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To better understand the origins and seasonality of atmospheric aerosols in North China, we collected fine aerosols (PM2.5) at an urban site (Nankai District, ND) and a suburban site (Haihe Education Park, HEP) in Tianjin from July 2018 to July 2019. The PM2.5 was studied for carbonaceous, nitrogenous and ionic components and stable carbon and nitrogen isotope ratios of total carbon (δ13CTC) and nitrogen (δ15NTN). On average, the mass concentrations of PM2.5, organic carbon (OC), elemental carbon (EC) and water-soluble OC (WSOC) were higher in winter than in summer at both ND and HEP. SO42-, NO3- and NH4+ were the dominant ions, and their sum accounted for 89 % of the total ionic mass at ND and 87 % at HEP. NO3- and NH4+ peaked in winter and were at their minimum in summer, whereas SO42- was higher in summer than in all the other seasons at HEP and was comparable among the seasons, although it peaked in winter at ND. δ13CTC and δ15NTN were −26.5 ‰ to −21.9 ‰ and +1.01 ‰ to +22.8 ‰ at ND and −25.5 ‰ to −22.8 ‰ and +4.91 ‰ to +18.6 ‰ at HEP. Based on seasonal variations in the measured parameters, we found that coal and biomass combustion emissions are the dominant sources of PM2.5 in autumn and winter, while terrestrial and/or marine biological emissions are important in spring and summer in the Tianjin region, North China. In addition, our results implied that the secondary formation pathways of secondary organic aerosols in autumn/winter were different from those in spring/summer; i.e., they might be driven by NO3 radicals in the former period.

Redfield first reported a carbon: nitrogen (C:N) ratio of approximately 6.6 in marine phytoplankton. However, recent studies show that phytoplankton C:N ratio has a large range (marine: 6.5-9.9; freshwater: 7.8-10.5) and is species-specific.These studies pose a great challenge to phytoplankton stoichiometric homeostasis, which traditionally refers to their ability to maintain relatively stable elemental composition with the variation in external nutrient availability. The underlying mechanisms of the interaction between phytoplankton stoichiometric homeostasis and nutrient availability need further clarification. Therefore, in the field seven reservoirs in Tianjin, North China, were investigated to understand their phytoplankton C:N ratios and the influencing factors, and in the laboratory, Chlamydomonas reinhardtii, as a model organism, was used to investigate its C and N metabolism and relevant physiological parameters under different C and N availability. Transcriptome sequencing, nano-scale secondary ion mass spectrometry, and C stable isotope analysis were used to understand cellular C-N metabolism at the molecular level, cellular C-N compartmentation, and C utilization strategy, respectively, in the culture experiment. The main aim of this study was to understand how C-N availability affects the C:N ratio of freshwater phytoplankton at the molecular level.The results indicated that CO2 limitation had no significant effect on the phytoplankton C:N ratio in either scene, whereas limitation of dissolved inorganic N induced the ratio to be a 35% higher in the field and a 138% higher in the laboratory, respectively. Under CO2 limitation, algal CO2-concentrating mechanisms were operated to ensure a C supply, and coupled C-N molecular regulation remained the cellular C:N ratio stable. Under nitrate limitation, differentially expressed gene-regulated intensities increase enormously, and their increasing proportion was comparable to that of the algal C:N ratio; cellular metabolism was reorganized to form a “subhealthy” C-N stoichiometric state with high C:N ratios. In addition, the N transport system had a specific role under CO2 and nitrate limitations. This study implies that algal stoichiometric homeostasis depends on the involved limitation element and will help to deepen the understanding of C-N stoichiometric homeostasis in freshwater phytoplankton.

Little is known about the formation processes of nitrooxy organosulfates (OSs) by nighttime chemistry. Here we characterize nitrooxy OSs at a molecular level in firework-related aerosols in urban Beijing during Chinese New Year. High-molecular-weight nitrooxy OSs with relatively low H / C and O / C ratios and high unsaturation are potentially aromatic-like nitrooxy OSs. They considerably increased during New Year's Eve, affected by the firework emissions. We find that large quantities of carboxylic-rich alicyclic molecules possibly formed by nighttime reactions. The sufficient abundance of aliphatic-like and aromatic-like nitrooxy OSs in firework-related aerosols demonstrates that anthropogenic volatile organic compounds are important precursors of urban secondary organic aerosols (SOAs). In addition, more than 98 % of those nitrooxy OSs are extremely low-volatility organic compounds that can easily partition into and consist in the particle phase and affect the volatility, hygroscopicity, and even toxicity of urban aerosols. Our study provides new insights into the formation of nitrooxy organosulfates from anthropogenic emissions through nighttime chemistry in the urban atmosphere.

Organic aerosols (OA) that make up a large fraction (up to 90%) of the fine aerosol (PM2.5) mass have severe impact on the Earth’s climate system and can cause adverse risk to human health. Diacids and related compounds are ubiquitous in PM2.5 in different environments and accounts for a substantial fraction in OA. Because of their high water-solubility, they can influence the hygroscopic properties and capacity of cloud condensation nuclei formation activity of aerosols and thus affect the indirect radiative forcing in the atmosphere. However, their origins, secondary formation and transformations and seasonality are not fully understood yet. To better understand the seasonal characteristics, origins and photochemical processing of OA in the Tianjin region, North China, we studied the molecular distributions and seasonal variations of water-soluble diacids, oxoacids and α-dicarbonyls in PM2.5 collected at an urban and a suburban sites in Tianjin, an ideal location to study the aerosols, over a one-year period from July 2018 to June 2019. We found significant changes in concentrations and composition of diacids and related compounds from season to season at both the sites. Here, based on the results obtained together with the meteorology, oxidants (O3 and NO2) and SO2, loading and the backward air mass trajectories, we discuss the possible origins and possible secondary formation pathways of diacids and related compounds in the Tianjin region.

Soil water stable isotope compositions (SWSI; i.e., δD and δ18O) and soil moisture content (SMC) are widely used to illuminate water exchange processes across the atmosphere-land interface. Thus, the knowledge of spatiotemporal dynamics of these two variables is critical to help our understanding of relevant ecohydrological processes. However, in comparison to the efforts for elucidating the spatiotemporal variability in SMC, much less attention was paid to understand the spatiotemporal variability in SWSI, which also raises the question as to whether SWSI and SMC share similar spatiotemporal features. To this end, the spatiotemporal dynamics of SWSI and SMC were jointly investigated on a karst hillslope with eight sampling campaigns among two years. The method of temporal stability analysis (TSA) was adopted to evaluate the spatiotemporal patterns of SWSI and SMC in this study. Generally, both δD and δ18O exhibited considerable temporal and spatial variations; meanwhile, the variations in δD and δ18O values were relatively smaller than that of SMC. In addition, in comparison with the spatial pattern of SMC, there were no clear relationships between the standard deviation (SD) and the spatial mean of δD or δ18O. However, the SD of line-conditioned excess (lc-excess) and its mean values displayed a strong negative correlation, indicating that the spatial variations in lc-excess increased with soil evaporation. Moreover, SWSI displayed weaker temporal stability than SMC and no clear controlling factors were identified, suggesting that the spatiotemporal dynamics of SWSI might be more complex than that of SMC. This study provided comprehensive field evidence that there existed profound spatiotemporal variability in SWSI and its spatiotemporal features were different from SMC, highlighting that the spatiotemporal variability in SWSI needs to be considered in isotope-based estimations and it should be investigated separately from the spatiotemporal characteristics of SMC in future studies.

Secondary organic aerosols (SOA) that account for a substantial and often a dominant fraction of total OA mass are formed by photooxidation of various precursors derived from anthropogenic and biogenic sources in the atmosphere. They have serious impacts on the Earth’s climate system directly by scattering and absorbing solar radiation and indirectly by acting as cloud condensation nuclei, and adverse effects on human health. In recent times, considerable attention has been paid on laboratory studies, preferably in gas-phase, in order to understand the chemistry of SOA formation. However, the studies on SOA formation in aqueous phase are limited, which are mainly focused on high abundant volatile organic compounds (e.g., isoprene) and/or their oxidation products, but not on fatty acids (except oleic acid). To better understand the air-water interface photochemistry of fatty acids and their transformations to lower homologous monoacids and more oxygenated species such as diacids and related compounds in atmospheric waters (fog, cloud and aqueous aerosol), we conducted batch UV irradiation experiments on a saturated (stearic acid, C18H36O2) and an unsaturated (linoleic acid, C18H32O2) fatty acids for different time periods (age, 0-120 h) in aqueous-phase. All the irradiated samples were analyzed for measurements of mono- and di-acids, oxoacids and α-dicarbonyls. We found high abundances of monoacids followed by diacids, pyruvic acid and α-dicarbonyls in less aged samples, whereas C3 and C4 diacids were abundant in the more aged samples. Our results imply that the photochemical oxidation of fatty acids and subsequent transformations of the product species in atmospheric waters are significant and their contribution to more oxygenated SOA is increased with aging in the atmosphere.

The present study seeks to evaluate the application of the 238U-234U-230Th radioactive disequilibrium methodology for the determination of the regolith production rates in thick weathering profiles marked by long histories, encountered under various climate regimes, but still very little studied by these techniques. For this purpose, 238U-234U-230Th disequilibria have been analyzed in a ≈ 11 m-deep profile developed on a granitic bedrock in south China (Longnan, Jiangxi Province) under a subtropical climate. The results demonstrate that in such deep weathering profiles the determination of weathering rates from the analysis of U-series nuclides in bulk rock samples cannot be recovered by applying in one step to the entire alteration profile the modeling approach classically used to interpret the U-series nuclides, i.e. the “gain and loss” model. The modeling has to be made on subsections of relatively small size (10Be data from the same profile, when assuming non steady-state erosion of the upper part of the profile. Slow denudation rates similar to the U-series derived production rates of 2 m/Ma can thus be obtained with a minimum exposure time of 40 ky, and an inherited component of 20-25*104 at/g originating from the exhumed deeper part of the profile. Altogether the data demonstrate that the combined analysis of U-series and cosmogenic nuclides, which has the potential to become a relevant approach to constrain the dynamics of continental surfaces, requires (a) dense and deep sampling for both nuclides studies, and (b) also to consider more systematically the polyphased and variable history of erosion of the continental surface during the Quaternary. These results have implications for the interpretation of long-term accumulation of 10Be at depth and 10Be data variations in granitic alteration profiles.

Firework (FW) emission has strong impacts on air quality and public health. However, little is known about the molecular composition of FW-related airborne particulate matter (PM) especially the organic fraction. Here we describe the detailed molecular composition of Beijing PM collected before, during, and after a FW event in New Year's Eve evening in 2012. Subgroups of CHO, CHNO, and CHOS were characterized using ultrahigh resolution Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry. These subgroups comprise substantial fraction of aromatic-like compounds with low O/C ratio and high degrees of unsaturation, some of which plausibly contributed to the formation of brown carbon in Beijing PM. Moreover, we found that the number concentration of sulfur-containing compounds especially the organosulfates was increased dramatically by the FW event, whereas the number concentration of CHO and CHON doubled after the event. The co-variation of CHO, CHON, and CHOS subgroups was suggested to be associated with multiple atmospheric aging processes of aerosols including the multiphase redox chemistry driven by NOx, O3, and •OH. These findings highlight that FW emissions can lead to a sharp increase of high molecular weight compounds particularly aromatic-like substances in urban PM, which may affect the light absorption properties and adverse health effects of atmospheric aerosols.

Using isotope mixing model (IsoSource) and natural δ15N method, this study evaluated contributions of major sources to N of PM2.5 at Beijing (collected during a severe haze episode of January 22nd–30th, 2013) and a background site (Menyuan, Qinghai province; collected from September to October of 2013) of China. At Beijing, δ15N values of PM2.5 (−4.1 – +13.5 ‰; mean = +2.8 ± 6.4 ‰) distributed within the range reported for major anthropogenic sources (including NH3 and NO2 from coal combustion, vehicle exhausts and domestic wastes/sewage). However, δ15N values of PM2.5 at the background site (+8.0 – +27.9 ‰; mean = +18.5 ± 5.8 ‰) were significantly higher than that of potential sources (including NH3 and NO2 from biomass burning, animal wastes, soil N cycle, fertilizer application, and organic N of soil dust). Evidences from molecular ratios of NH4+ to NO3− and/or SO42− in PM2.5, NH3 to NO2 and/or SO2 in ambient atmosphere suggested that the equilibrium of NH3 ↔ NH4 + caused apparent 15N enrichment only in NH4 + of PM2.5 at the background site due to more abundant NH3 than SO2 and NO2. Therefore, a net 15N enrichment (33 ‰) was assumed for NH3 sources of background PM2.5 when fractional contributions were estimated by IsoSource model. Results showed that 41 %, 30 % and 14 % of N in PM2.5 of Beijing originated from coal combustion, vehicle exhausts and domestic wastes/sewage, respectively. Background PM2.5 derived N mainly from biomass burning (58 %), animal wastes (15 %) and fertilizer application (9 %). These results revealed the regulation of the stoichiometry between ammonia and acidic gases on δ15N signals in PM2.5. Emissions of NO2 from coal combustion and NH3 from urban transportation should be strictly controlled to advert the risk of haze episodes in Beijing.