A total of 106 24-h PM₂.₅ aerosol samples were collected in an urban area (Shijiazhuang, SJZ) and a suburban area (Liulihe, LLH, Fangshan County, Beijing) in the Beijing-Tianjin-Hebei (BTH) region in 2 periods: the first is from 10 July to 10 August, which is before Sept. Third Parade (Period I); the second is from 20 Aug. to 6 Sept. 2015, which is during Sept. Third Parade (Period II). Polar organic tracers, including isoprene, α-pinene, β-caryophyllene and toluene oxidation products, as well as sugars and carboxylic acids were measured. In Period II, rigorous emission-reduction measures were taken in the BTH region. With the anthropogenic emission being cut down significantly, the average concentrations of isoprene, α-pinene, β-caryophyllene and toluene oxidation products and all carboxylic acids (except tetradecanoic, palmitic, and stearic acids), were lower in Period II than those in Period I in LLH, indicating that the SOA tracers were decreased with precursor emission volumes and yields in the atmosphere. Moreover, sugar compounds were shown with comparable levels during the two periods in LLH, suggesting that no measures were taken to reduce the intensities of the biogenic sources. On the contrary, tetradecanoic, palmitic, and stearic acids were shown with obviously higher concentrations in Period II than those in Period I, demonstrating that cooking fumes increased during Sept. Third Parade period.The positive matrix factorization (PMF) model combining with tracer-based method was applied to explore the sources of secondary organic carbon (SOC). It reveals that the sources of SOC include isoprene, α-pinene, β-caryophyllene and toluene oxidation products, fossil fuel combustion, cooking fumes and regionally transferred aged aerosols. These sources accounted for 11.3%, 9.0%, 15.5%, 10.9%, 29.2%, 2.9%, 21.1% of SOC for SJZ, and 12.7%, 11.2%, 9.7%, 14.4%, 25.3%, 0%, 26.7% of SOC for LLH, during the whole sampling periods respectively.

The spatial distributions, fluxes, and environmental effects of non-methane hydrocarbons (NMHCs) were investigated in the Yellow Sea (YS) and the East China Sea (ECS) in spring. The average concentrations of ethane, propane, i-/n-butane, ethylene, propylene and isoprene in the seawater were 18.1 ± 6.4, 15.4 ± 4.7, 6.8 ± 2.9, 6.4 ± 3.2, 67.1 ± 26.7, 20.5 ± 8.7 and 17.1 ± 11.1 pmol L⁻¹, respectively. The alkenes in the surface seawater were more abundant than their saturated homologs and NMHCs concentrations (with the exception of isoprene) decreased with carbon number. The spatial variations of isoprene were consistent with the distributions of chlorophyll a (Chl-a) and Chaetoceros, Skeletonema, Nitzschia mainly contributed to the production of isoprene, while the others’ distributions might be related to their photochemical production. Observations in atmospheric NMHCs indicated alkanes in the marine atmosphere decreased from inshore to offshore due to influence of the continental emissions, while alkenes were largely derived from the oceanic source. In addition, no apparent diurnal discrepancy of atmospheric NMHCs (except for isoprene) were found between daytime and night. As the main sink of NMHCs in seawater, the average sea-to-air fluxes of ethane, propane, i-/n-butane, ethylene and propylene were 31.70, 29.75, 18.49, 15.89, 239.6, 67.94 and 52.41 nmol m⁻² d⁻¹, respectively. The average annual emissions of isoprene accounted for 0.1–1.3% of the global ocean emissions, which indicated that the coastal and shelf areas might be significant sources of isoprene. Furthermore, this study represents the first effort to estimate the environmental effects caused by NMHCs over the YS and the ECS and the results demonstrated contributions of alkanes to ozone and secondary organic aerosol (SOA) formation were lower than those of the alkenes and the largest contributor was isoprene.

Tropospheric ozone (O₃) impairs physiological processes of plants while nitrogen (N) deposition may cause imbalances in soil N and other nutrients such as phosphorus (P) suggesting an increase of P demand for plants. However, the combined effect of O₃, soil N and P on isoprene emission from leaves has never been tested. We therefore examined isoprene emission in leaves of Oxford poplar clone exposed to O₃ (ambient, AA [35.0 nmol mol⁻¹ as daily mean]; 1.5 × AA; 2.0 × AA), soil N (0 and 80 kg N ha⁻¹) and soil P (0, 40 and 80 kg P ha⁻¹) in July and September in a Free-Air Controlled Exposure (FACE) facility. We also investigated the response of isoprene emission to foliar N, P and abscisic acid (ABA) contents in September because the 2-C-methylerythritol-5-phosphate (MEP) pathway of isoprenoid biosynthesis produces ABA. We found that O₃ increased isoprene emission in July, which was associated to increased dark respiration, suggesting an activation of metabolism against O₃ stress as an initial response. However, O₃ decreased isoprene emission in September which was associated to reduced net photosynthesis. In September, isoprene emission was positively correlated with leaf N content and negatively correlated with leaf P content in AA. However, no response of isoprene emission to foliar N and P was found in elevated O₃, suggesting that the isoprene responses to foliar N and P depended on the O₃ exposure levels. Isoprene emission rate in 1.5 × AA and 2.0 × AA increased with increasing leaf ABA content, indicating accelerated senescence of injured leaves to favor new leaf growth when high O₃ and nutritional availability in the soil were combined. Even though foliar N and P usually act as a proxy for isoprene emission rate, the impact of recent abiotic factors such as O₃ should be always considered for modeling isoprene emission under climate change.

There is growing evidence that the very presence of human beings in an enclosed environment can impact air quality by affecting the concentrations of certain airborne volatile organic compounds (VOC). This influence increases considerably when humans perform different activities, such as using toiletries, or simply eating and drinking. To understand the influence of these parameters on the concentrations of selected airborne constituents, a study was performed under simulated residential conditions in an environmentally-controlled exposure room. The human subjects either simply remained for a certain time in the exposure room, or performed pre-defined activities in the room (drinking wine, doing sport, using toiletries, and preparation of a meal containing melted cheese). The impact of each activity was assessed separately using our analytical platform and exposure room under controlled environmental conditions. The results showed that prolonged human presence leads to increased levels of isoprene, TVOCs, formaldehyde and, to a lesser extent, acetaldehyde. These outcomes were further supported by results of meta-analyses of data acquired during several internal studies performed over two years. Furthermore, it was seen that the indoor concentrations of several of the selected constituents rose when the recreational and daily living activities were performed. Indeed, an increase in acetaldehyde was observed for all tested conditions, and these higher indoor levels were especially notable during wine-drinking as well as cheese meal preparation. Formaldehyde increased during the sessions involving sport, using toiletries, and cheese meal preparation. Like acetaldehyde, acrolein, crotonaldehyde and particulate matter levels rose significantly during the cheese meal preparation session. In conclusion, prolonged human residence indoors and some recreational and daily living activities caused substantial emissions of several airborne pollutants under ventilation typical for residential environments.

This is the first study to characterize the variation and emission of C₂-C₅ non-methane volatile organic compounds (NMVOCs) in a semi-urban site of western India based on measurements during February–December 2015. Anthropogenic NMVOCs show clear seasonal dependence with highest in winter and lowest in monsoon season. Biogenic NMVOCs likes isoprene show highest mixing ratios in the pre-monsoon season. The diurnal variation of NMVOC species can be described by elevated values from night till morning and lower values in the afternoon hours. The elevated levels of NMVOCs during night and early morning hours were caused mainly by weaker winds, temperature inversion and reduced chemical loss. The correlations between NMVOCs, CO and NOx indicate the dominant role of various local emission sources. Use and leakage of liquefied petroleum gas (LPG) contributed to the elevated levels of propane and butanes. Mixing ratios of ethylene, propylene, CO, NOx, etc. show predominant emissions from combustion of fuels in automobiles and industries. The Positive Matrix Factorization (PMF) source apportionments were performed for the seven major emission sectors (i.e. Vehicular exhaust, Mixed industrial emissions, Biomass/Fired brick kilns/Bio-fuel, Petrochem, LPG, Gas evaporation, Biogenic). Emissions from vehicle exhaust and industry-related sources contributed to about 19% and 40% of the NMVOCs, respectively. And the rest (41%) was attributed to the emissions from biogenic sources, LPG, gasoline evaporation and biomass burning. Diurnal and seasonal variations of NMVOCs were controlled by local emissions, meteorology, OH concentrations, long-range transport and planetary boundary layer height. This study provides a good reference for framing environmental policies to improve the air quality in western region of India.

Energy crops are an important renewable source for energy production in future. To ensure high yields of crops, N fertilization is a common practice. However, knowledge on environmental impacts of bioenergy plantations, particularly in systems involving trees, and the effects of N fertilization is scarce. We studied the emission of volatile organic compounds (VOC), which negatively affect the environment by contributing to tropospheric ozone and aerosols formation, from Miscanthus and willow plantations. Particularly, we aimed at quantifying the effect of N fertilization on VOC emission. For this purpose, we determined plant traits, photosynthetic gas exchange and VOC emission rates of the two systems as affected by N fertilization (0 and 80 kg ha−1 yr−1). Additionally, we used a modelling approach to simulate (i) the annual VOC emission rates as well as (ii) the OH. reactivity resulting from individual VOC emitted. Total VOC emissions from Salix was 1.5- and 2.5-fold higher compared to Miscanthus in non-fertilized and fertilized plantations, respectively. Isoprene was the dominating VOC in Salix (80–130 μg g−1 DW h−1), whereas it was negligible in Miscanthus. We identified twenty-eight VOC compounds, which were released by Miscanthus with the green leaf volatile hexanal as well as dimethyl benzene, dihydrofuranone, phenol, and decanal as the dominant volatiles. The pattern of VOC released from this species clearly differed to the pattern emitted by Salix. OH. reactivity from VOC released by Salix was ca. 8-times higher than that of Miscanthus. N fertilization enhanced stand level VOC emissions, mainly by promoting the leaf area index and only marginally by enhancing the basal emission capacity of leaves. Considering the higher productivity of fertilized Miscanthus compared to Salix together with the considerably lower OH. reactivity per weight unit of biomass produced, qualified the C4-perennial grass Miscanthus as a superior source of future bioenergy production.

Peroxy acetyl nitrate (PAN) is a key component of photochemical smog and plays an important role in atmospheric chemistry. Though it has been known that PAN is produced via reactions of nitrogen oxides (NOx) with some volatile organic compounds (VOCs), it is difficult to quantify the contributions of individual precursor species. Here we use an explicit photochemical model – Master Chemical Mechanism (MCM) model – to dissect PAN formation and identify principal precursors, by analyzing measurements made in Beijing in summer 2008. PAN production was sensitive to both NOx and VOCs. Isoprene was the predominant VOC precursor at suburb with biogenic impact, whilst anthropogenic hydrocarbons dominated at downtown. PAN production was attributable to a relatively small class of compounds including NOx, xylenes, trimethylbenzenes, trans/cis-2-butenes, toluene, and propene. MCM can advance understanding of PAN photochemistry to a species level, and provide more relevant recommendations for mitigating photochemical pollution in large cities.

The toxicity of organic aerosols has been largely ascribed to the generation of reactive oxygen species, which could subsequently induce oxidative stress in biological systems. The reaction of DTT with redox-active species in PM has been generally assumed to be pseudo-first order, with the oxidative potential of PM being represented by the DTT consumption per minute of reaction time per μg of PM. Although catalytic reactive species such as transition metals and quinones are long believed to be the main contributors of DTT responses, the role of non-catalytic DTT reactive species such as organic hydroperoxides (ROOH) and electron-deficient alkenes (e.g., conjugated carbonyls) in DTT consumption has been recently highlighted. Thus, understanding the reaction kinetics and mechanisms of DTT consumption by various PM components is required to interpret the oxidative potential measured by DTT assays more accurately. In this study, we measured the DTT consumptions over time and characterized the reaction products using model compounds and secondary organic aerosols (SOA) with varying initial concentrations. We observed that the DTT consumption rates linearly increased with both initial DTT and sample concentrations. The overall reaction order of DTT with non-catalytic reactive species and SOA in this study is second order. The reactions of DTT with different functional groups have significantly different rate constants. The reaction rate constant of isoprene SOA with DTT is mainly determined by the concentration of ROOH. For toluene SOA, both ROOH and electron-deficient alkenes may dominate its DTT reaction rates. These results provide some insights into the interpretation of DTT-based aerosol oxidative potential and highlight the need to study the toxicity mechanism of ROOH and electron-deficient alkenes in PM for future work.

We investigated isoprene (ISO) emission and gas exchange in leaves from different positions along the vertical canopy profile of poplar saplings (Populus euramericana cv. ‘74/76’). For a growing season, plants were subjected to four N treatments, control (NC, no N addition), low N (LN, 50 kg N ha⁻¹year⁻¹), middle N (MN, 100 kg N ha⁻¹year⁻¹), high N (HN, 200 kg N ha⁻¹year⁻¹) and three O₃ treatments (CF, charcoal-filtered ambient air; NF, non-filtered ambient air; NF + O₃, NF + 40 ppb O₃). Our results showed the effects of O₃ and/or N on standardized ISO rate (ISOᵣₐₜₑ) and photosynthetic parameters differed along with the leaf position, with larger negative effects of O₃ and positive effects of N on ISOᵣₐₜₑ and photosynthetic parameters in the older leaves. Expanded young leaves were insensitive to both treatments even at very high O₃ concentration (67 ppb as 10-h average) and HN treatment. Significant O₃ × N interactions were only found in middle and lower leaves, where ISOᵣₐₜₑ declined by O₃ just when N was limited (NC and LN). With increasing light-saturated photosynthesis and chlorophyll content, ISOᵣₐₜₑ was reduced in the upper leaves but on the contrary increased in middle and lower leaves. The responses of ISOᵣₐₜₑ to AOT40 (accumulated exposure to hourly O₃ concentrations > 40 ppb) and PODY (accumulative stomatal uptake of O₃ > Y nmol O₃ m⁻² PLA s⁻¹) were not significant in upper leaves, but ISOᵣₐₜₑ significantly decreased with increasing AOT40 or PODY under limited N supply in middle leaves but at all N levels in lower leaves. Overall, ISOᵣₐₜₑ changed along the vertical canopy profile in response to combined O₃ and N exposure, a behavior that should be incorporated into multi-layer canopy models. Our results are relevant for modelling regional isoprene emissions under current and future O₃ pollution and N deposition scenarios.

Isoprene, formaldehyde and acetaldehyde are important reactive organic compounds which strongly impact atmospheric oxidation processes and formation of tropospheric ozone. Monsoon meteorology and the topography of Himalayan foothills cause surface emissions to get rapidly transported both horizontally and vertically, thereby influencing atmospheric processes in distant regions. Further in monsoon, Indo-Gangetic Plain is a major rice growing region of the world and daytime hourly ozone can frequently exceed phytotoxic dose of 40 ppb O₃. However, the sources and ambient variability of these compounds which are potent ozone precursors are unknown. Here, we investigate the sources and photochemical processes driving their emission/formation during monsoon season from a sub-urban site at the foothills of the Himalayas. The measurements were performed in July, August and September using a high sensitivity mass spectrometer. Average ambient mixing ratios (±1σ variability) of isoprene, formaldehyde, acetaldehyde, and the sum of methyl vinyl ketone and methacrolein (MVK+MACR), were 1.4 ± 0.3 ppb, 5.7 ± 0.9 ppb, 4.5 ± 2.0 ppb, 0.75 ± 0.3 ppb, respectively, and much higher than summertime values in May. For isoprene these values were comparable to mixing ratios observed over tropical forests. Surprisingly, despite occurrence of anthropogenic emissions, biogenic emissions were found to be the major source of isoprene with peak daytime isoprene driven by temperature (r ≥ 0.8) and solar radiation. Photo-oxidation of precursor hydrocarbons were the main sources of acetaldehyde, formaldehyde and MVK+MACR. Ambient mixing ratios of all the compounds correlated poorly with acetonitrile (r ≤ 0.2), a chemical tracer for biomass burning suggesting negligible influence of biomass burning during monsoon season. Our results suggest that during monsoon season when radiation and rain are no longer limiting factors and convective activity causes surface emissions to be transported to upper atmosphere, biogenic emissions can significantly impact the remote upper atmosphere, climate and ozone affecting rice yields.