Variability of ambient air ammonia in urban Europe (Finland, France, Italy, Spain, and the UK).

This study addressed the scarcity of NH3 measurements in urban Europe and the diverse monitoring protocols, hindering direct data comparison. Sixty-nine datasets from Finland, France, Italy, Spain, and the UK across various site types, including industrial (IND, 8), traffic (TR, 12), urban (UB, 22), suburban (SUB, 12), and regional background (RB, 15), are analyzed to this study. Among these, 26 sites provided 5, or more, years of data for time series analysis. Despite varied protocols, necessitating future harmonization, the average NH3 concentration across sites reached 8.0 ± 8.9 µg/m3. Excluding farming/agricultural hotspots (FAHs), IND and TR sites had the highest concentrations (4.7 ± 3.2 and 4.5 ± 1.0 µg/m3), followed by UB, SUB, and RB sites (3.3 ± 1.5, 2.7 ± 1.3, and 1.0 ± 0.3 µg/m3, respectively) indicating that industrial, traffic, and other urban sources were primary contributors to NH3 outside FAH regions. When referring exclusively to the FAHs, concentrations ranged from 10.0 ± 2.3 to 15.6 ± 17.2 µg/m3, with the highest concentrations being reached in RB sites close to the farming and agricultural sources, and that, on average for FAHs there is a decreasing NH3 concentration gradient towards the city. Time trends showed that over half of the sites (18/26) observed statistically significant trends. Approximately 50 % of UB and TR sites showed a decreasing trend, while 30 % an increasing one. Meta-analysis revealed a small insignificant decreasing trend for non-FAH RB sites. In FAHs, there was a significant upward trend at a rate of 3.51[0.45,6.57]%/yr. Seasonal patterns of NH3 concentrations varied, with urban areas experiencing fluctuations influenced by surrounding emissions, particularly in FAHs. Diel variation showed differing patterns at urban monitoring sites, all with higher daytime concentrations, but with variations in peak times depending on major emission sources and meteorological patterns. These results offer valuable insights into the spatio-temporal patterns of gas-phase NH3 concentrations in urban Europe, contributing to future efforts in benchmarking NH3 pollution control in urban areas.

PM2.5-bound silicon-containing secondary organic aerosols (Si-SOA) in Beijing ambient air.

Volatile methyl siloxanes (VMS) have been widely used in personal care products and industrial applications, and are an important component of VOCs (volatile organic compounds) indoors. They have sufficiently long lifetimes to undergo long-range transport and to form secondary aerosols through atmospheric oxidation. To investigate these silicon-containing secondary organic aerosols (Si-SOA), we collected PM2.5 samples during 8th-21st August 2018 (summer) and 3rd-23rd January 2019 (winter) at an urban site of Beijing. As the oxidation of VMS mainly results in hydrophilic polar semi-volatile and non-volatile oxidation products, the differences between total water-soluble Si and total water-soluble inorganic Si were used to estimate water-soluble organic Si, considered to be secondary organic Si (SO-Si). The average concentrations of SO-Si during the summer and winter campaigns were 4.6 ± 3.7 and 13.2 ± 8.6 ng m-3, accounting for approximately 80.1 ± 10.1% and 80.2 ± 8.7% of the total water-soluble Si, and 1.2 ± 1.2% and 5.0 ± 6.9% of total Si in PM2.5, respectively. The estimated Si-SOA concentrations were 12.7 ± 10.2 ng m-3 and 36.6 ± 23.9 ng m-3 on average in summer and winter, which accounted for 0.06 ± 0.07% and 0.16 ± 0.22% of PM2.5 mass, but increased to 0.26% and 0.92% on certain days. We found that net solar radiation is positively correlated with SO-Si levels in the summer but not in winter, suggesting seasonally different formation mechanisms.

An evaluation of source apportionment of fine OC and PM2.5 by multiple methods: APHH-Beijing campaigns as a case study.

This study aims to critically evaluate the source apportionment of fine particles by multiple receptor modelling approaches, including carbon mass balance modelling of filter-based radiocarbon (14C) data, Chemical Mass Balance (CMB) and Positive Matrix Factorization (PMF) analysis on filter-based chemical speciation data, and PMF analysis on Aerosol Mass Spectrometer (AMS-PMF) or Aerosol Chemical Speciation Monitor (ACSM-PMF) data. These data were collected as part of the APHH-Beijing (Atmospheric Pollution and Human Health in a Chinese Megacity) field observation campaigns from 10th November to 12th December in winter 2016 and from 22nd May to 24th June in summer 2017. 14C analysis revealed the predominant contribution of fossil fuel combustion to carbonaceous aerosols in winter compared with non-fossil fuel sources, which is supported by the results from other methods. An extended Gelencsér (EG) method incorporating 14C data, as well as the CMB and AMS/ACSM-PMF methods, generated a consistent source apportionment for fossil fuel related primary organic carbon. Coal combustion, traffic and biomass burning POC were comparable for CMB and AMS/ACSM-PMF. There are uncertainties in the EG method when estimating biomass burning and cooking OC. The POC from cooking estimated by different methods was poorly correlated, suggesting a large uncertainty when differentiating this source type. The PM2.5 source apportionment results varied between different methods. Through a comparison and correlation analysis of CMB, PMF and AMS/ACSM-PMF, the CMB method appears to give the most complete and representative source apportionment of Beijing aerosols. Based upon the CMB results, fine aerosols in Beijing were mainly secondary inorganic ion formation, secondary organic aerosol formation, primary coal combustion and from biomass burning emissions.

Insights into air pollution chemistry and sulphate formation from nitrous acid (HONO) measurements during haze events in Beijing.

Wintertime urban air pollution in many global megacities is characterised by episodic rapid increase in particulate matter concentrations associated with elevated relative humidity - so-called haze episodes, which have become characteristic of cities such as Beijing. Atmospheric chemistry within haze combines gas- and condensed-phase chemical processes, leading to the growth in secondary species such as sulphate aerosols. Here, we integrate observations of reactive gas phase species (HONO, OH, NOx) and time-resolved aerosol composition, to explore observational constraints on the mechanisms responsible for sulphate growth during the onset of haze events. We show that HONO abundance is dominated by established fast gas-phase photochemistry, but the consideration of the additional formation potentially associated with condensed-phase oxidation of S species by aqueous NO2 leading to NO2- production and hence HONO release, improves agreement between observed and calculated gas-phase HONO levels. This conclusion is highly dependent upon aerosol pH, ionic strength and particularly the parameterisation employed for S(iv) oxidation kinetics, for which an upper limit is derived.

PCDHGB7 Increases Chemosensitivity to Carboplatin by Inhibiting HSPA9 via Inducing Apoptosis in Breast Cancer.

Breast cancer is one of the most serious cancers worldwide, and chemotherapy resistance frequently drives cancer progression. Triple-negative breast cancer (TNBC) has a high recurrence rate and poor prognosis given its resistance to chemotherapy. In our previous study, we found a remarkable abnormal methylation modification of the PCDHGB7 gene in breast cancer. However, the roles of PCDHGB7 in the progression and treatment of breast cancer are unclear. In this study, we examined the effects of PCDHGB7 on the sensitivity of TNBC cells to carboplatin and investigated the underlying mechanism. By knocking down and overexpressing PCDHGB7 in HS578T and BT549 cells, we confirmed that PCDHGB7 increases TNBC cell chemosensitivity to carboplatin. Mechanistically, we found that PCDHGB7 negatively regulates the expression of HSPA9, uplifting its inhibition on P53 translocation and caspase-3 activation. Thus, we demonstrated that PCDHGB7 increases chemosensitivity of TNBC cells to carboplatin by inhibiting HSPA9 via inducing apoptosis. PCDHGB7 and HSPA9 represent potential therapeutic targets for chemosensitivity in breast cancer.

Variations and sources of nitrous acid (HONO) during a severe pollution episode in Beijing in 2016.

HONO is an important precursor of OH radical and plays a key role in atmospheric chemistry, but its source and formation mechanism remain uncertain, especially during complex atmospheric pollution processes. In this study, HONO mixing ratios were measured by a custom-made instrument during a severe pollution event from 16 to 23 December 2016, at an urban area of Beijing. The measurement was divided into three periods: I (haze), II (severe haze) and III (clean), according to the levels of PM2.5. This pollution episode was characterized by high levels of NO (75 ±â€¯39 and 94 ±â€¯40 ppbV during periods I and II, respectively) and HONO (up to 10.7 ppbV). During the nighttime, the average heterogeneous conversion frequency during the two haze periods were estimated to be 0.0058 and 0.0146 h-1, and it was not the important way to form HONO. Vehicle emissions contributed 52% (±16)% and 40% (±18)% to ambient HONO at nighttime during periods I and II. The contribution of homogeneous reaction of NO with OH should be reconsidered under high-NOx conditions and could be noticeable to HONO sources during this pollution event. Furthermore, HONO was positively correlated with PM2.5 during periods I and II, suggesting a potential chemical link between HONO and haze particles.

The influence of relative humidity on the heterogeneous oxidation of sulfur dioxide by ozone on calcium carbonate particles.

Heterogeneous reactions of SO2 and O3 with CaCO3 particles were investigated at a series of relative humidity (RH, 1% to 90%) and 298K using a diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The uptake coefficients of SO2 on CaCO3 at different RHs were obtained for the first time. Our results proved that high RH could substantially promote the formation of sulfate, for which the highest concentration (80% RH and reaction time of 200min) and highest formation rate in stable stage (85% RH) were 14 times and 43 times that at 1% RH, respectively. The surface products, increment of concentration and formation rate of sulfate changed with RH which were due to the surface adsorbed water (SAW) on the particles. SAW could increase the reactive sites on the particles and thus accelerate the conversion of SO2 into sulfite, and sulfite could be oxidized rapidly. Liquid-like water layers formed on the particle surface could enhance the ion mobility and promote the aggregation of CaSO4 hydrates, which could expose more reactive sites and result in additional adsorption of SO2. Piecewise equations of uptake coefficient with RH were given and could be referred by model simulation. The results are of importance in understanding the explosive growth of sulfate during severe haze episodes accompanied with high RH.

The formation and growth of calcium sulfate crystals through oxidation of SO2 by O3 on size-resolved calcium carbonate.

Calcium sulfate is a major constituent of atmospheric sulfate, with a typical rod-like morphology ranging from several hundred nanometers to approximately two micrometers observed in field studies. However, the chemical formation mechanism is still not well known. In this study, the kinetics and mechanism for the formation and growth of rod-like calcium sulfate crystals through oxidation of SO2 by O3 on size-resolved CaCO3 at different relative humidity (RH) were investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and scanning electron microscopy (SEM). We found that the concentration and formation rate of sulfate decreased with the increasing diameter of CaCO3 particles, and thus smaller particles could enhance the formation of sulfate due to more reactive sites on smaller particles. The rod-like calcium sulfate crystals were formed only at RH above 60% and in the presence of reactant gases through the heterogeneous pathway. The liquid-like water layer formed by promotion of high RH in the presence of reactant gases could facilitate the formation and aggregation of calcium sulfate hydrates and thus promote the formation and growth of rod-like calcium sulfate crystals. This study provides a possible mechanism for the formation and growth of rod-like calcium sulfate crystals existing in the atmosphere.

Heterogeneous Uptake of Gas-Phase Acetic Acid on the Surface of α-Al2 O3 Particles: Temperature Effects.

Heterogeneous reactions are thought to play a significant role in the formation of haze, especially in wintertime, which suggests that temperature may affect the heterogeneous formation of organic aerosols. As the most-abundant carboxylic acid in the Earth's atmosphere, we chose acetic acid to study the effect of temperature on its heterogeneous reaction with α-Al2 O3 between 248 and 298 K. The products were characterized by in situ DRIFTS, which indicated that lowering the temperature slowed the formation of acetate, but promoted the formation of crystalline acetic acid. Moreover, low temperatures promoted a different reaction mechanism to that at room temperature. Owing to the formation of chain structures at low temperatures, crystalline acetic acid molecules covered the surface active sites on α-Al2 O3 , thereby inhibiting the formation of acetate. However, crystalline acetic acid reacted with α-Al2 O3 itself in a sequential manner. Furthermore, the reactive uptake coefficients, active energies, and acetic acid lifetimes at different temperatures were investigated.

Exploring the nitrous acid (HONO) formation mechanism in winter Beijing: direct emissions and heterogeneous production in urban and suburban areas.

Continuous measurements of nitrous acid (HONO) were performed from December 12 to December 22, 2015 in both urban and suburban areas of Beijing to study the formation mechanism of HONO. The measurement campaign in both sites included a clean-haze-clean transformation process. HONO concentrations showed similar variations in the two sites, while they were always higher in the urban area. Moreover, correlations of HONO with NOx, NO2, NO, PM2.5 and relative humidity (RH) were studied to explore possible HONO formation pathways, and the contributions of direct emissions, heterogeneous reactions, and homogeneous reactions were also calculated. This showed that HONO in urban and suburban areas underwent totally different formation procedures, which were affected by meteorological conditions, PM2.5 concentrations, direct emissions, homogeneous reactions and heterogeneous reactions. PM2.5 concentrations and RH would influence the NO2 conversion efficiency. Heterogeneous reactions of NO2 were more efficient in suburban areas and in clean periods while direct emissions and homogeneous reactions contributed more in urban areas and in polluted periods when the concentrations of NOx and NO were at a high level.

Heterogeneous uptake of nitrogen dioxide on Chinese mineral dust.

Mineral dust is one of the major aerosols in the atmosphere. To assess its impact on trace atmospheric gases, in this work we present a laboratory study of the effect of temperature on the heterogeneous reaction of NO2 on the surface of ambient Chinese dust over the temperature range from 258 to 313K. The results suggest that nitrogen dioxide could mainly be adsorbed on these types of Chinese mineral dust reversibly with little temperature dependence. Similar to a previous study on NO2 uptake on mineral aerosols, the uptake coefficients are mainly on the order of 10(-6) for the Chinese dust, when BET areas are taken into account. HONO was observed as a product, and its formation and decomposition on Chinese mineral dust during the uptake processes were also studied. The complete dataset from this study was compiled with previous literature determinations. Atmospheric implications of the heterogeneous reaction between NO2 and mineral dust are also discussed, in an effort to understand this important heterogeneous process.

Influence of temperature on the heterogeneous reaction of formic acid on α-Al2O3.

Despite increased awareness of the role played by heterogeneous reactions of formic acid on mineral aerosol, the experimental determination of how these atmospheric reaction rates vary with temperature remain a crucially important part of atmosphere science. Here we report the first measurement of heterogeneous uptake of formic acid on α-Al(2)O(3) as a function of temperature (T = 240-298 K) at ambient pressure using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). From the analysis of the spectral features, crystalline HCOOH was identified at low temperature besides common product (formate ions) on the surface. It was also interesting to find that crystalline HCOOH can continue to react with α-Al(2)O(3). The reaction mechanisms at both room and low temperature were discussed. Furthermore, the reactive uptake coefficients were acquired and found to increase with decreasing temperature. Finally, the atmospheric lifetime of formic acid because of heterogeneous loss on mineral aerosol was estimated at temperatures related to the upper troposphere.