Long-term winter observation of nitrous acid in the urban area of Beijing.

The particulate matter (PM) pollution has been significantly improved by carrying out various valid emission control strategies since 2013 in China. Meanwhile the variation trend of nitrous acid (HONO) is worthy to investigate due to its vital role in the atmospheric oxidation process. In this study, field observation in the winter is conducted to investigate the concentration of HONO in an urban area of Beijing. In the winter of 2019, the mean HONO concentration is 1.38 ppbV during the whole winter. Photo-enhanced NO2 heterogeneous reactions on the ground and aerosol surfaces were found as the possible daytime sources of HONO. Compared to O3, photolysis of HONO dominates the primary OH sources during the winter time. To understand the HONO pollution patterns by years variation, multi-year data is summarized and finds that primary pollutants including CO and NO decreased, but secondary pollutants i.e., HONO (mostly generated via secondary process) increased. Our study highlights the requirement to mitigate secondary pollution by control HONO concentration.

HONO Budget and Its Role in Nitrate Formation in the Rural North China Plain.

Nitrous acid (HONO) is a major precursor of tropospheric hydroxyl radical (OH) that accelerates the formation of secondary pollutants. The HONO sources, however, are not well understood, especially in polluted areas. Based on a comprehensive winter field campaign conducted at a rural site of the North China Plain, a box model (MCM v3.3.1) was used to simulate the daytime HONO budget and nitrate formation. We found that HONO photolysis acted as the dominant source for primary OH with a contribution of more than 92%. The observed daytime HONO could be well explained by the known sources in the model. The heterogeneous conversion of NO2 on ground surfaces and the homogeneous reaction of NO with OH were the dominant HONO sources with contributions of more than 36 and 34% to daytime HONO, respectively. The contribution from the photolysis of particle nitrate and the reactions of NO2 on aerosol surfaces was found to be negligible in clean periods (2%) and slightly higher during polluted periods (8%). The relatively high OH levels due to fast HONO photolysis at the rural site remarkably accelerated gas-phase reactions, resulting in the fast formation of nitrate as well as other secondary pollutants in the daytime.

Aerosol optical properties under different pollution levels in the Pearl River Delta (PRD) region of China.

To clarify the aerosol hygroscopic growth and optical properties of the Pearl River Delta (PRD) region, integrated observations were conducted in Heshan City of Guangdong Province from October 19 to November 17, 2014. The concentrations and chemical compositions of PM2.5, aerosol optical properties and meteorological parameters were measured. The mean value of PM2.5 increased from less than 35 (excellent) to 35-75 µg/m3 (good) and then to greater than 75 µg/m3 (pollution), corresponding to mean PM2.5 values of 24.9, 51.2, and 93.3 µg/m3, respectively. The aerosol scattering hygroscopic growth factor (f(RH = 80%)) values were 2.0, 2.12, and 2.18 for the excellent, good, and pollution levels, respectively. The atmospheric extinction coefficient (σext) and the absorption coefficient of aerosols (σap) increased, and the single scattering albedo (SSA) decreased from the excellent to the pollution levels. For different air mass sources, under excellent and good levels, the land air mass from northern Heshan had lower f(RH) and σsp values. In addition, the mixed aerosol from the sea and coastal cities had lower f(RH) and showed that the local sources of coastal cities have higher scattering characteristics in pollution periods.

Effect of potential HONO sources on peroxyacetyl nitrate (PAN) formation in eastern China in winter.

As an important secondary photochemical pollutant, peroxyacetyl nitrate (PAN) has been studied over decades, yet its simulations usually underestimate the corresponding observations, especially in polluted areas. Recent observations in north China found unusually high concentrations of PAN during wintertime heavy haze events, but the current model still cannot reproduce the observations, and researchers speculated that nitrous acid (HONO) played a key role in PAN formation. For the first time we systematically assessed the impact of potential HONO sources on PAN formation mechanisms in eastern China using the Weather Research and Forecasting/Chemistry (WRF-Chem) model in February of 2017. The results showed that the potential HONO sources significantly improved the PAN simulations, remarkably accelerated the ROx (sum of hydroxyl, hydroperoxyl, and organic peroxy radicals) cycles, and resulted in 80%-150% enhancements of PAN near the ground in the coastal areas of eastern China and 10%-50% enhancements in the areas around 35-40°N within 3 km during a heavy haze period. The direct precursors of PAN were aldehyde and methylglyoxal, and the primary precursors of PAN were alkenes with C > 3, xylenes, propene and toluene. The above results suggest that the potential HONO sources should be considered in regional and global chemical transport models when conducting PAN studies.

Insights into the phenomenon of an explosive growth and sharp decline in haze: A case study in Beijing.

A severe haze episode occurred in winter in the North China Plain (NCP), and the phenomenon of an explosive growth and sharp decline in PM2.5 (particulate matter with an aerodynamic diameter equal to or less than 2.5 µm) concentration was observed. To study the systematic causes for this phenomenon, comprehensive observations were conducted in Beijing from November 26 to December 2, 2015; during this period, meteorological parameters, LIDAR data, and the chemical compositions of aerosols were determined. The haze episode was characterized by rapidly varying PM2.5 concentration, and the highest PM2.5 concentration reached 667 µg/m3. During the haze episode, the NCP was dominated by a weak high-pressure system and continuously low PBL (planetary boundary layer) heights, which are unfavorable conditions for the diffusion of pollutants. The large increases in the concentrations of SNA (SO42-, NO3- and NH4+) during the haze implied that the formation of SNA was the largest contribution. Water vapor also played a vital role in the formation of haze by promoting the chemical transformation of secondary pollutants, which led to higher PM2.5 concentrations. The spatial distributions of PM2.5 in Beijing at different times and the backward trajectories of the air masses also indicated that pollutants from surrounding provinces in particular, contributed to the higher PM2.5 concentration.

Characteristics of one-year observation of VOCs, NOx, and O3 at an urban site in Wuhan, China.

A continuous online observation of ozone and its precursors (NOx, VOCs) was carried out in central urban Wuhan from September 2016 to August 2017. The concentration levels of ozone, NOx, VOCs and their variations in urban Wuhan were analyzed, as well as effects of VOCs on ozone photochemical generation and the main controlling factors for ozone production. During the observation period, the average concentrations of ozone and NOx in Wuhan was 22.63 and 30.14 ppbv, respectively, and the average concentration of VOCs was 32.61 ppbv (42.3% alkanes, 13.0% alkenes, 10.0% aromatics, 7.3% acetylene, 9.9% OVOCs, and 10.5% halohydrocarbons). Ozone concentration was higher in spring and summer as compared with autumn and winter, wheras VOCs and NOx concentratios were lower in spring and summer but higher in autumn and winter. Aromatics and alkenes, two of VOCs species, showed the highest contributions to ozone formation potential in Wuhan (35.7% alkenes, 35.4 aromatics, 17.5% alkanes, 8.6% OVOCs, 1.6% halogenated hydrocarbons, and 1.4% acetylene). Among all VOCs species, those with the highest contribution were ethylene, m-xylene, toluene, propylene and o-xylene. The contribution of these five compounds to the total ozone formation potential concentration was 43.90%. Ozone-controlling factors in Wuhan changed within one day; during the early morning hours (6:00-9:00), VOCs/NOx was low, and ozone generation followed a VOCs-limited regime. However, during the peak time of ozone concentration (12:00-16:00), the ratio of VOCs/NOx was relatively high, suggesting that ozone generation followed a NOx-limited regime.

Characteristics and formation mechanism of regional haze episodes in the Pearl River Delta of China.

To investigate the characteristics and the specific mechanism of continuous haze, comprehensive measurements were conducted from 15 October to 19 November in the Atmospheric Environment Monitoring Super-Station in Heshan of Guangdong province. Five haze episodes occurred in October and November 2014 in the Pearl River Delta (PRD) region. The meteorological parameters, gas data, chemical compositions, and optical parameters of the aerosols were obtained. Among these events, the second haze episode, with the highest concentration of PM2.5 of 187.51µg/m3, was the most severe. NO3- was always higher than SO42-, which indicated that motor vehicles played an important role in the haze, even though the oxidation rate from SO2 to SO42- was faster than that of NOX to NO3-. The difference between the hourly averages of Na+ and K+ during the haze episode and clean days was small, implying that straw combustion and sea salt had no significant effect on the occurrence of haze, and the backward trajectories of the air masses also conformed with this result. The air pollutants were difficult to disperse because of the significant decrease in the planetary boundary layer (PBL) height. Relative humidity played a crucial role in the formation of haze by leading to hygroscopic growth of the diameter of aerosols.

An overview of emissions of SO2 and NOx and the long-range transport of oxidized sulfur and nitrogen pollutants in East Asia.

The long-range transport of oxidized sulfur (sulfur dioxide (SO2) and sulfate) and oxidized nitrogen (nitrogen oxides (NOx) and nitrate) in East Asia is an area of increasing scientific interest and political concern. This paper reviews various published papers, including ground- and satellite-based observations and numerical simulations. The aim is to assess the status of the anthropogenic emissions of SO2 and NOx and the long-range transport of oxidized S and N pollutants over source and downwind region. China has dominated the emissions of SO2 and NOx in East Asia and urgently needs to strengthen the control of their emissions, especially NOx emissions. Oxidized S and N pollutants emitted from China are transported to Korea and Japan, due to persistent westerly winds, in winter and spring. However, the total contributions of China to S and N pollutants across Korea and Japan were not found to be dominant over longer time scales (e.g., a year). The source-receptor relationships for oxidized S and N pollutants in East Asia varied widely among the different studies. This is because: (1) the nonlinear effects of atmospheric chemistry and deposition processes were not well considered, when calculating the source-receptor relationships; (2) different meteorological and emission data inputs and solution schemes for key physical and chemical processes were used; and (3) different temporal and spatial scales were employed. Therefore, simulations using the same input fields and similar model configurations would be of benefit, to further evaluate the source-receptor relationships of the oxidized S and N pollutants.

Chemical characterization of size-resolved aerosols in four seasons and hazy days in the megacity Beijing of China.

Size-resolved aerosol samples were collected by MOUDI in four seasons in 2007 in Beijing. The PM10 and PM1.8 mass concentrations were 166.0±120.5 and 91.6±69.7 µg/m3, respectively, throughout the measurement, with seasonal variation: nearly two times higher in autumn than in summer and spring. Serious fine particle pollution occurred in winter with the PM1.8/PM10 ratio of 0.63, which was higher than other seasons. The size distribution of PM showed obvious seasonal and diurnal variation, with a smaller fine mode peak in spring and in the daytime. OM (organic matter=1.6×OC (organic carbon)) and SIA (secondary inorganic aerosol) were major components of fine particles, while OM, SIA and Ca2+ were major components in coarse particles. Moreover, secondary components, mainly SOA (secondary organic aerosol) and SIA, accounted for 46%-96% of each size bin in fine particles, which meant that secondary pollution existed all year. Sulfates and nitrates, primarily in the form of (NH4)2SO4, NH4NO3, CaSO4, Na2SO4 and K2SO4, calculated by the model ISORROPIA II, were major components of the solid phase in fine particles. The PM concentration and size distribution were similar in the four seasons on non-haze days, while large differences occurred on haze days, which indicated seasonal variation of PM concentration and size distribution were dominated by haze days. The SIA concentrations and fractions of nearly all size bins were higher on haze days than on non-haze days, which was attributed to heterogeneous aqueous reactions on haze days in the four seasons.

Research progress in tumor therapy of carrier-free nanodrug.

Carrier-free nanodrugs are a novel type of drug constructed by the self-assembly of drug molecules without carrier involvement. They have the characteristics of small particle size, easy penetration of various barriers, targeting tumors, and efficient release. In recent years, carrier-free nanodrugs have become a hot topic in tumor therapy as they solve the problems of low drug loading, poor biocompatibility, and low uptake efficiency of carrier nanodrugs. A series of recent studies have shown that carrier-free nanodrugs play a vital role in the treatment of various tumors, with similar or better effects than carrier nanodrugs. Based on the literature published in the past decades, this paper first summarizes the recent progress in the assembly modes of carrier-free nanodrugs, then describes common therapeutic modalities of carrier-free nanodrugs in tumor therapy, and finally depicts the existing challenges along with future trends of carrier-free nanodrugs. We hope that this review can guide the design and application of carrier-free nanodrugs in the future.

Dominant physical and chemical processes impacting nitrate in Shandong of the North China Plain during winter haze events.

Nitrate has been a dominant component of PM2.5 since the stringent emission control measures implemented in China in 2013. Clarifying key physical and chemical processes influencing nitrate concentrations is crucial for eradicating heavy air pollution in China. In this study, we explored dominant processes impacting nitrate concentrations in Shandong of the North China Plain during three haze events from 9 to 25 December 2021, named cases P1 (94.46 (30.85) µg m-3 for PM2.5 (nitrate)), P2 (148.95 (50.12) µg m-3) and P3 (88.03 (29.21) µg m-3), by using the Weather Research and Forecasting/Chemistry model with an integrated process rate analysis scheme and updated heterogeneous hydrolysis of dinitrogen pentoxide on the wet aerosol surface (HET-N2O5) and additional nitrous acid (HONO) sources (AS-HONO). The results showed that nitrate increases in the three cases were attributed to aerosol chemistry, whereas nitrate decreases were due mainly to the vertical mixing process in cases P1 and P2 and to the advection process in case P3. HET-N2O5 (the reaction of OH + NO2) contributed 45 % (51 %) of the HNO3 production rate during the study period. AS-HONO produced a nitrate enhancement of 24 % in case P1, 12 % in case P2 and 19 % in case P3, and a HNO3 production rate enhancement of 0.79- 0.97 (0.18- 0.60) µg m-3 h-1 through the reaction of OH + NO2 (HET-N2O5) in the three cases. This study implies that using suitable parameterization schemes for heterogeneous reactions on aerosol and ground surfaces and nitrate photolysis is vital in simulations of HONO and nitrate, and the MOSAIC module for aerosol water simulations needs to be improved.

Impact of soil-atmosphere HONO exchange on concentrations of HONO and O3 in the North China Plain.

Nitrous acid (HONO) is an important precursor of the hydroxyl radical (OH) and plays a vital role in atmospheric photochemistry and nitrogen cycling. Soil emissions have been considered as a potential source of HONO. Lately, the HONO emission via soil-atmosphere exchange (ESA-exchange) from soil nitrite has been validated and quantified through chamber experiments, but has not been assessed in the real atmosphere. We coupled ESA-exchange and the other seven potential sources of HONO (i.e., traffic, indoor and soil bacterial emissions, heterogeneous reactions on ground and aerosol surfaces, nitrate photolysis, and acid displacement) into the Weather Research and Forecasting model with Chemistry (WRF-Chem), and found that diurnal variations of the soil emission flux at the Wangdu site were well simulated. During the non-fertilization period, ESA-exchange contributed ∼28 % and âˆ¼35 % of nighttime and daytime HONO, respectively, and enhanced the net ozone (O3) production rate by ∼8 % across the North China Plain (NCP). During the preintensive/intensive fertilization period, the maximum ESA-Exchange contributions attained ∼70 %/83 % of simulated HONO in the afternoon across the NCP, definitely asserting its dominance in HONO production. ESA-Exchange enhanced the OH production rate via HONO photolysis by ∼3.5/7.0 times, and exhibited an increase rate of ∼13 %/20 % in the net O3 production rate across the NCP. The total enhanced O3 due to the eight potential HONO sources ranged from ∼2 to 20 ppb, and ESA-exchange produced O3 enhancements of ∼1 to 6 ppb over the three periods. Remarkably, the average contribution of ESA-exchange to the total O3 enhancements remained ∼30 %. This study suggests that ESA-exchange should be included in three-dimensional chemical transport models and more field measurements of soil HONO emission fluxes and soil nitrite levels are urgently required.

Synergistic impacts of anthropogenic and biogenic emissions on summer surface O3 in East Asia.

A factor separation technique and an improved regional air quality model (RAQM) were applied to calculate synergistic contributions of anthropogenic volatile organic compounds (AVOCs), biogenic volatile organic compounds (BVOCs) and nitrogen oxides (NOx) to daily maximum surface 03 (O3DM) concentrations in East Asia in summer (June to August 2000). The summer averaged synergistic impacts of AVOCs and NOx are dominant in most areas of North China, with a maximum of 60 ppbv, while those of BVOCs and NOx are notable only in some limited areas with high BVOC emissions in South China, with a maximum of 25 ppbv. This result implies that BVOCs contribute much less to summer averaged O3DM concentrations than AVOCs in most areas of East Asia at a coarse spatial resolution (1 degree x 1 degree) although global emissions of BVOCs are much greater than those of AVOCs. Daily maximum total contributions of BVOCs can approach 20 ppbv in North China, but they can reach 40 ppbv in South China, approaching or exceeding those in some developed countries in Europe and North America. BVOC emissions in such special areas should be considered when 03 control measures are taken. Synergistic contributions among AVOCs, BVOCs and NOx significantly enhance O3 concentrations in the Beijing-Tianjin-Tangshan region and decrease them in some areas in South China. Thus, the total contributions of BVOCs to O3DM vary significantly from day to day and from location to location. This result suggests that 03 control measures obtained from episodic studies could be limited for long-term applications.

Divergent summertime surface O3 pollution formation mechanisms in two typical Chinese cities in the Beijing-Tianjin-Hebei region and Fenwei Plain.

Recently, severe summertime ozone (O3) pollution has swept across most areas of China, especially the Beijing-Tianjin-Hebei (BTH) region and Fenwei Plain. By focusing on Beijing and Yuncheng, which are two typical cities in the BTH region and the Fenwei Plain, we intended to reveal the neglected fact that they had disparate emission features and atmospheric movements but suffered from similar high-O3 pollution levels. Field observations indicated that Yuncheng had lower volatile organic compound (VOC) and NOx concentrations but higher background O3 levels. The model simulation verified that both photochemical reactions and net O3 generation were stronger in Beijing. Ultimately, faster net O3 generation rates (8.4 ppbv/h) plus lower background O3 values in Beijing and lower net O3 generation rates (6.2 ppbv/h) plus higher background O3 values in Yuncheng caused both regions to reach similar O3 peak values in July 2020. However, different O3 control measures were appropriate for the two cities according to the different simulated O3-VOCs-NOx responses. Additionally, as surface O3 levels are greatly affected by the ongoing O3 production/depletion process that occurs in three dimensions, exploring the effects of spatially distributed O3 on surface O3 should be high on the agenda in the future.

ASPP1/2 positive patients with invasive breast cancers have good prognosis.

Although the expression of ASPP family members in multiple tumors has been studied, especially in various cell lines of breast cancer (BC), but the expressions pattern of ASPP family members in invasive BC tissues are not clear. We studied the expression and expression pattern of ASPPs family member in BCs, the relationship between ASPP family members and clinic-pathologic features of BCs was also analyzed. The results showed that the expression of ASPP1, ASPP2 and iASPP was observed on AE1/AE3+ tumor cells, and not on infiltrated lymphocytes and capillaries. The relationship between ASPP1 expression and pTNM stage has statistical difference (p＜0.01). The relationship between expression of ASPP2 and SBR grade has statistical difference (p＜0.05). The relationship between expression of iASPP and clinic-pathologic feature of patients has no statistical difference (p＞0.05). The patients with positive expression of ASPP1 and the patients with negative expression of ASPP1 have statistical difference in 3-year survival rate and 5-year survival rate (χ2 = 4.49, P = 0.03; χ2 = 3.79, P = 0.048). Overall, our work demonstrated that the expression of ASPP1/2 contributes to predict the prognosis of patients with BC.

A comprehensive investigation on volatile organic compounds (VOCs) in 2018 in Beijing, China: Characteristics, sources and behaviours in response to O3 formation.

Observations of volatile organic compounds (VOCs) are a prerequisite for evaluating the effectiveness of government efforts targeting VOC pollution. Here, based on the one-year online VOC measurement in 2018 in Beijing, systematic analyses and model simulation were conducted to illuminate VOC characteristics, emission sources, regional hotspots and behaviours in response to O3 formation. The observed mean VOC concentration in 2018 was 29.12 ± 17.64 ppbv declined distinctly compared to that in 2015 and 2016. Vehicle exhaust (39.95%), natural gas/liquefied petroleum gas (22.04%) and industrial sources (20.64%) were the main contributors to VOCs in Beijing. Regional transport, mainly from the south-south-east (SSE) and south-south-west (SSW), quantitatively contributed 36.65%-55.06% to VOCs based on our developed method. O3 sensitivity tended to be in the transition regime in summer identified by ground-based and satellite observations. Strong solar radiation along with high temperature and low humidity aggravated O3 pollution that was further intensified by regional transport from southern polluted regions. The model simulation determined that turning off CH3CHO related reactions brought about the most predominantly short-term and long-run O3 reduction, indicating that control policies in VOC species should be tailored, instead of one-size-fits-all. Overall, region-collaborated and active VOC-species-focused strategies on VOC controls are imperative.

High crop yield losses induced by potential HONO sources - A modelling study in the North China Plain.

Nitrous acid (HONO) is a major source of hydroxyl radicals in the troposphere through its photolysis, and can significantly influence ozone (O3) levels, thereby causing considerable crop yield losses. Previous studies have assessed relative crop yield losses by using exposure-response equations with observed or simulated O3, however, the contribution of enhanced O3 due to potential HONO sources to the crop yield losses has never been quantified. In this study, for the first time, we evaluated the crop yield losses caused by potential HONO sources in the North China Plain (NCP), which is one of the major grain-producing areas in China suffering from heavy O3 pollution, by using the Weather Research and Forecasting/Chemistry (WRF-Chem) model during the wheat and maize growing seasons of 2016. HONO simulations were significantly improved after including six potential HONO sources in the WRF-Chem model. The potential HONO sources produced a daily maximum 8-h O3 enhancement of 8.1/8.2 ppb during the wheat/maize growing seasons, respectively, and led to ~11.4%/3.3% relative yield losses for wheat/maize, respectively, corresponding to approximately US$3.78/0.66 billion losses, respectively, in NCP in 2016. The above results suggest that potential HONO sources play a significant role in O3 formation and could induce high crop yield losses globally.

Immunohistochemical examination of intracerebral aquaporin-4 expression and its application for differential diagnosis between freshwater and saltwater drowning.

Human brain samples were collected from 70 autopsy cases including 22 freshwater drowning (FWD), 26 saltwater drowning (SWD), and 22 non-drowning cases as controls. Then, immunohistochemical study combined with morphometry was carried out in order to examine the differential expression of AQP1 and AQP4 in the brain samples. Immunohistochemically, star-shaped cells bearing highly branched processes, often surrounding blood vessels, showed positive reactions for AQP1 and AQP4 in FWD, SWD, as well as control groups. Additionally, with double-color immunofluorescence analysis, AQP1- or AQP4-positive cells could be identified as GFAP-positive astrocytes. Moreover, AQP1-positive reaction was also observed in blood vessels. Morphometrically, there were no significant differences in AQP1 expression in astrocytes or in blood vessels among the three groups. In contrast, the average value of AQP4-positive astrocytes was significantly higher in FWD cases than in SWD and control groups. Moreover, AQP4 expression was significantly lower in SWD than in the control group (p < 0.05). Moreover, there was no significant correlation between post-submerged interval and AQP expression in drowning cases. Therefore, immunohistochemical analysis of intracerebral AQP4 expression would be forensically useful for differentiation between FWD and SWD.

Biocompatible and biodegradable scaffold based on polytrimethylene carbonate-tricalcium phosphate microspheres for tissue engineering.

Biocompatible polymers and drug delivery vehicles have been driving development in bone regeneration. However, most bone scaffolds show poor degradation and proliferation. In this study, a composite microsphere scaffold was prepared using vancomycin hydrochloride(VH)-loaded polytrimethylene carbonate(PTMC) microsphere (PTMC-VH). Adopting a thermal technique, a three-dimensional oleic acid-modified tricalcium phosphate (PTMC-OA-TCP)/PTMC-VH microsphere scaffold was prepared. It had a porosity of 41-47 % and pore size of 129-154 µm. The highest drug loading and release efficiency were obtained with the scaffold produced using 2.4 % polymer concentration and 0.5 %polyvinyl alcohol. The scaffold with PTMC-VH microsphereshad enhancedmechanical properties, water absorption capacity, and degradation. In addition, the PTMC-OA-TCP scaffold had comparable performance with bone cement control in terms of bone regeneration in vivo. In summary, the prepared bioactive scaffolds, which had favorable mechanical properties and facilitated osteogenesis, could be a promising alternative for bone cement in bone tissue engineering.