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) affects isoprenoid emissions, and floral emissions in particular, which may result in potential impacts on the interactions of plants with other organisms. The effects of ozone (O₃) on isoprenoid emissions have been investigated for many years, while knowledge on O₃ effects on floral emissions is still scarce and the relevant mechanism has not been clarified so far. We investigated the effects of O₃ on floral and foliar isoprenoid emissions (mainly isoprene, monoterpenes and sesquiterpenes) and their synthase substrates from three rose varieties (CH, Rosa chinensis Jacq. var. chinensis; SA, R. hybrida ‘Saiun’; MO, R. hybrida ‘Monica Bellucci’) at different exposure durations. Results indicated that the O₃-induced stimulation after short-term exposure (35 days after the beginning of O₃ exposure) was significant only for sesquiterpene emissions from flowers, while long-term O₃ exposure (90 days after the beginning of O₃ exposure) significantly decreased both foliar and floral monoterpene and sesquiterpene emissions. In addition, the observed decline of emissions under long-term O₃ exposure resulted from the limitation of synthase substrates, and the responses of emissions and substrates varied among varieties, with the greatest variation in the O₃-sensitive variety. These findings provide important insights on plant isoprenoid emissions and species selection for landscaping, especially in areas with high O₃ concentration.

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.

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.

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.

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.

Seasonal and diurnal variations of carbonyl compounds were investigated in the ambient air of a mountainous city in China, from September 2014 to July 2015. The most abundant carbonyl compounds are formaldehyde, acetaldehyde and acetone, propionaldehyde and methacryladehyde (MACR), which were all measured in most samples. The average concentrations of formaldehyde, acetaldehyde, acetone, propionaldehyde and MACR in the atmosphere in Changsha were broken down into each season: 6.57, 3.29, 3.66, 0.67 and 0.54 μg/m³ respectively during Spring, 14.09, 8.28, 9.02, 1.28 and 0.6 μg/m³, respectively during Summer, 9.24, 5.48, 8.62, 0.73 and 0.62 μg/m³, respectively during Autumn, and 5.88, 4.84, 7.84, 0.87 and 0.26 μg/m³ respectively during Winter. And majority of the species had higher concentration during noon, showing photochemical oxidation and human activities played an important role in diurnal variation. The highest average C1/C2 (formaldehyde/acetaldehyde) ratio was observed in summer (2.10) compared to those (1.33–2.03) in other seasons, implying the photochemical activities had a positive effect on increasing the ratio of C1/C2. In this study, the monthly concentration of formaldehyde produced from isoprene accounts for 4.8%–39.1% of formaldehyde in ambient air. Strong correlation among some carbonyl compounds means that they came from the same sources. Photochemical reaction was the main source of carbonyl compounds in summer and vehicular exhaust (gasoline and diesel engines) in winter. Changsha is not a completely urbanized city and it is rich in vegetation of broadleaf evergreen shrubs. Both atmospheric photochemical reactions and anthropogenic sources, including vehicular exhaust and industrial processes, dominate the levels of carbonyls. The ILTCR and HQ values of formaldehyde and acetaldehyde are 1.23E-04 and 1.34E-05, 2.80E-01 and 1.86E-01, respectively.

Thirteen secondary organic aerosol (SOA) tracers of isoprene, monoterpenes and sesquiterpenes were measured for PM₂.₅ aerosols collected at the summit of Mt. Wuyi (1139 m, a.s.l.), to investigate their seasonality and formation mechanism. Concentrations of the isoprene and monoterpene SOA tracers were much higher in summer than those in other seasons. In contrast, β-caryophyllinic acid was found to be the lowest in summer. Concentrations of those BSOA tracers showed a positive correlation with temperature (R² = 0.52–0.70), and a negative correlation with relative humidity (R² = 0.43–0.78). Moreover, thermodynamic model (i.e., ISORROPIA-II) calculation results showed that acidity conditions are favorable for BSOA formation. Robust linear correlations between the BSOA tracers and anthropogenic pollutants such as SO₂ (R² = 0.53–0.7) and NO₂ (R² = 0.37–0.54) were observed for all the samples, suggesting that SO₂ and NOx can enhance BSOA production in the remote mountain area of southeast China, which is related to an acid-catalyzed heterogeneous chemistry. Moreover, we also found a significant correlation between the concentrations of the BSOA tracers and levoglucosan especially for β-caryophyllinic acid, indicating that biomass burning plumes from the distant lowland regions could influence the production of BSOA in the mountain free troposphere. Our results clearly demonstrated that anthropogenic emissions in China could enhance BSOA formation in the distant mountain regions.

Chemical mass balance (CMB) modeling and radiocarbon measurements were combined to evaluate the sources of carbonaceous fine particulate matter (PM2.5) in Shenzhen, China during and after the 2011 summer Universiade games when air pollution control measurements were implemented to achieve air quality targets. Ambient PM2.5 filter samples were collected daily at two sampling sites (Peking University Shenzhen campus and Longgang) over 24 consecutive days, covering the controlled and uncontrolled periods. During the controlled period, the average PM2.5 concentration was less than half of what it was after the controls were lifted. Organic carbon (OC), organic molecular markers (e.g., levoglucosan, hopanes, polycyclic aromatic hydrocarbons), and secondary organic carbon (SOC) tracers were all significantly lower during the controlled period. After pollution controls ended, at Peking University, OC source contributions included gasoline and diesel engines (24%), coal combustion (6%), biomass burning (12.2%), vegetative detritus (2%), biogenic SOC (from isoprene, α-pinene, and β-caryophyllene; 7.1%), aromatic SOC (23%), and other sources not included in the model (25%). At Longgang after the controls ended, similar source contributions were observed: gasoline and diesel engines (23%), coal combustion (7%), biomass burning (17.7%), vegetative detritus (1%), biogenic SOC (from isoprene, α-pinene, and β-caryophyllene; 5.3%), aromatic SOC (13%), and other sources (33%). The contributions of the following sources were smaller during the pollution controls: biogenic SOC (by a factor of 10–16), aromatic SOC (4–12), coal combustion (1.5–6.8), and biomass burning (2.3–4.9). CMB model results and radiocarbon measurements both indicated that fossil carbon dominated over modern carbon, regardless of pollution controls. However, the CMB model needs further improvement to apportion contemporary carbon (i.e. biomass burning, biogenic SOC) in this region. This work defines the major contributors to carbonaceous PM2.5 in Shenzhen and demonstrates that control measures for primary emissions could significantly reduce secondary organic aerosol (SOA) formation.

In the efforts at controlling automobile emissions, it is important to know in what extent air pollutants from on-road vehicles could be truly reduced. In 2014 we conducted tests in a heavily trafficked tunnel in south China to characterize emissions of volatile organic compounds (VOC) from on-road vehicle fleet and compared our results with those obtained in the same tunnel in 2004. Alkanes, aromatics, and alkenes had average emission factors (EFs) of 338, 63, and 42 mg km⁻¹ in 2014 against that of 194, 129, and 160 mg km⁻¹ in 2004, respectively. In 2014, LPG-related propane, n-butane and i-butane were the top three non-methane hydrocarbons (NMHCs) with EFs of 184 ± 21, 53 ± 6 and 31 ± 3 mg km⁻¹; the gasoline evaporation marker i-pentane had an average EF of 17 ± 3 mg km⁻¹; ethylene and propene were the top two alkenes with average EFs of 16 ± 1 and 9.7 ± 0.9 mg km⁻¹, respectively; isoprene had no direct emission from vehicles; toluene showed the highest EF of 11 ± 2 mg km⁻¹ among the aromatics; and acetylene had an average EF of 7 ± 1 mg km⁻¹. While EFs of total NMHCs decreased only 9% from 493 ± 120 mg km⁻¹ in 2004 to 449 ± 40 mg km⁻¹ in 2014, their total ozone formation potential (OFP) decreased by 57% from 2.50 × 10³ mg km⁻¹ in 2004 to 1.10 × 10³ mg km⁻¹ in 2014, and their total secondary organic aerosol formation potential (SOAFP) decreased by 50% from 50 mg km⁻¹ in 2004 to 25 mg km⁻¹ in 2014. The large drop in ozone and SOA formation potentials could be explained by reduced emissions of reactive alkenes and aromatics, due largely to fuel transition from gasoline/diesel to LPG for taxis/buses and upgraded vehicle emission standards.