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Atmospheric brown carbon (BrC) makes a substantial contribution to aerosol light absorption and thus global radiative forcing. Although BrC may change the lifetime of the clouds and ultimately affect precipitation, little is known regarding the optical properties and formation of BrC in the clouds. In the present study, the light-absorption properties of cloud droplet residual (cloud RES) were measured by coupled a ground-based counterflow virtual impactor (GCVI) and an aethalometer (AE-33), in addition to the cloud interstitial (cloud INT) and ambient (cloud-free) particles by PM2.5 inlet-AE-33 at Mt. Tianjing (1690 m a.s.l.), a remote mountain site in southern China, from November to December 2020. Meanwhile, the light-absorption and fluorescence properties of water-soluble organic carbon (WSOC) in the collected cloud water and PM2.5 samples were also obtained, associated with the concentration of water-soluble ions. The mean light-absorption coefficient (Abs370) of the cloud RES, cloud INT, and cloud-free particles were 0.25 ± 0.15, 1.16 ± 1.14, and 1.47 ± 1.23 Mm−1, respectively. The Abs365 of WSOC was 0.11 ± 0.08 Mm−1 in cloud water and 0.40 ± 0.31 Mm−1 in PM2.5, and the corresponding mass absorption efficiency (MAE365) was 0.17 ± 0.07 and 0.31 ± 0.21 m2 g−1, respectively. A comparison of the light-absorption coefficient between BrC in cloud RES and cloud INT particles, and WSOC in cloud water and PM2.5 indicates a considerable contribution (48 %–75 %) of water-insoluble BrC to total BrC light absorption. Secondary BrC estimated by minimum R squared (MRS) method dominated the total BrC in cloud RES (67 %–85 %), rather than in the cloud-free (11 %–16 %) and cloud INT (9 %–23 %) particles. It may indicate the formation of secondary BrC during cloud processing. Supporting evidence includes the enhanced WSOC and dominant contribution of the secondary formation and biomass burning factor (>80 %) to Abs365 in cloud water provided by positive matrix factorization (PMF) analysis. In addition, we showed that the light absorption of BrC in cloud water was closely related to humic-like substances and tyrosine-like and/or protein-like substances (r>0.63, p

While laboratory studies have demonstrated that aqueous reactions between carbonyls and reduced nitrogen species may contribute to the production of N-heterocycle brown carbon (BrC) such as imidazo...

While the formation and evolution of nitrate in airborne particles are extensively investigated, little is known about the processing of nitrate in clouds. Here we present a detailed investigation on the in-cloud formation of nitrate, based on the size-resolved mixing state of nitrate in the individual cloud residual and cloud-free particles obtained by single particle mass spectrometry, and also the mass concentrations of nitrate in the cloud water and PM2.5 at a mountain site (1690 m a.s.l. – above sea level) in southern China. The results show a significant enhancement of nitrate mass fraction and relative intensity of nitrate in the cloud water and the cloud residual particles, respectively, reflecting a critical role of in-cloud processing in the formation of nitrate. We first exclude the gas-phase scavenging of HNO3 and the facilitated activation of nitrate-containing particles as the major contribution for the enhanced nitrate, according to the size distribution of nitrate in individual particles. Based on regression analysis and theoretical calculations, we then highlight the role of N2O5 hydrolysis in the in-cloud formation of nitrate, even during the daytime, attributed to the diminished light in clouds. Nitrate is highly related (R2= ∼ 0.6) to the variations in [NOx][O3], temperature, and droplet surface area in clouds. Accounting for droplet surface area greatly enhances the predictability of the observed nitrate, compared with using [NOx][O3] and temperature. The substantial contribution of N2O5 hydrolysis to nitrate in clouds with diminished light during the daytime can be reproduced by a multiphase chemical box model. Assuming a photolysis rate at 30 % of the default setting, the overall contribution of N2O5 hydrolysis pathway to nitrate formation increases by ∼ 20 % in clouds. Given that N2O5 hydrolysis acts as a major sink of NOx in the atmosphere, further model updates would improve our understanding about the processes contributing to nitrate production in cloud and the cycling of odd nitrogen.

Nine amine species in atmospheric particles during haze and low-pollution days with low and high relative humidity (RH) were analyzed in urban Guangzhou, China. The mean concentrations of total measured amines (Ʃamines) in fine particles were 208 ± 127, 63.7 ± 21.3, and 120 ± 20.1 ng m

Atmospheric brown carbon (BrC) makes a substantial contribution to aerosol light-absorbing and thus the global radiative forcing. Although BrC may change the lifetime of the cloud and ultimately affect precipitation, little is known regarding the optical properties and formation of BrC in the cloud. In the present study, the light-absorption properties of cloud droplet residual (cloud RES) were measured by coupled a ground-based counterflow virtual impactor (GCVI) and an Aethalometer (AE-33), in addition to the cloud interstitial (cloud INT) and ambient (cloud-free) particles by PM2.5 inlet-AE-33, at Mt. Tianjing (1690 m a.s.l.), a remote mountain site in southern China, from November to December 2020. Meanwhile, the light-absorption and fluorescence properties of water-soluble organic carbon (WSOC) in the collected cloud water and PM2.5 samples were also obtained, associated with the concentration of water-soluble ions. The mean light-absorption coefficient (Abs370) of the cloud RES, cloud INT, and cloud-free particles were 0.25 ± 0.15, 1.16 ± 1.14, and 1.47 ± 1.23 Mm−1, respectively. The Abs365 of WSOC was 0.11 ± 0.08 Mm−1 in cloud water and 0.40 ± 0.31 Mm−1 in PM2.5, and the corresponding mass absorption efficiency (MAE365) was 0.17 ± 0.07 and 0.31 ± 0.21 m2·g−1, respectively. A comparison of the light-absorption coefficient between BrC in the cloud RES/cloud INT and WSOC in cloud water/PM2.5 indicates a considerable contribution (48–75 %) of water-insoluble BrC to total BrC light-absorption. Secondary BrC estimated by minimum R squared (MRS) method dominated the total BrC in cloud RES (67–85 %), rather than in the cloud-free (11–16 %) and cloud INT (9–23 %) particles. It may indicate the formation of secondary BrC during cloud processing. Supporting evidence includes the enhanced WSOC and dominant contribution of secondary formation/biomass burning factor (> 80 %) to Abs365 in cloud water provided by Positive Matrix Factorization (PMF) analysis. In addition, we showed that the light-absorption of BrC in cloud water was closely related to humic-like substances and tyrosine/proteins-like substances (r > 0.63, p < 0.01), whereas only humic-like substances for PM2.5, as identified by excitation-emission matrix fluorescence spectroscopy.

The coexistence of numerous Mississippi Valley-type (MVT) Pb–Zn deposits and oil/gas reservoirs in the world suggests a close genetic relationship between mineralization and hydrocarbon accumulation. The Wusihe MVT Pb–Zn deposits are located along the southwestern margin of the Sichuan Basin. Based on the spatiotemporal relation between Pb–Zn deposits and paleo-oil/gas reservoirs, ore material sources, and processes of mineralization and hydrocarbon accumulation, a new genetic relationship between mineralization and hydrocarbon accumulation is suggested for these deposits. The Wusihe Pb–Zn deposits are hosted in the Ediacaran Dengying Formation dolostone, accompanied by a large amount of thermally cracked bitumen in the ore bodies. The Pb–Zn deposits and paleo-oil/gas reservoirs are distributed along the paleokarst interface; they overlap spatially, and the ore body occupies the upper part of the paleo-oil/gas reservoirs. Both the Pb–Zn ore and sphalerite are rich in thermally cracked bitumen, in which µm sized galena and sphalerite may be observed, and the contents of lead and zinc in the bitumen are higher than those required for Pb–Zn mineralization. The paleo-oil/gas reservoirs experienced paleo-oil reservoir formation, paleo-gas reservoir generation, and paleo-gas reservoir destruction. The generation time of the paleo-gas reservoirs is similar to the metallogenic time. The source rocks from the Cambrian Qiongzhusi Formation not only provided oil sources for paleo-oil reservoirs but also provided ore-forming metal elements for mineralization. Liquid oil with abundant ore-forming metals accumulated to form paleo-oil reservoirs with mature organic matter in source rocks. As paleo-oil reservoirs were buried, the oil underwent in situ thermal cracking to form overpressure paleo-gas reservoirs and a large amount of bitumen. Along with the thermal cracking of the oil, the metal elements decoupled from organic matter and H2S formed by thermochemical sulfate reduction (TSR) and minor decomposition of the organic matter dissolved in oilfield brine to form the ore fluid. The large-scale Pb–Zn mineralization is mainly related to the destruction of the overpressured paleo-gas reservoir; the sudden pressure relief caused the ore fluid around the gas–water interface to migrate upward into the paleo-gas reservoirs and induced extensive metal sulfide precipitation in the ore fluid, resulting in special spatiotemporal associated or paragenetic relations of galena, sphalerite, and bitumen.

Characterizing the molecular composition of cloud water could provide unique insights into aqueous chemistry. Field measurements were conducted at Mt. Tianjing in southern China in May, 2018. There are thousands of formulas (C$_{5-30}$H$_{4-55}$O$_{1-15}$N$_{0-2}$S$_{0-2}$) identified in cloud water by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). CHON formulas (formulas containing C, H, O, and N elements; the same is true for CHO and CHOS) represent the dominant component (43.6 %���65.3 % of relative abundance), followed by CHO (13.8 %���52.1%). S-containing formulas constitute ���5 %���20 % of all assigned formulas. Cloud water has a relative-abundance-weighted average O/C of 0.45���0.56, and the double bond equivalent of 5.10���5.70. Most of the formulas (>85 %) are assigned as aliphatic and olefinic species. No statistical difference in the oxidation state is observed between cloud water and interstitial PM$_{2.5}$. CHON with aromatic structures are abundant in cloud water, suggesting their enhanced in-cloud formation. Other organics in cloud water are mainly from biomass burning and oxidation of biogenic volatile organic compounds. The cloud water contains more abundant CHON and CHOS at night, which are primarily contributed by ���N$_{2}$O$_{5}$ function and organosulfates, demonstrating the enhanced formation in dark aqueous or multi-phase reactions. While more abundant CHO is observed during the daytime, likely due to the photochemical oxidation and photolysis of N- or S-containing formulas. The results provide an improved understanding of the in-cloud aqueous-phase reactions.

Various water-soluble inorganic compounds, including Na+, NH4+, K+, Ca2+, Mg2+, Cl–, NO3–, PO43– and SO42–, were analyzed in 130 sets of size-segregated (< 0.49, 0.49–0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2 and 7.2–10.0 µm) aerosol samples collected from March 2013 to April 2014 in Guangzhou, China. SO42– was unimodally distributed and peaked during a typical droplet mode (0.49–0.95 µm). However, the distribution of NO3– significantly varied across the four seasons. It was unimodally distributed in summer and autumn, peaking in the coarse mode (3.0–7.2 µm), and bimodally distributed in winter and spring, peaking in the size ranges of 0.49–0.95 µm and 3.0–7.2 µm, respectively. The coarse-mode NO3– was mainly related to the influence of soil/dust. The additional mode during winter and spring was attributable to the formation of ammonium nitrate. Compared to clean days, polluted days favored the formation of SO42– in summer and autumn and NO3– in winter and spring. The sulfur oxidation ratios (SORs) for < 0.49, 0.49–0.95 and 0.95–1.5 µm particles were negatively correlated with the relative humidity (RH) in spring, summer and autumn, respectively. However, the SORs for 0.49–3.0 µm particles were positively correlated with the RH in winter, implying an important contribution from the aqueous oxidation of SO2. Further analysis shows that the SO42– in < 0.49 µm particles was formed primarily through gas-phase photochemical oxidation of SO2 during all four seasons. The formation of NO3– was mainly attributable to heterogeneous reactions for 1.5–3.0 µm particles year-round and homogeneous gas-phase reactions for < 0.49 µm particles in winter. Correlation analysis also indicates a positive influence from biomass burning on the formation of nitrate and sulfate. The average pH of PM3 was calculated to be 2.6–5.6. Thus, the aqueous oxidation of SO2 by NO2 plays a limited role in the formation of sulfate in the atmosphere of Guangzhou.

The effect of the mixing state of black carbon (BC) on light absorption is of enduring interest due to its close connection to regional/global climate. Herein, we present concurrent measurements of both BC absorption enhancement (Eabs) and the chemical mixing state in southern China. Eabs was obtained by simultaneous measuring the light absorption coefficient using an aethalometer before and after being heated. The observed Eabs was categorized into non- (Eabs ≤ 1.0), slight (1.0 1.2) enhancement groups, and it was compared to the mixing state of elemental carbon (EC) particles detected by a single particle aerosol mass spectrometer (SPAMS). The individual EC-containing particles were classified into four types, including EC with sodium and potassium ion peaks (NaK-EC), long EC cluster ions (Cn+/−, n ≥ 6) with sulfate (EC-Sul1), short EC cluster ions (Cn+/−, n

Inland transported sea spray aerosol (SSA) particles along with multiphase reactions are essential to drive the regional circulation of nitrogen, sulfur and halogen species in the atmosphere. Specially, the physicochemical properties of SSA will be significantly affected by the displacement reaction of chloride. However, the role of organic species and the mixing state on the chloride depletion of SSA during long-range inland transport remains unclear. Hence, a single particle aerosol mass spectrometer (SPAMS) was employed to investigate the particle size and chemical composition of individual SSA particles over inland southern China during the East Asian summer monsoon. Based on the variation of chemical composition, SSA particles were clustered into SSA-Aged, SSA-Bio and SSA-Ca. SSA-Aged was regarded as the aged Na-rich SSA particles. In comparison to the SSA-Aged, SSA-Bio involved some extra organic species associated with biological origin (i.e., organic nitrogen and phosphate). Each type occupies for approximately 50% of total detected SSA particles. Besides, SSA-Ca may relate to organic shell of Na-rich SSA particles, which is negligible (~3%). Tight correlation between Na and diverse organic acids was exhibited for the SSA-Aged (r2 = 0.52, p < 0.01) and SSA-Bio (r2 = 0.61, p < 0.01), reflecting the impact of organic acids to the chloride displacement during inland transport SSA particles. The chloride depletion occupied by organic acids is estimated to be up to 34%. It is noted that distinctly different degree of chloride depletion was observed between SSA-Aged and SSA-Bio. It is more likely to be attributed to the associated organic coatings for the SSA-Bio particles, which inhibits the displacement reactions between acids and chloride. As revealed from the mixing state of SSA-Bio, defined hourly mean peak area ratio of Cl / Na increases with the increasing phosphate and organic nitrogen. This finding provides additional basis for the improvement of modeling simulations in chlorine circulation and a comprehensive understanding of the effects of organics on chloride depletion of SSA particles.

Heterogeneous reactions on sea spray aerosols (SSA) are the main pathway to drive the circulation of chlorine, nitrogen, and sulfur in the atmosphere. The release of Cl will significantly affect the physicochemical properties of SSA. However, the impact of organic acids and mixing state on chloride depletion of SSA is still unclear. Hence, the size and chemical composition of individual SSA particles during the East Asian summer monsoon were investigated by a single particle aerosol mass spectrometer (SPAMS). According to the chemical composition, SSA particles were classified into SSA-Aged, SSA-Bio and SSA-Ca. In comparison to the aged Na-rich SSA particles (SSA-Aged), some additional organic species related to biological origin were observed in SSA-Bio, and each of two types accounts for approximately 50 % of total SSA particles. SSA-Ca may associated with organic shell of Na-rich SSA particles, which only accounts for ~ 3 %. Strongly positive correlations between Na and organic acids (including formate, acetate, propionate, pyruvate, oxalate, malonate, succinate, and glutarate) were observed for the SSA-Aged (r2 = 0.52, p 2 = 0.61, p&thinsp

The uploaded data contains (1) time series of meterological parameters (temperature,RH, wind direction,wind speed,PM2.5,visibility), LWC, mass concentration of EBC, number concentration of submicron particles and BC-containing particles, (2) size-resolved NSEs for different cloud stages of submicron and BC-containing particles, (3) mass spectrum plots and particle number of three types of BC-containing particles, (4) size distributions of SMPS and SPAMS, and (5) stage-resolved average NSEs and particle sizes for SPAMS detected particles.

The composition, morphology, and mixing structure of individual cloud residues (RES) and interstitial particles (INT) at a mountaintop site were investigated. Eight types of particles were identified, including sulfate-rich (S-rich), S-organic matter (OM), aged soot, aged mineral dust, aged fly ash, aged metal, refractory, and aged refractory mixture. A shift of dominant particle types from S-rich (29 %) and aged soot (27 %) in the INT to aged refractory mixture (23 %) and S-OM (22 %) in the RES is observed. In particular, particles with organic shells are enriched in the RES (27 %) relative to the INT (12 %). Our results highlight that the formation of more oxidized organic matter in the cloud contributes to the existence of organic shells after cloud processing. The fractal dimension (D$_{f}$), a morphologic parameter to represent the branching degree of particles, for soot particles in the RES (1.82 ± 0.12) is lower than that in the INT (2.11 ± 0.09), which indicates that in-cloud processes may result in less compact soot. This research emphasizes the role of in-cloud processes in the chemistry and microphysical properties of individual particles. Given that organic coatings may determine the particle hygroscopicity, activation ability, and heterogeneous chemical reactivity, the increase of OM-shelled particles upon in-cloud processes should have considerable implications.

Amines play an important role in the formation and transformation of atmospheric aerosols. Gaseous phase and PM2.5 samples were collected simultaneously at Nanling Mountains, southern China during autumn 2016 and summer 2017. The site is strongly affected by long distance transport from marine and continental air masses. Five amines, methylamine (MA), dimethylamine (DMA), diethylamine (DEA), dibutylamine (DBA) and morpholine (MOR), were detected by gas chromatography-mass spectrometry (GC-MS) after derivatization. The backward trajectory analyses suggested that different origins of air masses led to seasonal variation of amines. In gaseous phase samples, the average concentrations of total measured amines (Ʃamines) were 193.4 ± 111.7 ng m−3 in autumn 2016 and 307.5 ± 196.7 ng m−3 in summer 2017. In PM2.5 samples, the average concentrations of Ʃamines were 12.4 ± 10.8 ng m−3 in autumn 2016 and 20.7 ± 11.0 ng m−3 in summer 2017. MA and DMA were the dominant amines, together contributing approximately 70% to gaseous amines and 80% to particulate amines. A strong linear relationship was found between Ʃamines and NO3− in PM2.5, implying that amines might mainly exist in the form of aminium nitrate. Ammonium (NH4+) was found mostly likely in the form of ammonia sulfate. Approximately 7.4% of the gaseous total amines partitioned to PM2.5. A good linear relationship between the fraction of total atmospheric concentration sorbed by PM2.5 (Φ) and the concentrations of O3 was found, suggesting that O3 likely played an important factor in the gas-to-particle partitioning of amines. Additionally, under high relative humidity circumstances (92% ± 7.0%), direct dissolution was a crucial step for gaseous amines partitioning into particles. The ratios of amines-C to water-soluble organic carbon (WSOC) and amines-N to water-soluble organic nitrogen (WSON) were 0.21% and 1.57% in autumn 2016 and 0.54% and 2.08% in summer 2017, respectively. The results of this study provide essential information on the formation mechanism of particulate amines.

The formation of secondary organic aerosol (SOA) from isoprene ozonolysis was investigated using a FEP Teflon reactor with and without the presence of H2O, CO, SO2 and UV-light irradiation (365 nm) to reveal their possible influence on SOA formation. Compared with the base experiment (isoprene + O3) under dark condition, the presence of 2000 ppm H2O and 1000 ppm CO could remarkably suppress SOA formation from isoprene ozonolysis, with SOA yields reduced from 2.96% to 1.47% and 2.08%, respectively. The evident reduction of SOA yields from isoprene ozonolysis with the presence of H2O and CO was mainly ascribed to the suppression of Stable Criegee Intermediates (SCIs). In contrast, the particle yield from isoprene ozonolysis with the presence of SO2 pronouncedly increased from 2.96% to 57.9%, suggesting that the oxidation of SO2 by SCIs made great contribution to the particle formation. The SOA or particle yields from all the reaction systems with and without presence of H2O, CO and SO2 reduced more than 27% under the UV-light irradiation with respect to dark condition, which were mainly attributed to the SCIs photolysis. The contribution of OH channel to SOA formation from isoprene ozonolysis was estimated to be less than 30%. Considering the 50% reduction of SOA yield from isoprene ozonolysis under light irradiation, the disappearance of the component with low O:C and H:C and high molecule weight in the SOA sample collected under light irradiation indicated the polymerization of unsaturated SCIs might be an important SOA formation channel besides the oligomerization of SCIs, HCHO, and MACR from isoprene ozonolysis under dark condition.

The coexistence of Zn-Pb deposits and oil/gas reservoirs demonstrates that a close genetic link between them. The Nanmushu is a large Mississippi Valley-Type (MVT) Zn-Pb deposit discovered on the northern margin of the Yangtze block in recent years. The deposit is hosted in the Ediacaran Dengying Formation dolostone, accompanied by large amount of bitumen in the orebodies. The MVT Zn-Pb deposit overlaps with the paleo-oil/gas reservoir horizontally, and sandwiched in the paleo-oil/gas reservoirs at depth. The Cambrian Guojiaba Formation may have provided not only the oil for paleo-oil/gas reservoirs, but also ore metals for the Zn-Pb mineralization. With increasing burial depth, the Guojiaba Formation may have become more mature to form metal-rich fluids, and the metals migrated and accumulated with hydrocarbons to form a paleo-oil reservoir. Large-scale Zn-Pb mineralization may have occurred in the destruction process of paleo-gas reservoir. With the deep burial of paleo-oil reservoir, the paleo-oil reservoir may have transformed into a paleo-gas reservoir. Decoupling of metals and hydrocarbons during the paleo-gas reservoir formation may have provided the ore metals. Thermal sulfate reduction (TSR) during the paleo-oil/gas reservoirs formation may have provided the hydrogen sulfide for mineralization. Decompression and cooling during the paleo-gas reservoir destruction may have formed extensive metal sulfide precipitation and mineralization.

Aims Hair cell reduction was related to diabetes-induced hearing loss. Oxidative stress, endoplasmic reticulum stress, and autophagy participate in this process. Thioredoxin (Trx) is a protein with many biological functions which can regulate them. In this study, aiming to clarify protective effect of Trx on diabetic hearing loss and to identify an early potential therapeutic target for diabetic hearing impairment in the future. Methods Trx transgenic (Tg) mice were used to establish a diabetic model by intraperitoneally injecting streptozotocin (STZ) and with/without SF or PX12 treatment. Succinate dehydrogenase (SDH) staining was used to evaluate the loss of hair cells. The relative expression of related proteins and genes was detected using western blotting and qRT-PCR. Results In vivo, loss of outer hair cells was observed. However, it can be delayed Trx overexpression. Moreover, the expression of PGC-1α, bcl-2 and LC3 was increased in Tg(+)-DM mice compared with Tg(-)-DM mice. The expression of ASK1, Txnip, GRP78, CHOP and p62 was decreased in Tg(+)-DM mice compared with Tg(-)-DM mice. Conclusions Upregulation of Trx protects diabetes-induced cochlear hair cells reduction. The underlying mechanisms were related to the regulation of ER stress through ASK1 and the mitochondrial pathway or autophagy via Txnip.

Size-segregated PM 10 samples were collected in Guangzhou, China during autumn of 2014. Nine amines, including seven aliphatic amines and two heterocyclic amines, were detected using a gas chromatography-mass spectrometer after derivatization by benzenesulfonyl chloride. The total concentration of the nine amines (Ʃamines) was 79.6–140.9 ng m −3 in PM 10 . The most abundant species was methylamine (MA), which had a concentration of 29.2–70.1 ng m −3 . MA, dimethylamine (DMA), diethylamine (DEA) and dibutylamine (DBA) were the predominant amines in the samples and accounted for approximately 80% of Ʃamines in each size segment. Two heterocyclic amines, pyrrolidine (PYR) and morpholine (MOR), were detected in all samples and had average concentrations of 1.14 ± 0.37 and 1.89 ± 0.64 ng m −3 , respectively, in particles with aerodynamic diameters 10 were 7.9 ± 1.6 μg m −2 d −1 and 0.084 ± 0.0021 cm s −1 , respectively. The results of this study provide essential information on the contribution of amines to secondary organic aerosols and dry removal mechanisms in urban areas.

// Xiang Ren 1, * , Chen Li 1, * , Junli Liu 1 , Chenghong Zhang 1 , Yuzhen Fu 1 , Nina Wang 1 , Haiying Ma 1 , Heyuan Lu 1 , Hui Kong 2 and Li Kong 1 1 Department of Histology and Embryology, Dalian Medical University, Dalian 116044, Liaoning Province, China 2 Department of Otorhinolaryngology, The Second Hospital of Dalian Medical University, Dalian 116023, Liaoning Province, China * These authors have contributed equally to this work Correspondence to: Li Kong, email: kongli@dmu.edu.cn Hui Kong, email: konghui6905@163.com Keywords: thioredoxin, diabetes, retina, apoptosis, sulforaphane Received: March 01, 2017 Accepted: April 11, 2017 Published: May 24, 2017 ABSTRACT Diabetes is a chronic metabolic syndrome that results in changes in carbohydrate, lipid and protein metabolism. With diabetes for a long time, it increases the risk of diabetic retinopathy (DR) and long-term morbidity and mortality. Moreover, emerging evidence suggests that neuron damage occurs earlier than microvascular complications in DR patients, but the underlying mechanism is unclear. We investigated diabetes-induced retinal neuropathy and elucidated key molecular events to identify new therapeutic targets for the clinical treatment and prevention of DR. For in vivo studies, a high-fat diet and streptozotocin (STZ) injection were used to generate the diabetes model. Hematoxylin-eosin staining was used for morphological observations and measurements of the outer nuclear layer thickness. Electroretinography (ERG) was used to assess retinal function. For in vitro studies, Neuro2a cells were incubated in normal (5.5 mM) and high-glucose (30 mM) conditions. Flow cytometry assays were performed to analyze apoptosis. Additionally, real-time PCR and Western blotting analyses were carried out to determine gene and protein expression in vitro and in vivo . Taken together, the results indicated that retinal neuropathy occurred prior to endothelial damage induced by diabetes, and thioredoxin (Trx) plays a key role in this process. This underlying mechanism may be related to activation of the Trx/ASK1/p-p38/Trx-interacting protein pathway.

The effects of chemical composition and size of sea salt-containing particles on their cloud condensation nuclei (CCN) activity are incompletely understood. We used a ground-based counterflow virtual impactor (GCVI) coupled with a single particle aerosol mass spectrometer (SPAMS) to characterize chemical composition of submicron (dry diameter of 0.2–1.0 μm) and supermicron (dry diameter of 1.0–2.0 μm) sea salt-containing cloud residues (dried cloud droplets) at Mount Nanling, southern China. Seven cut sizes (7.5–14 μm) of cloud droplets were set in the GCVI system. Approximately 20 % (by number) of the submicron cloud residues included sea salt-containing particles at the cut size of 7.5 μm, which was significantly higher than the percentages at the cut sizes of 8–14 μm (below 2 %). This difference was likely to be involved in the change in the chemical composition. For the cut size of 7.5 μm, nitrate was internally mixed with over 90 % of the submicron sea salt-containing cloud residues, which was higher than sulfate (20 %), ammonium (below 1 %), amines (6 %), hydrocarbon organic species (2 %), and organic acids (4 %). However, nitrate, sulfate, ammonium, amines, hydrocarbon organic species, and organic acids were internally mixed with over 90 %, over 80 %, 39–84 %, 71–86 %, 52–90 %, and 32–77 %, respectively, of the submicron sea salt-containing cloud residues for the cut sizes of 8–14 μm. The proportion of sea salt-containing particles in the supermicron cloud residues generally increased as a function of cut size, and their CCN activity was less influenced by chemical composition. This study highlights the different distribution of the submicron and supermicron sea salt-containing particles in various cloud droplets, which might further influence their atmospheric residence time.

Interactions between clouds and black carbon (BC) represent a significant uncertainty in aerosol radiative forcing. To investigate the influence of cloud processing on the scavenging of BC, concurrent measurement of individual cloud droplet residue particles (cloud RES) and interstitial particles (cloud INT) throughout a cloud event was deployed at Mt. Tianjing (1690 m a.s.l.) in southern China. An aethalometer (AE-33), a single particle aerosol mass spectrometer (SPAMS) and a scanning mobility particle sizer (SMPS) were used to investigate the mass concentration of equivalent BC (EBC), size-resolved number of BC-containing particles, and size-resolved number concentration of submicron particles in real-time, respectively. The number-based SEs of the submicron particles varied between 2.7 and 31.1%. Mass scavenging efficiency (MSE) ranged from 4.7% to 52.6% for EBC, consistent with the number-based SE (from 11.3% to 59.6%) of the BC-containing particles throughout the cloud event. Several factors that may influence the SEs of the BC-containing particles are considered and examined. SEs are most likely determined by a single factor, i.e., liquid water content (LWC), with R2 > 0.8 in a power function throughout the cloud event. Stage-resolved investigation of SEs further reveals that particle size matters more than other factors in the cloud formation stage, whereas there is an increasing role of the mixing state in the development and stability stage. We also observed lower SEs for the BC-containing particles internally mixed organics, consistent with previous literature.

Amines are ubiquitous in the environment and pose potential impacts on atmospheric chemistry; however, their seasonal variations and atmospheric processes remain unclear. In this study, a single-particle aerosol mass spectrometer is employed to investigate the seasonal variations of amine-containing particles as well as the oxidation of trimethylamine (TMA) in the urban region of Guangzhou, China. Number fractions of the amine-containing particles exhibit distinct seasonal variations, with higher fractions in spring and summer. Four amines, namely, TMA, diethylamine (DEA), dipropylamine, and tripropylamine are observed over all the seasons. DEA and TMA are the most dominant and account for approximately 90% of all these amine-containing particles. They are mainly clustered into eight types, comprised of internally mixed organics and elemental carbon (OCEC), OC–K, EC, Metal–rich, Dust, NaK–EC, Amine–rich, and high molecular weight organic compounds. DEA and TMA distribute differently over particle types and exhibit a distinct mixing state because of their different physicochemical properties. Compared with TMA, DEA is associated with more sulfate. The possible oxidation of TMA is also investigated, and the results indicate the potential contribution of aqueous oxidation or NO3 radical oxidation to the formation of TMA oxide. Overall, the results improve the comprehension of the formation and evolution processes of amines in atmospheric environment.

Understanding how historical climate and land cover changes have affected tropospheric ozone in East Asia would help constrain the large uncertainties associated with future East Asian air quality projections. We perform a series of simulations using a global chemical transport model driven by assimilated meteorological data and a suite of land cover and land use data to examine the public health effects associated with changes in climate, land cover, land use, and anthropogenic emissions between the 5-year periods 1981–1985 and 2007–2011 in East Asia. We find that between these two periods land cover change alone could lead to a decrease in summertime surface ozone by up to 4 ppbv in East Asia and ~ 2000 fewer ozone-related premature deaths per year, driven mostly by enhanced dry deposition resulting from climate- and CO2-induced increase in vegetation density, which more than offsets the effect of reduced isoprene emission arising from cropland expansion. Climate change alone could lead to an increase in summertime ozone by 2–10 ppbv in most regions of East Asia and ~ 6000 more premature deaths annually, mostly attributable to warming. The combined impacts (−2 to +12 ppbv) show that while the effect of climate change is more pronounced, land cover change could offset part of the climate effect and lead to a previously unknown public health benefit. While the changes in anthropogenic emissions remain the largest contributor to deteriorating ozone air quality in East Asia over the past 30 years, we show that climate change and land cover changes could lead to a substantial modification of ozone levels, and thus should come into consideration when formulating future air quality management strategies. We also show that the sensitivity of surface ozone to land cover change is more dependent on dry deposition than on isoprene emission in most of East Asia, leading to ozone responses that are quite distinct from that in North America, where most ozone-vegetation sensitivity studies to date have been conducted.

We have developed a novel framework ("Tan-Tracker") for assimilating observations of atmospheric CO2 concentrations, based on the POD-based (proper orthogonal decomposition) ensemble four-dimensional variational data assimilation method (PODEn4DVar). The high flexibility and the high computational efficiency of the PODEn4DVar approach allow us to include both the atmospheric CO2 concentrations and the surface CO2 fluxes as part of the large state vector to be simultaneously estimated from assimilation of atmospheric CO2 observations. Compared to most modern top-down flux inversion approaches, where only surface fluxes are considered as control variables, one major advantage of our joint data assimilation system is that, in principle, no assumption on perfect transport models is needed. In addition, the possibility for Tan-Tracker to use a complete dynamic model to consistently describe the time evolution of CO2 surface fluxes (CFs) and the atmospheric CO2 concentrations represents a better use of observation information for recycling the analyses at each assimilation step in order to improve the forecasts for the following assimilations. An experimental Tan-Tracker system has been built based on a complete augmented dynamical model, where (1) the surface atmosphere CO2 exchanges are prescribed by using a persistent forecasting model for the scaling factors of the first-guess net CO2 surface fluxes and (2) the atmospheric CO2 transport is simulated by using the GEOS-Chem three-dimensional global chemistry transport model. Observing system simulation experiments (OSSEs) for assimilating synthetic in situ observations of surface CO2 concentrations are carefully designed to evaluate the effectiveness of the Tan-Tracker system. In particular, detailed comparisons are made with its simplified version (referred to as TT-S) with only CFs taken as the prognostic variables. It is found that our Tan-Tracker system is capable of outperforming TT-S with higher assimilation precision for both CO2 concentrations and CO2 fluxes, mainly due to the simultaneous estimation of CO2 concentrations and CFs in our Tan-Tracker data assimilation system. A experiment for assimilating the real dry-air column CO2 retrievals (XCO2) from the Japanese Greenhouse Gases Observation Satellite (GOSAT) further demonstrates its potential wide applications.

Black carbon (BC) aerosol is of great importance not only for its strong potential in heating air and impacts on cloud, but also because of its hazards to human health. Wet deposition is regarded as the main sink of BC, constraining its lifetime and thus its impact on the environment and climate. However, substantial controversial and ambiguous issues in the wet scavenging processes of BC are apparent in current studies. Despite of its significance, there are only a small number of field studies that have investigated the incorporation of BC-containing particles into cloud droplets and influencing factors, in particular, the in-cloud scavenging, because it was simplicitly considered in many studies (as part of total wet scavenging). The mass scavenging efficiencies (MSEs) of BC were observed to be varied over the world, and the influencing factors were attributed to physical and chemical properties (e.g., size and chemical compositions) and meteorological conditions (cloud water content, temperature, etc.). In this review, we summarized the MSEs and potential factors that influence the in-cloud and below-cloud scavenging of BC. In general, MSEs of BC are lower at low-altitude regions (urban, suburban, and rural sites) and increase with the rising altitude, which serves as additional evidence that atmospheric aging plays an important role in the chemical modification of BC. Herein, higher altitude sites are more representative of free-tropospheric conditions, where BC is usually more aged. Despite of increasing knowledge of BC–cloud interaction, there are still challenges that need to be addressed to gain a better understanding of the wet scavenging of BC. We recommend that more comprehensive methods should be further estimated to obtain high time-resolved scavenging efficiency (SE) of BC, and to distinguish the impact of in-cloud and below-cloud scavenging on BC mass concentration, which is expected to be useful for constraining the gap between field observation and modeling simulation results.

The complexity of multi-objective evolutionary algorithms based on the non-dominated principles mainly depends on finding non-dominated fronts. In order to reduce complexity and improve construction efficiency, this paper introduces a non-dominated set construction algorithm based on Two Dimensional Sequence (TSNS). When the non-dominated set closes to the Pareto optimal front, it always maintains one dimension by ascending order while the other dimension by descending order. In order to verify the effectiveness of the proposed algorithm, we integrate the algorithm into GA, DE, PSO, then we tested and compared it with classical benchmark functions. The experimental results indicate that the proposed algorithm performs better than NSGA-II in terms of the quality of solutions and the speed of convergence.