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.

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.

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.

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.

Thirteen secondary organic aerosol (SOA) tracers of isoprene (SOAI), monoterpenes (SOAM), sesquiterpenes (SOAS) and aromatics (SOAA) in fine particulate matter (PM2.5) were measured at a Pearl River Delta (PRD) regional site for one year. The characteristics including their seasonal cycles and the factors influencing their formation in this region were studied. The seasonal patterns of SOAI, SOAM and SOAS tracers were characterized over three enhancement periods in summer (I), autumn (II) and winter (III), while the elevations of SOAA tracer (i.e., 2,3-dihydroxy-4-oxopentanoic acid, DHOPA) were observed in Periods II and III. We found that SOA formed from different biogenic precursors could be driven by several factors during a one-year seasonal cycle. Isoprene emission controlled SOAI formation throughout the year, while monoterpene and sesquiterpene emissions facilitated SOAM and SOAS formation in summer rather than in other seasons. The influence of atmospheric oxidants (Ox) was found to be an important factor of the formation of SOAM tracers during the enhancement periods in autumn and winter. The formation of SOAS tracer was influenced by the precursor emissions in summer, atmospheric oxidation in autumn and probably also by biomass burning in both summer and winter. In this study, we could not see the strong contribution of biomass burning to DHOPA as suggested by previous studies in this region. Instead, good correlations between observed DHOPA and Ox as well as [NO2][O3] suggest the involvement of both ozone (O3) and nitrogen dioxide (NO2) in the formation of DHOPA. The results showed that regional air pollution may not only increase the emissions of aromatic precursors but also can greatly promote the formation processes.

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.

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.

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.

Oxygenated volatile organic compounds (OVOCs) are critical atmospheric ozone and secondary organic aerosol (SOA) precursors and radical sources, while understanding of OVOC sources in the atmosphere, especially with large anthropogenic emissions, still has large uncertainties. A high-sensitivity proton transfer reaction mass spectrometer (PTR-MS) was deployed in vastly different atmospheres in southern China, including an urban site (SZ-U), a regional site (NA-R), and a background site (NL-B). Four critical OVOCs, i.e., methanol, acetone, methyl ethyl ketone (MEK) and acetaldehyde, five groups of aromatic hydrocarbons, isoprene and acetonitrile were measured with a high time resolution. The featured relative abundance and diurnal variations of the OVOCs indicated that methanol, acetone and MEK had prominent contributions from urban industrial activities, while acetaldehyde was closely related to the photochemical formation at all three sites. The photochemical age-based parameterization method was improved locally and then applied to quantify different sources of daytime OVOCs: anthropogenic secondary and biogenic sources (together 60–73%) were always the dominant source for acetaldehyde in various atmospheres; in addition to a significant background for methanol, acetone and MEK, anthropogenic primary emissions (mostly industrial) were their dominant source at SZ-U (38–73%), while biogenic sources played the key role for them at NL-B (30–43%); biomass burning contributed a small fraction of 5–17% for the four OVOCs at the three sites.