Search

Simple Summary: Triple-negative breast cancer (TNBC) is characterized by a quick and high rate of recurrence. The benefits from neo-adjuvant chemotherapy associated with anti-PDL1 have been shown to be efficient in this aggressive form of breast cancer. Ferroptosis inducers (erastin/RSL3) induced the upregulation of CD274 in TNBC cells. Basal and TNBC subtypes of breast cancers overexpressed CD274 conjointly with three ferroptosis drivers: TNFAIP3, IFNG and IDO1 (IDO1: inhibitory immune checkpoint). These tumors present higher levels of recurrence. A potential synergy of ferroptosis inducers with anti-PD-L1 immunotherapy is suggested in recurrent TNBC. (1) Background: Triple-negative breast cancer (TNBC) is a distinct subgroup of breast cancer presenting a high level of recurrence, and neo-adjuvant chemotherapy is beneficial in its therapy management. Anti-PD-L1 immunotherapy improves the effect of neo-adjuvant therapy in TNBC. (2) Methods: Immune-modulation and ferroptosis-related R-packages were developed for integrative omics analyses under ferroptosis-inducer treatments: TNBC cells stimulated with ferroptosis inducers (GSE173905, GSE154425), single cell data (GSE191246) and mass spectrometry on breast cancer stem cells. Clinical association analyses were carried out with breast tumors (TCGA and METABRIC cohorts). Protein-level validation was investigated through protein atlas proteome experiments. (3) Results: Erastin/RSL3 ferroptosis inducers upregulate CD274 in TNBC cells (MDA-MB-231 and HCC38). In breast cancer, CD274 expression is associated with overall survival. Breast tumors presenting high expression of CD274 upregulated some ferroptosis drivers associated with prognosis: IDO1, IFNG and TNFAIP3. At the protein level, the induction of Cd274 and Tnfaip3 was confirmed in breast cancer stem cells under salinomycin treatment. In a 4T1 tumor treated with cyclophosphamide, the single cell expression of Cd274 was found to increase both in myeloid- and lymphoid-infiltrated cells, independently of its receptor Pdcd1. The CD274 ferroptosis-driver score computed on a breast tumor transcriptome stratified patients on their prognosis: low score was observed in the basal subgroup, with a higher level of recurrent risk scores (oncotypeDx, ggi and gene70 scores). In the METABRIC cohort, CD274, IDO1, IFNG and TNFAIP3 were found to be overexpressed in the TNBC subgroup. The CD274 ferroptosis-driver score was found to be associated with overall survival, independently of TNM classification and age diagnosis. The tumor expression of CD274, TNFAIP3, IFNG and IDO1, in a biopsy of breast ductal carcinoma, was confirmed at the protein level (4) Conclusions: Ferroptosis inducers upregulate PD-L1 in TNBC cells, known to be an effective target of immunotherapy in high-risk early TNBC patients who received neo-adjuvant therapy. Basal and TNBC tumors highly expressed CD274 and ferroptosis drivers: IFNG, TNFAIP3 and IDO1. The CD274 ferroptosis-driver score is associated with prognosis and to the risk of recurrence in breast cancer. A potential synergy of ferroptosis inducers with anti-PD-L1 immunotherapy is suggested for recurrent TNBC. [ABSTRACT FROM AUTHOR]

Particulate secondary organic nitrates play a key role in understanding secondary organic aerosol production, ozone formation, and the atmospheric nitrogen cycle. However, the formation of particulate secondary organic nitrates in ambient air remains poorly understood. In this study, the nighttime formation processes of particulate secondary organic nitrates were investigated based on size‐resolved aerosols measured in urban air of China with a soot particle long‐time‐of‐flight aerosol mass spectrometer. The results show a bimodal size distribution of particulate secondary organic nitrates, peaking at ∼350 nm in condensation mode (100–400 nm) and ∼750 nm in droplet mode (400–2,500 nm), respectively. The nighttime formation processes of particulate secondary organic nitrates in the two size modes were respectively governed by temperature‐dependent condensation and aqueous‐phase processing. In particular, the mass concentration of particulate secondary organic nitrates in condensation mode was positively correlated with nitrate radical production and negatively correlated with temperature, suggesting that the formation processes were associated with the gas‐particle conversion of nitrate radical oxidation products. In contrast, the enhanced particulate secondary organic nitrates in droplet mode were predominantly contributed by aqueous‐phase processing, as indicated by the strong positive correlation with aerosol liquid water content and typical fragment ions from aqueous processing products (r = 0.52–0.59, P < 0.01). Our results highlight the potential of a size‐dependent mechanism to elucidate the formation processes of particulate secondary organic nitrates. Plain Language Summary: Particulate organic nitrates are an important nitrogen‐containing compound in the ambient atmosphere and have significant effects on air quality. However, the formation processes of particulate organic nitrates are complex in ambient air, leading to difficulties in understanding of their atmospheric processes and impacts. Here, nighttime formation of particulate secondary organic nitrates in different size particles is investigated in urban air. The results show that the nighttime formation pathways of particulate secondary organic nitrates in different size particles are distinct. Furthermore, aqueous processing plays an important role in the nighttime formation of particulate secondary organic nitrates in large size particles, especially in fog‐rain days. This information provides for a better understanding of the formation of particulate secondary organic nitrates in ambient air and is useful for future design of laboratory and atmospheric chemistry model studies. Key Points: Particulate secondary organic nitrates concentrations were significantly enhanced during fog‐rain days compared to non‐fog‐rain daysSize distributions of secondary organic nitrates were characterized by bimodal structure, peaking at ∼350 and ∼750 nm, respectivelyThe nighttime formation of organic nitrates in two size modes was respectively dominated by gas‐particle partitioning and aqueous processing [ABSTRACT FROM AUTHOR]

(1) Background: Breast cancer is a frequent heterogeneous disorder diagnosed in women and causes a high number of mortality among this population due to rapid metastasis and disease recurrence. Ferroptosis can inhibit breast cancer cell growth, improve the sensitivity of chemotherapy and radiotherapy, and inhibit distant metastases, potentially impacting the tumor microenvironment. (2) Methods: Through data mining, the ferroptosis/extracellular matrix remodeling literature text-mining results were integrated into the breast cancer transcriptome cohort, taking into account patients with distant relapse-free survival (DRFS) under adjuvant therapy (anthracyclin + taxanes) with validation in an independent METABRIC cohort, along with the MDA-MB-231 and HCC338 transcriptome functional experiments with ferroptosis activations (GSE173905). (3) Results: Ferroptosis/extracellular matrix remodeling text-mining identified 910 associated genes. Univariate Cox analyses focused on breast cancer (GSE25066) selected 252 individual significant genes, of which 170 were found to have an adverse expression. Functional enrichment of these 170 adverse genes predicted basal breast cancer signatures. Through text-mining, some ferroptosis-significant adverse-selected genes shared citations in the domain of ECM remodeling, such as TNF, IL6, SET, CDKN2A, EGFR, HMGB1, KRAS, MET, LCN2, HIF1A, and TLR4. A molecular score based on the expression of the eleven genes was found predictive of the worst prognosis breast cancer at the univariate level: basal subtype, short DRFS, high-grade values 3 and 4, and estrogen and progesterone receptor negative and nodal stages 2 and 3. This eleven-gene signature was validated as regulated by ferroptosis inductors (erastin and RSL3) in the triple-negative breast cancer cellular model MDA-MB-231. (4) Conclusions: The crosstalk between ECM remodeling-ferroptosis functionalities allowed for defining a molecular score, which has been characterized as an independent adverse parameter in the prognosis of breast cancer patients. The gene signature of this molecular score has been validated to be regulated by erastin/RSL3 ferroptosis activators. This molecular score could be promising to evaluate the ECM-related impact of ferroptosis target therapies in breast cancer. [ABSTRACT FROM AUTHOR]

Oxygenated organic molecules (OOMs) are dominated by the N-containing species in polluted urban environments. As N-containing OOMs, especially those with more than one nitrogen atom, prevail in the high m/z (mass-to-charge) range (m/z> 350 Th), unambiguous identification of N-containing OOMs is highly desirable for understanding of their formation processes, precursors and influencing factors. To achieve this, we applied an ultra-high-resolution chemical-ionization Orbitrap (CI-Orbitrap) in a field campaign and found that OOMs contain one (1N-OOMs), two (2N-OOMs) and three (3N-OOMs) nitrogen atoms comprised 50 %, 26 % and 4 %, respectively, of total OOMs. More interestingly, the fraction of 2N-OOMs increased with the increase in carbon number (nC) and was dominated by the ones derived from aliphatic precursors (2N-OOM Ali , 64.2 %), indicating the importance of multistep oxidation. Plausible precursors of 2N-OOMs were aliphatics (2N-OOM Ali , 64.2 %), aromatics (2N-OOM Aro , 16 %) and monoterpenes (2N-OOM MT , 15.4 %). The absolute concentrations of 2N-OOMs were greatly affected by the pollution level for most cases. The 2N-OOM Ali was the most abundant 2N-OOM, and its fraction even increased on the polluted day with an enhanced proportion of the ones with nC >10. While 2N-OOM Ali and 2N-OOM Aro were dominated by daytime photochemical production, nighttime NO 3 -initiated oxidation played a comparable role to the daytime photochemistry in the formation of 2N-OOM MT. The 2N-OOM Aro species were of the highest oxygenation level, followed by 2N-OOM MT and 2N-OOM Ali , which were affected by photochemistry and NO x concentrations. These results highlight the significant formation of 2N-OOMs and the influencing factors on their formation in polluted urban environments, where various volatile organic compound (VOC) precursors and atmospheric oxidants are present. [ABSTRACT FROM AUTHOR]

Growing evidence links intra-urban gradients in atmospheric fine particles (PM2.5), a complex and variable cocktail of toxic chemicals, to adverse health outcomes. Here, we propose an improved hierarchical deep learning model framework to estimate the hourly variation of PM2.5 mass concentration at the street level. By using a full-year monitoring data (including meteorological parameters, hourly concentrations of PM2.5, and gaseous precursors) from multiple stations in Shanghai, the largest city in China, as a training dataset, we first apply a convolutional neural network to obtain cross-domain and time-series features so that the inherent features of air quality and meteorological data associated with PM2.5 can be effectively extracted. Next, a Gaussian weight calculation layer is used to determine the potential interaction effects between different regions and neighboring stations. Finally, a long and short-term memory model layer is used to efficiently extract the temporal evolution characteristics of PM2.5 concentrations from the previous output layer. Further comparative analysis reveals that our proposed model framework significantly outperforms previous benchmark methods in terms of the stability and accuracy of PM2.5 prediction, which has important implications for the intra-urban health assessment of PM2.5-related pollution exposures. [ABSTRACT FROM AUTHOR]

Gaseous amines have recently been identified as the key precursors for frequent new particle formation in polluted urban atmospheres. An open question that arises is why amines are abundant in urban areas despite the absence of agricultural emissions. Here, using the Vocus Proton‐Transfer‐Reaction Time‐of‐Flight Mass‐Spectrometry Mobile Laboratory, we present highly time‐resolved and ultrasensitive measurements of amines to elucidate their atmospheric abundance and source distribution over the Yangtze River Delta city cluster. Our results show strong spatiotemporal heterogeneity in atmospheric C2‐ and C3‐amine levels across various landscapes. Unexpectedly, we found that urban areas were ubiquitous hotspots of amines while amine source strength from agricultural areas were rather low. Corroborated by source measurements and source tracers, all of the evidence suggest that nonagricultural emissions are the most important sources responsible for the observed patterns of urban atmospheric amines, implying significant consequences for the global amine emission inventory. Plain Language Summary: Recently, the cluster formation of sulfuric acid‐dimethylamine‐H2O has been identified as an important mechanism to explain the frequent formation of new particles in urban polluted atmospheres. However, the interest in gaseous amines across the aerosol scientific community contrasts sharply with the extremely sparse information on their sources and atmospheric abundance. In this study, we present the first mobile measurements showing that the source strength of amines from agricultural areas is modest, thus questing the long‐held assumption that the agricultural sources of amines are similar to those of ammonia. In the case of C2 amines, industrial processes are considered to be an important emission pathway. The dominance of nonagricultural sources, such as fuel combustion, in C3 amines is likely to assign these volatile amine compounds a key function in enhancing new particle formation in polluted atmospheres. Key Points: Mobile measurements are a powerful approach to map major sources of gaseous aminesIn highly urbanized areas, nonagricultural emission sources dominate atmospheric aminesC2 and C3 amines are mainly originated from industrial and mobile sources, respectively [ABSTRACT FROM AUTHOR]

Ammonia (NH3) is an important agent involved in atmospheric chemistry and nitrogen cycling. Current estimates of NH3 emissions from biomass burning (BB) differ by more than a factor of 2, impeding a reliable assessment of their environmental consequences. Combining high-resolution satellite observations of NH3 columns with network measurements of the concentration and stable nitrogen isotope composition (δ15N) of NH3 , we present coherent estimates of the amount of NH3 derived from BB in the heartland of Southeast Asia, a tropical monsoon environment. Our results reveal a strong variability in atmospheric NH3 levels in time and space across different landscapes. All of the evidence on hand suggests that anthropogenic activities are the most important modulating control with respect to the observed patterns of NH3 distribution in the study area. N-isotope balance considerations revealed that during the intensive fire period, the atmospheric input from BB accounts for no more than 21±5 % (1σ) of the ambient NH3 , even at the rural sites and in the proximity of burning areas. Our N-isotope-based assessment of the variation in the relative contribution of BB-derived NH3 is further validated independently through the measurements of particulate K+ , a chemical tracer of BB. Our findings underscore that BB-induced NH3 emissions in tropical monsoon environments can be much lower than previously anticipated, with important implications for future modeling studies to better constrain the climate and air quality effects of wildfires. [ABSTRACT FROM AUTHOR]

Ammonia (NH3) is an important agent involved in atmospheric chemistry and nitrogen cycling. Current estimates of NH3 emissions from biomass burning (BB) differ by more than a factor of two, impeding a reliable assessment of their environmental consequences. Combining high-resolution satellite observations of NH3 columns with network measurements of the concentration and stable nitrogen isotope composition (δ15N) of NH3, we present coherent estimates on the amount of NH3 derived from BB in the heartland of Southeast Asia, a tropical monsoon environment. Our results reveal a strong variability of atmospheric NH3 levels in time and space across different landscapes. All evidence in hand suggests that anthropogenic activities are the most important modulating control with regards to the observed patterns of NH3 distribution in the study area. N-isotope balance considerations revealed that during the intensive fire period, the atmospheric input from BB accounts for not more than 21 ± 5 % (1σ) of the ambient NH3, even at the rural sites and in the proximity of burning areas. Our N-isotope based assessment of the variation of the relative contribution of BB-derived NH3 is further validated independently through the measurements of particulate K+, a chemical tracer of BB. Our findings underscore that BB-induced NH3 emissions in the tropical monsoon environments can be much lower than previously anticipated, with important implications for future modeling studies to better constrain the climate and air quality effects of wildfires. [ABSTRACT FROM AUTHOR]

It is a puzzle as to why more severe haze formed during the New Year Holiday in 2020 (NYH‐20), when China was in an unprecedented state of shutdown to contain the coronavirus (COVID‐19) outbreak, than in 2019 (NYH‐19). We performed a comprehensive measurement and modeling analysis of the aerosol chemistry and physics at multiple sites in China (mainly in Shanghai) before, during, and after NYH‐19 and NYH‐20. Much higher secondary aerosol fraction in PM2.5 were observed during NYH‐20 (73%) than during NYH‐19 (59%). During NYH‐20, PM2.5 levels correlated significantly with the oxidation ratio of nitrogen (r2 = 0.77, p < 0.01), and aged particles from northern China were found to impede atmospheric new particle formation and growth in Shanghai. A markedly enhanced efficiency of nitrate aerosol formation was observed along the transport pathways during NYH‐20, despite the overall low atmospheric NO2 levels. Plain Language Summary: In China, there are multiple cases (e.g., the 2008 Summer Olympics in Beijing and the 2010 World Expo in Shanghai) when combustion‐related emissions (e.g., NOx) were actively, and successfully, reduced to transiently improve air quality. During the extended Chinese Lunar New Year holiday in 2020 (between 24 January and 10 February), whole China was in an unprecedented state of shutdown, because most people were contained in their homes to reduce the spread of the novel coronavirus disease (COVID‐19). Mobility, energy demand, and industrial output remained far below their normal levels. Nevertheless, widespread haze pollution still occurred over Eastern China. To elucidate haze formation mechanisms, we performed comprehensive and continuous measurements of aerosol chemistry and physics in and out of Shanghai before, during, and after the Chinese New Year Holiday in 2019 and 2020, respectively. We argue that the synergistic effects of long‐range transport and atmospheric chemistry leading to the efficient conversion of NOx to particulate nitrate were the key of haze formation during the Chinese New Year Holiday of the COVID‐19 outbreak in Shanghai. Key Points: Higher concentrations and distinct compositions of aerosol particles were observed during the COVID‐19 shutdownFast formation of secondary inorganic aerosol contributed to high aerosol mass loadingLonger‐range, regional transport facilitated and enhanced particulate nitrate formation [ABSTRACT FROM AUTHOR]

Predicting tropospheric cloud formation and subsequent nutrient deposition relies on understanding the sources and processes affecting aerosol constituents of the atmosphere that are preserved in cloud water. However, this challenge is difficult to address quantitatively based on the sole use of bulk chemical properties. Nitrogenous aerosols, mainly ammonium (NH4+) and nitrate (NO3-), play a particularly important role in tropospheric cloud formation. While dry and wet (mainly rainfall) deposition of NH4+ and NO3- are regularly assessed, cloud water deposition is often underappreciated. Here we collected cloud water samples at the summit of Mt. Tai (1545 m above sea level) in eastern China during a long-lasting biomass burning (BB) event and simultaneously measured for the first time the isotopic compositions (mean ±1σ) of cloud water nitrogen species (δ15N-NH4+ = - 6.53 ‰ ± 4.96 ‰, δ15N-NO3- = - 2.35 ‰ ± 2.00 ‰, δ18O-NO3- = 57.80 ‰ ± 4.23 ‰), allowing insights into their sources and potential transformation mechanism within the clouds. Large contributions of BB to the cloud water NH4+ (32.9 % ± 4.6 %) and NO3- (28.2 % ± 2.7 %) inventories were confirmed through a Bayesian isotopic mixing model, coupled with our newly developed computational quantum chemistry module. Despite an overall reduction in total anthropogenic NOx emission due to effective emission control actions and stricter emission standards for vehicles, the observed cloud δ15N-NO3- values suggest that NOx emissions from transportation may have exceeded emissions from coal combustion. δ18O-NO3- values imply that the reaction of OH with NO2 is the dominant pathway of NO3- formation (57 % ± 11 %), yet the contribution of heterogeneous hydrolysis of dinitrogen pentoxide was almost as important (43 % ± 11 %). Although the limited sample set used here results in a relatively large uncertainty with regards to the origin of cloud-associated nitrogen deposition, the high concentrations of inorganic nitrogen imply that clouds represent an important source of nitrogen, especially for nitrogen-limited ecosystems in remote areas. Further simultaneous and long-term sampling of aerosol, rainfall, and cloud water is vital for understanding the anthropogenic influence on nitrogen deposition in the study region. [ABSTRACT FROM AUTHOR]

Biomass burning can significantly impact the chemical and optical properties of carbonaceous aerosols. Here, the biomass burning impacts were studied during wintertime in a megacity of Nanjing, eastern China. The high abundance of biomass burning tracers such as levoglucosan (lev), mannosan (man), galactosan (gal) and non-sea-salt potassium (nss- K+) was found during the studied period with the concentration ranges of 22.4–1476 ng m -3 , 2.1–56.2 ng m -3 , 1.4–32.2 ng m -3 and 0.2–3.8 µ g m -3 , respectively. The significant contribution of biomass burning to water-soluble organic carbon (WSOC; 22.3±9.9 %) and organic carbon (OC; 20.9±9.3 %) was observed in this study. Backward air mass origin analysis, potential emission sensitivity of elemental carbon (EC) and MODIS fire spot information indicated that the elevations of the carbonaceous aerosols were due to the transported biomass-burning aerosols from southeastern China. The characteristic mass ratio maps of lev/man and lev/nss - K+ suggested that the biomass fuels were mainly crop residuals. Furthermore, the strong correlation (p<0.01) between biomass burning tracers (such as lev) and light absorption coefficient (babs) for water-soluble brown carbon (BrC) revealed that biomass burning emissions played a significant role in the light-absorption properties of carbonaceous aerosols. The solar energy absorption due to water-soluble brown carbon and EC was estimated by a calculation based on measured light-absorbing parameters and a simulation based on a radiative transfer model (RRTMG_SW). The solar energy absorption of water-soluble BrC in short wavelengths (300–400 nm) was 0.8±0.4 (0.2–2.3) W m -2 (figures in parentheses represent the variation range of each parameter) from the calculation and 1.2±0.5 (0.3–1.9) W m -2 from the RRTMG_SW model. The absorption capacity of water-soluble BrC accounted for about 20 %–30 % of the total absorption of EC aerosols. The solar energy absorption of water-soluble BrC due to biomass burning was estimated as 0.2±0.1 (0.0–0.9) W m -2 , considering the biomass burning contribution to carbonaceous aerosols. Potential source contribution function model simulations showed that the solar energy absorption induced by water-soluble BrC and EC aerosols was mostly due to the regionally transported carbonaceous aerosols from source regions such as southeastern China. Our results illustrate the importance of the absorbing water-soluble brown carbon aerosols in trapping additional solar energy in the low-level atmosphere, heating the surface and inhibiting the energy from escaping the atmosphere. [ABSTRACT FROM AUTHOR]

Arsenic (As) has long been recognized as a toxic element of mainly anthropogenic origins, having adverse effects on human health. However, there is insufficient understanding regarding As released into atmosphere from biomass burning (BB). To this end, daily airborne As concentrations in total particulate matter (TSP) were determined at Mount Hehuan (24.16° N, 121.29° E, 3001ma.s.l.), Taiwan from September 2011 to September 2012. During the sampling period, As concentrations varied from 0.02 to 5.9 ngm-3 with a mean value of 0.5±.0 ngm-3. Significantly seasonal variations of As were found over the subtropical free troposphere, and higher As concentrations were observed in the southern (S) and southeastern (SE) Asian BB seasons (from January to May). Principal component analysis (PCA) results showed that BB activities seemed to be a major source of As during the S and SE Asian BB periods, which were very distinct from the major source of coal-fired power plant during the periods between July and December. Based on backward trajectory analyses and WRF-Chem model simulations, we found that the high As concentrations during the BB periods were attributed to the biomass burning activities over S Asia where groundwater, soil and crops are severely contaminated by arsenic. A strong correlation (r = 0:73 p < 0:05) between As and potassium ion (KC, a chemical tracer of BB activities) in S Asian BB events also supported this hypothesis. During the S Asian BB events, the high As = Pb ratios (> 0:2) were also observed, indicating that burning crops contaminated by lead arsenate might be a crucial candidate for high As concentrations at Mount Hehuan. Nevertheless, the net influence of S Asian BB activities on airborne As concentrations has been estimated by comparing the differences of As concentrations on BB and non-BB days. On average, the difference in As concentrations was 1.0 ngm-3, which accounted for 63% of the average As concentration on BB days. Moreover, a ratio of 1As=1CO (~ 0:00001) in the S Asian BB events was obtained. Using this value, arsenic emissions from S Asian BB activities were estimated to be 0.17 tons yr-1 , resulting in high airborne As concentrations over the subtropical free troposphere and impacting As cycles on a regional scale in the S and SE Asian BB seasons. [ABSTRACT FROM AUTHOR]

Atmospheric trace elements, especially metal species, are an emerging environmental and health concern with insufficient understanding of their levels and sources in Shanghai, the most important industrial megacity in China. Here we continuously performed a 1 year (from March 2016 to February 2017) and hourly resolved measurement of 18 elements in fine particles (PM2:5) at the Shanghai urban center with an Xact multi-metals monitor and several collocated instruments. Mass concentrations (mean±1σ; ngm-3) determined by Xact ranged from detection limits (nominally 0.1 to 20 ngm-3) to 15 µgm-3. Element-related oxidized species comprised an appreciable fraction of PM2:5 during all seasons, accounting for 8.3% on average. As a comparison, the atmospheric elements concentration level in Shanghai was comparable with that in other industrialized cities in East Asia but 1 or 2 orders of magnitude higher than at sites in North America and Europe. Positive matrix factorization (PMF) was applied to identify and apportion the sources of the elements in the PM2:5 mass. Five different factors were resolved (notable elements and relative contribution in parentheses): traffic-related (Ca, Fe, Ba, Si; 46%), shipping (V, Ni; 6%), nonferrous metal smelting (Ag, Cd, Au; 15%), coal combustion (As, Se, Hg, Pb; 18%) and ferrous metal smelting (Cr, Mn, Zn; 15%). The contribution from the exhaust and non-exhaust vehicle emissions, i.e., the traffic-related factor shows a strong bimodal diurnal profile with average concentration over 2 times higher during the rush hour than during nighttime. The shipping factor was firmly identified because V and Ni, two recognized tracers of shipping emissions, are almost exclusively transported from the East China Sea and their ratio (around 3.2) falls within the variation range of V= Ni ratios in particles emitted from heavy oil combustion. Interestingly, nearly half of the K was derived from coal combustion with high mineral affinity (elements associated with aluminosilicates, carbonates and other minerals in coal ash). The contributions of nonferrous metal smelting to the trace elements are consistent with a newly developed emission inventory. Although the precipitation scavenging effect on the mass concentration of the trace elements varied among different species and sources, precipitation could effectively lower the concentration of the trafficand coal combustion-related trace elements. Therefore, water spray to simulate natural types of precipitation could be one of the abatement strategies to facilitate the reduction of ambient PM2:5 trace elements in the urban atmosphere. Collectively, our findings in this study provide baseline levels and sources of trace elements with high detail, which are needed for developing effective control strategies to reduce the high risk of acute exposure to atmospheric trace elements in China's megacities. [ABSTRACT FROM AUTHOR]

Atmospheric fine-particle (PM2:5) pollution is frequently associated with the formation of particulate nitrate (pNO-3), the end product of the oxidation of NOx gases (NOCNO2) in the upper troposphere. The application of stable nitrogen (N) (and oxygen) isotope analyses of pNO-3 to constrain NOx source partitioning in the atmosphere requires knowledge of the isotope fractionation during the reactions leading to nitrate formation. Here we determined the δ15N values of fresh pNO-3 (δ15N-pNO-3) in PM2:5 at a rural site in northern China, where atmospheric pNO-3 can be attributed exclusively to biomass burning. The observed δ15N- pNO-3 (12:17±1:55 ; n D 8) was much higher than the N isotopic source signature of NOx from biomass burning (1:04±4:13). The large difference between δ15N-pNO-3 and δ15N-NOx (1(δ15N)) can be reconciled by the net N isotope effect ("N) associated with the gas-particle conversion from NOx to NO-3. For the biomass burning site, a mean "N.ε 1.δ15N)) of 10:99±0:74 was assessed through a newly developed computational quantum chemistry (CQC) module. "N depends on the relative importance of the two dominant N isotope exchange reactions involved (NO2 reaction with OH versus hydrolysis of dinitrogen pentoxide (N2O5) with H2O) and varies between regions and on a diurnal basis. A second, slightly higher CQC-based mean value for "N (15:33±4:90) was estimated for an urban site with intense traffic in eastern China and integrated in a Bayesian isotope mixing model to make isotope-based source apportionment estimates for NOx at this site. Based on the δ15N values (10:93±3:32; n D 43) of ambient pNO-3 determined for the urban site, and considering the location-specific estimate for "N, our results reveal that the relative contribution of coal combustion and road traffic to urban NOx is 32%±11% and 68%±11%, respectively. This finding agrees well with a regional bottom-up emission inventory of NOx. Moreover, the variation pattern of OH contribution to ambient pNO-3 formation calculated by the CQC module is consistent with that simulated by theWeather Research and Forecasting model coupled with Chemistry (WRF-Chem), further confirming the robustness of our estimates. Our investigations also show that, without the consideration of the N isotope effect during pNO-3 formation, the observed δ15N-pNO-3 at the study site would erroneously imply that NOx is derived almost entirely from coal combustion. Similarly, reanalysis of reported δ15N-NO-3 data throughout China and its neighboring areas suggests that NOx emissions from coal combustion may be substantively overestimated (by > 30%) when the N isotope fractionation during atmospheric pNO-3 formation is neglected. [ABSTRACT FROM AUTHOR]

Everolimus (EV), a rapamycin analogue mTOR inhibitor, is used in the clinic to treat Estrogen positive (ERC) breast cancer in order to avoid the resistance to hormonotherapy. Here, we investigated whether EV efficacy varied according to administration timing by using the ERC breast cancer cell line MCF-7 as model system. Our results showed that instead of apoptosis, EV induced a G0/G1 phase blockage of MCF-7 cells. Following serum shock, MCF-7 cells displayed a statistically significant 24h rhythm of mammalian target of Rapamycin (mTOR) activity, but perturbed circadian clock genes oscillations. Interestingly, the different delivery schedule of EV presented different efficacy in G0/G1 phase blockage in serum shocked MCF-7 cells. Moreover, serum shock induced also a circadian-like oscillation in expression or activity of several important G1 phase progression proteins, such as Cyclin D1 and phosphorylated Retinoblastoma protein (RB). Inhibition mTOR activity by EV reduced Cyclin D1 and Cyclin D3 protein level as well as RB phosphorylation level. Taken together, the results indicated that serum shock synchronization induced a circadian oscillation in mTOR activity in MCF-7 cells, which rhythmically regulated the synthesis or phosphorylation of key G1 progression proteins, such as Cyclin D1 and phosphorylated RB, ultimately resulting in different G0/G1 blockage efficiency according to different EV administration timing. [ABSTRACT FROM AUTHOR]

Fine particulate matter (PM2.5) samples were collected using a high-volume air sampler and pre-combusted quartz filters during May 2013 to January 2014 at a background rural site (47 ∘ 35 N, 133 ∘ 31 E) in Sanjiang Plain, Northeast China. A homologous series of dicarboxylic acids (C 2 -C 11 ) and related compounds (oxoacids, α-dicarbonyls and fatty acids) were analyzed by using a gas chromatography (GC) and GC-MS method employing a dibutyl ester derivatization technique. Intensively open biomass-burning (BB) episodes during the harvest season in fall were characterized by high mass concentrations of PM2.5, dicarboxylic acids and levoglucosan. During the BB period, mass concentrations of dicarboxylic acids and related compounds were increased by up to >20 times with different factors for different organic compounds (i.e., succinic (C 4 ) acid > oxalic (C 2 ) acid > malonic (C 3 ) acid). High concentrations were also found for their possible precursors such as glyoxylic acid ( ω C 2 ), 4-oxobutanoic acid, pyruvic acid, glyoxal, and methylglyoxal as well as fatty acids. Levoglucosan showed strong correlations with carbonaceous aerosols (OC, EC, WSOC) and dicarboxylic acids although such good correlations were not observed during non-biomass-burning seasons. Our results clearly demonstrate biomass burning emissions are very important contributors to dicarboxylic acids and related compounds. The selected ratios (e.g., C 3 /C 4 , maleic acid/fumaric acid, C 2 / ω C 2 , and C 2 /levoglucosan) were used as tracers for secondary formation of organic aerosols and their aging process. Our results indicate that organic aerosols from biomass burning in this study are fresh without substantial aging or secondary production. The present chemical characteristics of organic compounds in biomass-burning emissions are very important for better understanding the impacts of biomass burning on the atmosphere aerosols. [ABSTRACT FROM AUTHOR]

Atmospheric PM 2.5 poses a variety of health and environmental risks to urban environments. Ammonium is one of the main components of PM 2.5 , and its role in PM 2.5 pollution will likely increase in the coming years as NH 3 emissions are still unregulated and rising in many cities worldwide. However, partitioning urban NH 4 + sources remains challenging. Although the 15N natural abundance (δ15N) analysis is a promising approach for this purpose, it has seldom been applied across multiple cities within a given region. This limits our understanding of the regional patterns and controls of NH 4 + sources in urban environments. Here, we collected PM 2.5 samples using an active sampling technique during winter at six cities in the North China Plain to characterize the concentrations, δ15N and sources of NH 4 + in PM 2.5. We found substantial variations in both the concentrations and δ15N of NH 4 + among the sites. The mean NH 4 + concentrations across the six cities ranged from 3.6 to 12.1 μg m−3 on polluted days and from 0.9 to 10.6 μg m−3 on non-polluted days. The δ15N ranged from 6.5‰ to 13.9‰ on polluted days and from 8.7‰ to 13.5‰ on non-polluted days. The δ15N decreased with increasing NH 4 + concentrations at all six sites. We found that non-agricultural sources (vehicle exhaust, ammonia slip and urban wastes) contributed 72%–94% and 56%–86% of the NH 4 + on polluted and non-polluted days, respectively, and that during polluted days, combustion-related emissions (vehicle exhaust and ammonia slip) were positively associated with the proportion of urban area, population density and number of vehicles, highlighting the importance of local sources of particulate pollution. This study suggests that the analysis of 15N in aerosol NH 4 + is a promising approach for apportioning atmospheric NH 3 sources over a large region, and this approach has potential for mapping rapidly and precisely the sources of NH 3 emissions. [Display omitted] • Non-agricultural and agricultural sources contributed 82% and 18% to NH 4 + in PM 2.5. • Aerosol NH 4 + on polluted winter days in six cities was mainly of local origin. • Combustion-derived NH 4 + positively related to urban area size and vehicle numbers. • Agricultural contribution to NH 4 + increased with increasing agricultural coverage. [ABSTRACT FROM AUTHOR]

Although human excreta as a NH3 source has been recognized globally, this source has never been quantitatively determined in cities, hampering efforts to fully assess the causes of urban air pollution. In the present study, the exhausts of 15 ceiling ducts from collecting septic tanks in 13 buildings with 6 function types were selected to quantify NH3 emission rates in the megacity of Shanghai. As a comparison, the ambient NH3 concentrations across Shanghai were also measured at 13 atmospheric monitoring sites. The concentrations of NH3 in the ceiling ducts ( μg m-3) outweigh those of the open air (~10 μg m-3) by 2–3 orders of magnitude, and there is no significant difference between different seasons. δ15N values of NH3 emitted from two ceiling ducts are also seasonally consistent, suggesting that human excreta may be a stable source of NH3 in urban areas. The NH3 concentration levels were variable and dependent on the different building types and the level of human activity. NH3 emission rates of the six residential buildings (RBNH3) were in agreement with each other. Taking occupation time into account, we confined the range of the average NH3 emission factor for human excreta to be 2–4 times (with the best estimate of 3 times) of the averaged RBNH3 of 66.0±58.9 g NH3 capita-1 yr-1. With this emission factor, the population of ~21 million people living in the urban areas of Shanghai annually emitted approximately 1386 Mg NH3, which corresponds to over 11.4% of the total NH3 emissions in the Shanghai urban areas. The spatial distribution of NH3 emissions from human excreta based on population data was calculated for the city of Shanghai at a high-resolution (100×100 m). Our results demonstrate that human excreta should be included in official ammonia emission inventories. [ABSTRACT FROM AUTHOR]

China's unprecedented lockdown to contain the spread of the novel coronavirus disease (COVID-19) in early 2020, provided a tragic natural experiment to investigate the responses of atmospheric pollution to emission reduction at regional scale. Primarily driven by primary emissions, particulate trace elements is vitally important due to their disproportionally adverse impacts on human health and ecosystem. Here 14 trace elements in PM 2.5 were selected for continuous measurement hourly in urban representative site of Shanghai, for three different phases: pre-control period (1–23 January 2020), control period (24 January-10 February 2020; overlapped with Chinese Lunar New Year holiday) and post control period (11–26 February 2020) the city's lockdown measures. The results show that all meteorological parameters (including temperature, RH, mixing layer height et al.) were generally consistent among different periods. Throughout the study period, the concentrations of most species displayed a "V-shaped" trend, suggesting significant effects by the restriction measures imposed during the lockdown period. While this is not the case for species like K, Cu and Ba, indicating their unusual origins. As a case study, the geographical origins of Cu were explored. Seven major sources, i.e., Vehicle-related emission (including road dust; indicative of Ca, Fe, Ba, Mn, Zn, Cu; accounting for 30.1%), shipping (Ni; 5.0%), coal combustion (As, Pb; 4.2%), Se and Cr industry (24.9%), nonferrous metal smelting (Au, Hg; 7.5%) and fireworks burning (K, Cu, Ba; 28.3%) were successfully pinpointed based on positive matrix factorization (PMF) analysis. Our source apportionment results also highlight fireworks burning was one of the dominant source of trace elements during the Chinese Lunar New Year holiday. It is worth noting that 56% of the total mass vehicular emissions are affiliated with non-exhaust sources (tire wear, brake wear, and road surface abrasion). [Display omitted] • Trace elements in PM 2.5 were continuously measured at hourly resolution in Shanghai. • Seven major sources were successfully pinpointed based on PMF analysis. • Beyond expectation, elements of K, Cu, and Ba significantly increased during the control period. • 56% vehicular emissions were associated with non-exhaust sources. [ABSTRACT FROM AUTHOR]

Arid areas play a significant role in the global nitrogen cycle. Dry and wet deposition of inorganic nitrogen (N) species were monitored at one urban (SDS) and one suburban (TFS) site at Urumqi in a semi-arid region of central Asia. Atmospheric concentrations of NH3, NO2, HNO3, particulate ammonium and nitrate (pNH4+ and pNO3−) concentrations and NH4-N and NO3-N concentrations in precipitation showed large monthly variations and averaged 7.1, 26.6, 2.4, 6.6, 2.7 µg N m−3 and 1.3, 1.0 mg N L−1 at both SDS and TFS. Nitrogen dry deposition fluxes were 40.7 and 36.0 kg N ha−1 yr−1 while wet deposition of N fluxes were 6.0 and 8.8 kg N ha−1 yr−1 at SDS and TFS, respectively. Total N deposition averaged 45.8 kg N ha−1 yr−1at both sites. Our results indicate that N dry deposition has been a major part of total N deposition (83.8% on average) in an arid region of central Asia. Such high N deposition implies heavy environmental pollution and an important nutrient resource in arid regions. [ABSTRACT FROM AUTHOR]

A recent study (Wolf et al., 2010) suggests that short-lived pulses of N2O emission during spring thaw dominate the annual N2O budget and that grazing decreases N2O emissions during the spring thaw. To verify this we conducted year-round N2O flux measurements from June 2010 to May 2011 in Tianshan alpine grassland in central Asia. No pulse emissions of N2O were found at grazing management sites and nitrogen addition sites during the spring thaw. The contribution of the spring thaw to the total annual N2O budget was small and accounted for only 6.6% of the annual fluxes, with winter emissions accounting for 16.7% and growing season emissions accounting for 76.7%. The difference in N2O emissions attributable to grazing management was not significant ( P > 0.05). Nitrogen input tended to increase N2O emissions at N addition sites during the grass growing season compared with those at unfertilized sites. N2O fluxes showed a significant correlation with air temperature and also with both soil temperature and soil water content at 10 cm depth. [ABSTRACT FROM AUTHOR]