal change in breath composition was captured in the residuals of the ten factor PMF solution, highlighting the importance of their inclusion as part of the breath fraction. Increasing the number of PMF factors to 17 saw the identification of a 'diseased' factor, which coincided with the visits of the three 'diseased' cattle to the breath monitor platform. This work highlights the important role that factor analysis techniques can play in analysing passive breath monitoring data.

Anthropogenic air pollutants reduce insect-mediated pollination services.

Common air pollutants, such as nitrogen oxides (NOx), emitted in diesel exhaust, and ozone (O3), have been implicated in the decline of pollinating insects. Reductionist laboratory assays, focused upon interactions between a narrow range of flowering plant and pollinator species, in combination with atmospheric chemistry models, indicate that such pollutants can chemically alter floral odors, disrupting the cues that foraging insects use to find and pollinate flowers. However, odor environments in nature are highly complex and pollination services are commonly provided by suites of insect species, each exhibiting different sensitivities to different floral odors. Therefore, the potential impacts of pollution-induced foraging disruption on both insect ecology, and the pollination services that insects provide, are currently unknown. We conducted in-situ field studies to investigate whether such pollutants could reduce pollinator foraging and as a result the pollination ecosystem service that those insects provide. Using free-air fumigation, we show that elevating diesel exhaust and O3, individually and in combination, to levels lower than is considered safe under current air quality standards, significantly reduced counts of locally-occurring wild and managed insect pollinators by 62-70% and their flower visits by 83-90%. These reductions were driven by changes in specific pollinator groups, including bees, flies, moths and butterflies, and coincided with significant reductions (14-31%) in three different metrics of pollination and yield of a self-fertile test plant. Quantifying such effects provides new insights into the impacts of human-induced air pollution on the natural ecosystem services upon which we depend.

Emotional expression in human odour.

Recent work has demonstrated that human body odour alters with changing emotional state and that emotionally laden odours can affect the physiology and behaviour of people exposed to them. Here we review these discoveries, which we believe add to a growing recognition that the human sense of smell and its potential role in social interactions have been underappreciated. However, we also critically evaluate the current evidence, with a particular focus on methodology and the interpretation of emotional odour studies. We argue that while the evidence convincingly indicates that humans retain a capacity for olfactory communication of emotion, the extent to which this occurs in ordinary social interaction remains an open question. Future studies should place fewer restrictions on participant selection and lifestyle and adopt more realistic experimental designs. We also need to devote more consideration to underlying mechanisms and to recognise the constraints that these may place on effective communication. Finally, we outline some promising approaches to address these issues, and raise some broader theoretical questions that such approaches may help us to answer.

Sources of non-methane hydrocarbons in surface air in Delhi, India.

Rapid economic growth and development have exacerbated air quality problems across India, driven by many poorly understood pollution sources and understanding their relative importance remains critical to characterising the key drivers of air pollution. A comprehensive suite of measurements of 90 non-methane hydrocarbons (NMHCs) (C2-C14), including 12 speciated monoterpenes and higher molecular weight monoaromatics, were made at an urban site in Old Delhi during the pre-monsoon (28-May to 05-Jun 2018) and post-monsoon (11 to 27-Oct 2018) seasons using dual-channel gas chromatography (DC-GC-FID) and two-dimensional gas chromatography (GC×GC-FID). Significantly higher mixing ratios of NMHCs were measured during the post-monsoon campaign, with a mean night-time enhancement of around 6. Like with NOx and CO, strong diurnal profiles were observed for all NMHCs, except isoprene, with very high NMHC mixing ratios between 35-1485 ppbv. The sum of mixing ratios of benzene, toluene, ethylbenzene and xylenes (BTEX) routinely exceeded 100 ppbv at night during the post-monsoon period, with a maximum measured mixing ratio of monoaromatic species of 370 ppbv. The mixing ratio of highly reactive monoterpenes peaked at around 6 ppbv in the post-monsoon campaign and correlated strongly with anthropogenic NMHCs, suggesting a strong non-biogenic source in Delhi. A detailed source apportionment study was conducted which included regression analysis to CO, acetylene and other NMHCs, hierarchical cluster analysis, EPA UNMIX 6.0, principal component analysis/absolute principal component scores (PCA/APCS) and comparison with NMHC ratios (benzene/toluene and i-/n-pentane) in ambient samples to liquid and solid fuels. These analyses suggested the primary source of anthropogenic NMHCs in Delhi was from traffic emissions (petrol and diesel), with average mixing ratio contributions from Unmix and PCA/APCS models of 38% from petrol, 14% from diesel and 32% from liquified petroleum gas (LPG) with a smaller contribution (16%) from solid fuel combustion. Detailed consideration of the underlying meteorology during the campaigns showed that the extreme night-time mixing ratios of NMHCs during the post-monsoon campaign were the result of emissions into a very shallow and stagnant boundary layer. The results of this study suggest that despite widespread open burning in India, traffic-related petrol and diesel emissions remain the key drivers of gas-phase urban air pollution in Delhi.

Vertical profiles of biogenic volatile organic compounds as observed online at a tower in Beijing.

Vertical profiles of isoprene and monoterpenes were measured by a proton transfer reaction-time of flight-mass spectrometry (PTR-ToF-MS) at heights of 3, 15, 32, 64, and 102 m above the ground on the Institute of Atmospheric Physics (IAP) tower in central Beijing during the winter of 2016 and the summer of 2017. Isoprene mixing ratios were larger in summer due to much stronger local emissions whereas monoterpenes were lower in summer due largely to their consumption by much higher levels of ozone. Isoprene mixing ratios were the highest at the 32 m in summer (1.64 ± 0.66 ppbV) and at 15 m in winter (1.41 ± 0.64 ppbV) with decreasing concentrations to the ground and to the 102 m, indicating emission from the tree canopy of the surrounding parks. Monoterpene mixing ratios were the highest at the 3 m height in both the winter (0.71 ± 0.42 ppbV) and summer (0.16 ± 0.10 ppbV) with a gradual decreasing trend to 102 m, indicting an emission from near the ground level. The lowest isoprene and monoterpene mixing ratios all occurred at 102 m, which were 0.71 ± 0.42 ppbV (winter) and 1.35 ± 0.51 ppbV (summer) for isoprene, and 0.42 ± 0.22 ppbV (winter) and 0.07 ± 0.06 ppbV (summer) for monoterpenes. Isoprene in the summer and monoterpenes in the winter, as observed at the five heights, showed significant mutual correlations. In the winter monoterpenes were positively correlated with combustion tracers CO and acetonitrile at 3 m, suggesting possible anthropogenic sources.

Decoding the social volatilome by tracking rapid context-dependent odour change.

Odours can have a significant influence on the outcome of social interactions. However, we have yet to characterize the chemical signature of any specific social cue in human body odour, and we know little about how changes in social context influence odour chemistry. Here, we argue that adoption of emerging analytical techniques from other disciplines, such as atmospheric chemistry, might become game-changing tools in this endeavour. First, we describe the use of online chemical ionization time-of-flight mass spectrometry to sensitively measure many hundreds of gas-phase volatile organic compounds in real time. By analysing ambient air emanating from undisturbed individuals or groups, the technique enables a continuous recording of an instantaneous odour change in response to external stimuli and changing social context. This has considerable advantages over the traditional approach of periodic sampling for analysis by gas chromatography. We also discuss multivariate statistical approaches, such as positive matrix factorization, that can effectively sift through this complex datastream to identify linked groups of compounds that probably underpin functional chemosignals. In combination, these innovations offer new avenues for addressing outstanding questions concerning olfactory communication in humans and other species, as well as in related fields using odour, such as biometrics and disease diagnostics. This article is part of the Theo Murphy meeting issue 'Olfactory communication in humans'.

A review of stereochemical implications in the generation of secondary organic aerosol from isoprene oxidation.

The atmospheric reactions leading to the generation of secondary organic aerosol (SOA) from the oxidation of isoprene are generally assumed to produce only racemic mixtures, but aspects of the chemical reactions suggest this may not be the case. In this review, the stereochemical outcomes of published isoprene-degradation mechanisms contributing to high amounts of SOA are evaluated. Despite evidence suggesting isoprene first-generation oxidation products do not contribute to SOA directly, this review suggests the stereochemistry of first-generation products may be important because their stereochemical configurations may be retained through to the second-generation products which form SOA. Specifically, due to the stereochemistry of epoxide ring-opening mechanisms, the outcome of the reactions involving epoxydiols of isoprene (IEPOX), methacrylic acid epoxide (MAE) and hydroxymethylmethyl-α-lactone (HMML) are, in principle, stereospecific which indicates the stereochemistry is predefined from first-generation precursors. The products from these three epoxide intermediates oligomerise to form macromolecules which are proposed to form chiral structures within the aerosol and are considered to be the largest contributors to SOA. If conditions in the atmosphere such as pH, aerosol water content, relative humidity, pre-existing aerosol, aerosol coatings and aerosol cation/anion content (and other) variables acting on the reactions leading to SOA affect the tacticity (arrangement of chiral centres) in the SOA then they may influence its physical properties, for example its hygroscopicity. Chamber studies of SOA formation from isoprene encompass particular sets of controlled conditions of these variables. It may therefore be important to consider stereochemistry when upscaling from chamber study data to predictions of SOA yields across the range of ambient atmospheric conditions. Experiments analysing the stereochemistry of the reactions under varying conditions of the above variables would help elucidate whether there is stereoselectivity in SOA formation from isoprene and if the rates of SOA formation are affected.

Effects of land use on surface-atmosphere exchanges of trace gases and energy in Borneo: comparing fluxes over oil palm plantations and a rainforest.

This paper reports measurements of land-atmosphere fluxes of sensible and latent heat, momentum, CO(2), volatile organic compounds (VOCs), NO, NO(2), N(2)O and O(3) over a 30 m high rainforest canopy and a 12 m high oil palm plantation in the same region of Sabah in Borneo between April and July 2008. The daytime maximum CO(2) flux to the two canopies differs by approximately a factor of 2, 1200 mg C m(-2) h(-1) for the oil palm and 700 mg C m(-2) h(-1) for the rainforest, with the oil palm plantation showing a substantially greater quantum efficiency. Total VOC emissions are also larger over the oil palm than over the rainforest by a factor of 3. Emissions of isoprene from the oil palm canopy represented 80 per cent of the VOC emissions and exceeded those over the rainforest in similar light and temperature conditions by on average a factor of 5. Substantial emissions of estragole (1-allyl-4-methoxybenzene) from the oil palm plantation were detected and no trace of this VOC was detected in or above the rainforest. Deposition velocities for O(3) to the rainforest were a factor of 2 larger than over oil palm. Emissions of nitrous oxide were larger from the soils of the oil palm plantation than from the soils of the rainforest by approximately 25 per cent. It is clear from the measurements that the large change in the species composition generated by replacing rainforest with oil palm leads to profound changes in the net exchange of most of the trace gases measured, and thus on the chemical composition of the boundary layer over these surfaces.