A novel free-air diesel and ozone enrichment (FADOE) research platform

Air pollution is an escalating concern in the modern world, posing substantial threats to ecosystems processes. While the importance of comprehending the impact of pollutants on natural environments is evident, conducting rigorous field-based experiments presents formidable challenges. Elevating pollutant concentrations within open air environments in a controlled manner is complex. Nonetheless, such real-world experiments are invaluable for revealing the genuine influence of air pollutants on ecosystems and their functioning. Field-scale measurements have emerged as a pivotal avenue for advancing our understanding of the interactions between air pollutants and the natural world, providing unique insights into ecosystem dynamics, including critical processes like pollination and natural pest regulation. In atmospheric and ecological research, free-air exposure systems have proven effective in elevating carbon dioxide (CO2) and ozone (O3) concentrations, facilitating the exploration of their ecological consequences. Yet, nitrogen oxides (NOx), a class of pollutants with significant ecological and atmospheric relevance, have largely eluded field-based ecological investigations. This paper introduces the recently developed FADOE (Free-Air Diesel and Ozone Enrichment) platform, which allows the elevation of O3 and diesel exhaust (including NOx) within a field-scale context. Comprehensive information on the system's design, construction, and performance data from the 2023 summer season is presented

Concurrent anthropogenic air pollutants enhance recruitment of a specialist parasitoid

Air pollutants—such as nitrogen oxides, emitted in diesel exhaust, and ozone (O3)—disrupt interactions between plants, the insect herbivore pests that feed upon them and natural enemies of those herbivores (e.g. parasitoids). Using eight field-based rings that emit regulated quantities of diesel exhaust and O3, we investigated how both pollutants, individually and in combination, altered the attraction and parasitism rate of a specialist parasitoid (Diaeretiella rapae) on aphid-infested and un-infested Brassica napus plants. Individual effects of O3 decreased D. rapae abundance and emergence by 37% and 55%, respectively, compared with ambient (control) conditions. When O3 and diesel exhaust were emitted concomitantly, D. rapae abundance and emergence increased by 79% and 181%, respectively, relative to control conditions. This attraction response occurred regardless of whether plants were infested with aphids and was associated with an increase in the concentration of aliphatic glucosinolates, especially gluconapin (3-butenyl-glucosinolate), within B. napus leaves. Plant defensive responses and their ability to attract natural aphid enemies may be beneficially impacted by pollution exposure. These results demonstrate the importance of incorporating multiple air pollutants when considering the effects of air pollution on plant–insect interactions

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, β-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

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

Estimation of ammonia deposition to forest ecosystems in Scotland and Sri Lanka using wind-controlled NH3 enhancement experiments

Ammonia (NH3) pollution has emerged as a major cause of concern as atmospheric concentrations continue to increase globally. Environmentally damaging NH3 levels are expected to severely affect sensitive and economically important organisms, but evidence is lacking in many parts of the world. We describe the design and operation of a wind-controlled NH3 enhancement system to assess effects on forests in two contrasting climates. We established structurally identical NH3 enhancement systems in a temperate birch woodland in the UK and a tropical sub-montane forest in central Sri Lanka, both simulating real-world NH3 pollution conditions. Vertical and horizontal NH3 concentrations were monitored at two different time scales to understand NH3 transport within the forest canopies. We applied a bi-directional resistance model with four canopy layers to calculate net deposition fluxes. At both sites, NH3 concentrations and deposition were found to decrease exponentially with distance away from the source, consistent with expectations. Conversely, we found differences in vertical mixing of NH3 between the two experiments, with more vertically uniform NH3 concentrations in the dense and multi-layered sub-montane forest canopy in Sri Lanka. Monthly NH3 concentrations downwind of the source ranged from 3 to 29 μg m−3 at the UK site and 2–47 μg m−3 at the Sri Lankan site, compared with background values of 0.63 and 0.35 μg m−3, respectively. The total calculated NH3 dry deposition flux to all the canopy layers along the NH3 transects ranged from 12 to 162 kg N ha−1 yr−1 in the UK and 16–426 kg N ha−1 yr−1 in Sri Lanka, representative of conditions in the vicinity of a range of common NH3 sources. This multi-layer model is applicable for identifying the fate of NH3 in forest ecosystems where the gas enters the canopy laterally through the trunk space and exposes the understorey to high NH3 levels. In both study sites, we found that cuticular deposition was the dominant flux in the vegetation layers, with a smaller contribution from stomatal uptake. The new facilities are now allowing the first ever field comparison of NH3 impacts on forest ecosystems, with special focus on lichen bio-indicators, which will provide vital evidence to inform NH3 critical levels and associated nitrogen policy development in South Asia

Emissions of intermediate-volatility and semi-volatile organic compounds from domestic fuels used in Delhi, India

Biomass burning emits significant quantities of intermediate-volatility and semi-volatile organic compounds (I/SVOCs) in a complex mixture, probably containing many thousands of chemical species. These components are significantly more toxic and have poorly understood chemistry compared to volatile organic compounds routinely quantified in ambient air; however, analysis of I/SVOCs presents a difficult analytical challenge. The gases and particles emitted during the test combustion of a range of domestic solid fuels collected from across Delhi were sampled and analysed. Organic aerosol was collected onto Teflon (PTFE) filters, and residual low-volatility gases were adsorbed to the surface of solid-phase extraction (SPE) discs. A new method relying on accelerated solvent extraction (ASE) coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-ToF-MS) was developed. This highly sensitive and powerful analytical technique enabled over 3000 peaks from I/SVOC species with unique mass spectra to be detected. A total of 15 %-100% of gas-phase emissions and 7 %-100% of particle-phase emissions were characterised. The method was analysed for suitability to make quantitative measurements of I/SVOCs using SPE discs. Analysis of SPE discs indicated phenolic and furanic compounds were important for gas-phase I/SVOC emissions and levoglucosan to the aerosol phase. Gas- and particle-phase emission factors for 21 polycyclic aromatic hydrocarbons (PAHs) were derived, including 16 compounds listed by the US EPA as priority pollutants. Gas-phase emissions were dominated by smaller PAHs. The new emission factors were measured (mg kg-1) for PAHs from combustion of cow dung cake (615), municipal solid waste (1022), crop residue (747), sawdust (1236), fuelwood (247), charcoal (151) and liquefied petroleum gas (56). The results of this study indicate that cow dung cake and municipal solid waste burning are likely to be significant PAH sources, and further study is required to quantify their impact alongside emissions from fuelwood burning

Emissions of non-methane volatile organic compounds from combustion of domestic fuels in Delhi, India

Twenty-nine different fuel types used in residential dwellings in northern India were collected from across Delhi (76 samples in total). Emission factors of a wide range of non-methane volatile organic compounds (NMVOCs) (192 compounds in total) were measured during controlled burning experiments using dualchannel gas chromatography with flame ionisation detection (DC-GC-FID), two-dimensional gas chromatography (GC×GC-FID), proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) and solid-phase extraction two-dimensional gas chromatography with time-offlight mass spectrometry (SPE-GC×GC-ToF-MS). On average, 94% speciation of total measured NMVOC emissions was achieved across all fuel types. The largest contributors to emissions from most fuel types were small non-aromatic oxygenated species, phenolics and furanics. The emission factors (in g kg-1) for total gas-phase NMVOCs were fuelwood (18.7, 4.3-96.7), cow dung cake (62.0, 35.3-83.0), crop residue (37.9, 8.9-73.8), charcoal (5.4, 2.4-7.9), sawdust (72.4, 28.6-115.5), municipal solid waste (87.3, 56.6- 119.1) and liquefied petroleum gas (5.7, 1.9-9.8). The emission factors measured in this study allow for better characterisation, evaluation and understanding of the air quality impacts of residential solid-fuel combustion in India

Donepezil Impairs Memory in Healthy Older Subjects: Behavioural, EEG and Simultaneous EEG/fMRI Biomarkers

Rising life expectancies coupled with an increasing awareness of age-related cognitive decline have led to the unwarranted use of psychopharmaceuticals, including acetylcholinesterase inhibitors (AChEIs), by significant numbers of healthy older individuals. This trend has developed despite very limited data regarding the effectiveness of such drugs on non-clinical groups and recent work indicates that AChEIs can have negative cognitive effects in healthy populations. For the first time, we use a combination of EEG and simultaneous EEG/fMRI to examine the effects of a commonly prescribed AChEI (donepezil) on cognition in healthy older participants. The short- and long-term impact of donepezil was assessed using two double-blind, placebo-controlled trials. In both cases, we utilised cognitive (paired associates learning (CPAL)) and electrophysiological measures (resting EEG power) that have demonstrated high-sensitivity to age-related cognitive decline. Experiment 1 tested the effects of 5 mg/per day dosage on cognitive and EEG markers at 6-hour, 2-week and 4-week follow-ups. In experiment 2, the same markers were further scrutinised using simultaneous EEG/fMRI after a single 5 mg dose. Experiment 1 found significant negative effects of donepezil on CPAL and resting Alpha and Beta band power. Experiment 2 replicated these results and found additional drug-related increases in the Delta band. EEG/fMRI analyses revealed that these oscillatory differences were associated with activity differences in the left hippocampus (Delta), right frontal-parietal network (Alpha), and default-mode network (Beta). We demonstrate the utility of simple cognitive and EEG measures in evaluating drug responses after acute and chronic donepezil administration. The presentation of previously established markers of age-related cognitive decline indicates that AChEIs can impair cognitive function in healthy older individuals. To our knowledge this is the first study to identify the precise neuroanatomical origins of EEG drug markers using simultaneous EEG/fMRI. The results of this study may be useful for evaluating novel drugs for cognitive enhancement

Determination of Rn-222 in freshwater: development of a robust method of analysis by alpha/beta separation liquid scintillation spectrometry.

Liquid scintillation spectrometry is used widely for determining 222Rn in natural waters; however, the benefits of α/β separation have not been fully explored. The extractants toluene and Ultima Gold F were compared, and both performed well for a range of extreme waters. A robust method for calibrating extraction and counting efficiencies has been developed. Detection limits are 20 mBq l−1 (toluene) and 16 mBq l−1 (UGF) for a 60 min count and 600-ml sample, halving the required sample volume

Controls on the spatial and temporal variability of Rn-222 in riparian groundwater in a lowland Chalk catchment.

Radon is a powerful tracer of stream-aquifer interactions. However, it is important to consider the source and behaviour of radon in groundwater when interpreting observations of river radon in relation to groundwater discharge. Here we characterise the variability in groundwater radon concentrations in the riparian zone of a Chalk catchment. Groundwater 222Rn (radon) concentrations were determined in riparian zone boreholes at two sites in the Lambourn catchment, Berkshire, UK, over a two year period. In addition, borehole core material was analysed for 226Ra (radium) and to determine radon emanation. Radon and radium concentrations and radon emanation were found to change with depth and temporal variations in groundwater radon concentrations were found at different scales. The abundance of radium and emanation of radon increased nearer the surface leading to greater groundwater radon concentrations. It is shown that seasonal changes in water table elevation can to lead to variable radon concentrations in groundwater as zones of radon production become hydraulically active. Groundwater radon concentrations in shallow piezometers were found to respond to both seasonal changes in the water table and individual rainfall events. Riparian sources of radon can be variable and are therefore potentially influential in the radon signals observed in rivers and should be properly characterised when interpreting river radon inputs