Atmospheric Particles Research Articles

Monte Carlo-Simulated Annealing and Machine Learning-Based Funneled Approach for Finding the Global Minimum Structure of Molecular Clusters.

Understanding the physical underpinnings and geometry of molecular clusters is of great importance in many fields, ranging from studying the beginning of the universe to the formation of atmospheric particles. To this end, several approaches have been suggested, yet identifying the most stable cluster geometry (i.e., global potential energy minimum) remains a challenge, especially for highly symmetric clusters. Here, we suggest a new funneled Monte Carlo-based simulated annealing (SA) approach, which includes two key steps: generation of symmetrical clusters and classification of the clusters according to their geometry using machine learning (MCSA-ML). We demonstrate the merits of the MCSA-ML method in comparison to other approaches on several Lennard-Jones (LJ) clusters and four molecular clusters-Ser8(Cl-)2, H+(H2O)6, Ag+(CO2)8, and Bet4Cl-. For the latter of these clusters, the correct structure is unknown, and hence, we compare the experimental and simulated fragmentation patterns, and the fragmentation of the proposed global minimum matches experiments closely. Additionally, based on the fragmentation of the predicted betaine cluster, we were able to identify hitherto unknown neutral fragmentation channels. In comparison to results obtained with other methods, we demonstrated a superior ability of MCSA-ML to predict clusters with high symmetry and similar abilities to predict clusters with asymmetrical structures.

Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere

The main nucleating vapor in the atmosphere is thought to be sulfuric acid (H 2 SO 4 ), stabilized by ammonia (NH 3 ). However, in marine and polar regions, NH 3 is generally low, and H 2 SO 4 is frequently found together with iodine oxoacids [HIO x , i.e., iodic acid (HIO 3 ) and iodous acid (HIO 2 )]. In experiments performed with the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we investigated the interplay of H 2 SO 4 and HIO x during atmospheric particle nucleation. We found that HIO x greatly enhances H 2 SO 4 (-NH 3 ) nucleation through two different interactions. First, HIO 3 strongly binds with H 2 SO 4 in charged clusters so they drive particle nucleation synergistically. Second, HIO 2 substitutes for NH 3 , forming strongly bound H 2 SO 4 -HIO 2 acid-base pairs in molecular clusters. Global observations imply that HIO x is enhancing H 2 SO 4 (-NH 3 ) nucleation rates 10- to 10,000-fold in marine and polar regions.

Regional air quality study by assessing trace metal atmospheric deposition

This study addresses the atmospheric deposition of trace elements investigated in Albania, Croatia and Macedonia in 2010 as part of the European Moss Study. This study provides data on the concentration of ten metals (Cd, Cr, Cu, Ni, Pb, V, Zn, Fe, Al, and Li) in naturally growing mosses. In general, all concentration data follow a lognormal distribution. Cd, Cr, Ni, and Zn show strong fluctuations in the moss samples from Albania and Macedonia, and Pb, Fe, and Al in the mosses from Croatia. The concentrations of Cd, Cu, and Zn were higher in the samples from Croatia than in those from Albania and Macedonia; the concentrations of Cr, Ni, V, Fe, Al, and Li were higher in the samples from Albania than in those from Croatia and Macedonia; and a higher concentration of Pb was found in the samples from Macedonia. The observed relationship between the concentration of lithogenic elements (Al, Fe, and V) and the air quality index (AQI) confirms that moss species have a high capacity to retain atmospheric deposition particles. The anthropogenic emission sources of these elements from local and long-range transport were considered to be the most important factors affecting air quality in the studied areas.

Intrinsic and extrinsic techniques for quantification uncertainty of an interpretable GRU deep learning model used to predict atmospheric total suspended particulates (TSP) in Zabol, Iran during the dusty period of 120-days wind

Total suspended particulates (TSP), as a key pollutant, is a serious threat for air quality, climate, ecosystems and human health. Therefore, measurements, prediction and forecasting of TSP concentrations are necessary to mitigate their negative effects. This study applies the gated recurrent unit (GRU) deep learning model to predict TSP concentrations in Zabol, Iran, during the dust period of the 120-day wind (3 June - 4 October 2014). Three uncertainty quantification (UQ) techniques consisting of the blackbox metamodel, heteroscedastic regression and infinitesimal jackknife were applied to quantify the uncertainty associated with GRU model. Permutation feature importance measure (PFIM), based on the game theory, was employed for the interpretability of the predictive model's outputs. A total of 80 TSP samples were collected and were randomly divided as training (70%) and validation (30%) datasets, while eight variables were used in the TSP prediction model. Our findings showed that GRU performed very well for TSP prediction (with r and Nash Sutcliffe coefficient (NSC) values above 0.99 for both datasets, and RMSE of 57 μg m−3 and 73 μg m−3 for training and validation datasets, respectively). Among the three UQ techniques, the infinitesimal jackknife was the most accurate one, while all the observed and predicted TSP values fell within the continence limitation estimated by the model. PFIM plots showed that wind speed and air humidity were the most and least important variables, respectively, impacting the predictive model's outputs. This is the first attempt of using an interpretable DL model for TSP prediction modelling, recommending that future research should involve aspects of uncertainty and interpretability of the predictive models. Overall, UQ and interpretability techniques have a key role in reducing the impact of uncertainties during optimization and decision making, resulting in better understanding of sophisticated mechanisms related to the predictive model.

Environmental and health implications of Pb-bearing particles in settled urban dust from an arid city affected by Pb–Zn factory emissions

Metal-rich particles originating from non-ferrous metallurgical activities are the primary source of atmospheric metals in urban environments. These particles vary in size, morphology, and elemental compositions and they undergo weathering processes that alter their composition and affect their toxicity. This study focuses on lead (Pb)-rich particles in settled urban dust within an arid and dusty city, Torreón in North Mexico, affected by Met–Mex Peñoles complex, one of the world's largest Ag–Cd–Pb–Zn smelting and refining facilities in operating since 1901. Torreón is characterized by arid conditions, temperature fluctuations, and low humidity. Dry atmospheric particles were collected in 2015 and 2017 from Torreón's urban area within a 3 km radius of the Met–Mex Peñoles complex. We used various analytical techniques, including scanning electron microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), and X-ray powder diffraction (XRD) to determine the size, morphology, elemental composition and mineralogy of Pb-bearing particles. Our analysis revealed a range of Pb-bearing particle sizes and morphologies with varying Pb (0.3 to 51–87.2%) and other element contents, such as As (0.04 to 1–3.4%), Cd (0.4 to 3.3–5.1%), Cu (0.51–14.1%), Hg (ND-0.6%), and Zn (1.7 to 79–90.3%). XRD analysis confirmed the presence of Pb and Zn sulfides, Pb carbonates, Pb sulfate, and Pb oxides in urban dust, both as individual particles and agglomerates. Primary Pb minerals were linked to fugitive feed concentrates and smelter flue gas at Met–Mex Peñoles, while secondary Pb minerals, like Pb carbonates, Pb sulfate, and Pb oxides, resulted from direct emissions and weathering processes. Compared to galena, secondary Pb minerals exhibit higher chemical availability in the environment, posing greater risks to the environment and human health. As the particles analyzed are presumed to be resuspended rather than freshly emitted by Met–Mex, the presence of secondary Pb minerals in settled urban dust is predominantly linked to weathering processes. The physical and chemical transformations in Pb-rich particles contribute to increased Pb bioavailability and toxicity in urban dust, with substantial implications for environmental and human health. These findings highlight the potential consequences of weathered Pb-rich particle in urban areas, particularly in the arid and dusty city of Torreón.

Seasonal variations in composition and sources of atmospheric ultrafine particles in urban Beijing based on near-continuous measurements

Abstract. Understanding the composition and sources of atmospheric ultrafine particles (UFPs) is essential in evaluating their exposure risks. It requires long-term measurements with high time resolution, which are scarce to date. We performed near-continuous measurements of UFP composition during four seasons in urban Beijing using a thermal desorption chemical ionization mass spectrometer, accompanied by real-time size distribution measurements. We found that UFPs in urban Beijing are dominated by organic components, varying seasonally from 68 % to 81 %. CHO organics (i.e., molecules containing carbon, hydrogen, and oxygen) are the most abundant in summer, while sulfur-containing organics, some nitrogen-containing organics, nitrate, and chloride are the most abundant in winter. With the increase of particle diameter, the contribution of CHO organics decreases, while that of sulfur-containing and nitrogen-containing organics, nitrate, and chloride increases. Source apportionment analysis of the UFP organics indicates contributions from cooking and vehicle sources, photooxidation sources enriched in CHO organics, and aqueous/heterogeneous sources enriched in nitrogen- and sulfur-containing organics. The increased contributions of cooking, vehicle, and photooxidation components are usually accompanied by simultaneous increases in UFP number concentrations related to cooking emission, vehicle emission, and new particle formation, respectively, while the increased contribution of the aqueous/heterogeneous composition is usually accompanied by the growth of UFP mode diameters. The highest UFP number concentrations in winter are due to the strongest new particle formation, the strongest local primary particle number emissions, and the slowest condensational growth of UFPs to larger sizes. This study provides a comprehensive understanding of urban UFP composition and sources and offers valuable datasets for the evaluation of UFP exposure risks.

Development of a tunable, narrow, and ultraviolet Ce:LiCAF crystal multipass laser amplifier for environmental application

In this paper, the authors present results on the development of both an oscillator and a 4-pass amplifier of ultraviolet and narrow linewidth pulses using a Ce:LiCAF crystal. By using a grating at one end of the laser cavity, the output laser wavelength of the laser can be tuned from 285 nm to 296 nm with a maximum output power of 8 mW at 288.5 nm. Moreover, amplification in a 4-pass amplifier of the Ce:LiCAF laser was investigated theoretically and experimentally. From the results, 49.0 mW amplified pulses can be obtained using a 4-pass amplifier with 7.0 mW power and 3.6 ns pulse duration at 288.5 nm injection, corresponding to an amplifier gain of 7. Furthermore, the angular scattering intensity of some common single-particle aerosols such as black carbon, brown carbon, and polluted water has been studied using the Ce:LiCAF laser. This result can serve as the basis for the multipass laser amplifier’s environmental application, particularly in identifying atmospheric particles.

Evidence of nitrate-based nighttime atmospheric nucleation driven by marine microorganisms in the South Pacific.

Our understanding of ocean-cloud interactions and their effect on climate lacks insight into a key pathway: do biogenic marine emissions form new particles in the open ocean atmosphere? Using measurements collected in ship-borne air-sea interface tanks deployed in the Southwestern Pacific Ocean, we identified new particle formation (NPF) during nighttime that was related to plankton community composition. We show that nitrate ions are the only species for which abundance could support NPF rates in our semicontrolled experiments. Nitrate ions also prevailed in the natural pristine marine atmosphere and were elevated under higher sub-10 nm particle concentrations. We hypothesize that these nucleation events were fueled by complex, short-term biogeochemical cycling involving the microbial loop. These findings suggest a new perspective with a previously unidentified role of nitrate of marine biogeochemical origin in aerosol nucleation.

PH dependence of brown-carbon optical properties in cloud water

Abstract. Light-absorbing organic species present in aerosols, collectively called brown carbon (BrC), have important but highly uncertain effects on climate. Clouds likely represent a significant medium for secondary BrC production and for bleaching reactions, though the relative importance of the formation and loss processes in clouds is unknown at present. The acidity (or pH) of atmospheric particles and clouds affects the optical properties of BrC and bleaching rates. Given the wide variability of pH in the atmosphere (pH in particles and clouds ranges from −1 to 8), the optical properties of BrC and its bleaching behavior are expected to vary significantly, and the link between pH and BrC is yet another uncertainty in attempts to constrain its climate forcing effects. In this work, we characterize the pH dependence of BrC optical properties – including light absorption at 365 nm (Abs365), the mass absorption coefficient (MAC365), and the absorption Ångström exponent (AAE) – in bulk cloud water sampled from the summit of Whiteface Mountain, NY. In all samples (n=17), Abs365 and MAC365 increased linearly with increasing pH, highlighting the importance of reporting pH in studies of BrC in aqueous media. There was strong variability in the sensitivity of Abs365 to pH, with normalized slopes that ranged from 5.1 % to 17.2 % per pH unit. The normalized slope decreased strongly with increasing cloud water [K+], suggesting that the non-biomass-burning BrC has optical properties that are more sensitive to pH than BrC associated with biomass burning. AAE also showed a distinct pH dependence as it was relatively flat between pH 1.5–5 and then decreased significantly above pH 5. The cloud water composition was used to inform thermodynamic predictions of aerosol pH upwind and/or downwind of Whiteface Mountain and the subsequent changes in BrC optical properties. Overall, these results show that, in addition to secondary BrC production, photobleaching, and the altitudinal distribution, the climate forcing of BrC is quite strongly affected by its pH-dependent absorption.

Spatial and temporal patterns of organophosphate Esters flame retardants and plasticizers in airborne particles over the Mediterranean sea

We studied the co-occurrence of OPEs and other constituents in atmospheric particles at the two edges of the Mediterranean Sea, under the influence of the transport of polluted air from Europe and dust from the Sahara. The highest OPE concentrations were observed during the summer period in the East Mediterranean and in spring for the NW Mediterranean. The total average atmospheric concentration of Σ6OPEs in the NW Mediterranean was 2103 ± 2020 pg m−3 (n = 23) with EHDPP and TCPP to be the predominant OPEs, accounting on average for 46% and 37% of the total Ʃ6OPEs concentrations, respectively. The average concentration of Σ6OPEs in East Mediterranean was 156.4 ± 170.3 pg m−3 (n = 67) with TCPP showing the highest concentration (116.1 ± 92.8 pg m−3), followed by TCEP (67.5 ± 55.8 pg m−3). In both areas, OPEs were mostly associated with fossil fuel combustion and road traffic, while the air masses from Saharan desert influenced the concentration of EHDPP, TCEP in NW Mediterranean and the TCEP concentration levels in the East Mediterranean. The total annual deposition of reported OPEs to the Mediterranean basin was estimated to be 584 tonnes, accounting for about 8.5% of the total deposited anthropogenic phosphorus.

Contribution of chemical composition to oxidative potential of atmospheric particles at a rural and an urban site in the Po Valley: Influence of high ammonia agriculture emissions

The present study investigates the chemical composition and oxidative potential (OP) of PM10 particles at two sites in the Po Valley (Norther Italy), with the aim of evidence the impact of high level of atmosphere ammonia (NH3). Field measurements were conducted in a rural location (Bertonico) close to farms strongly impacted by high ammonia emissions from agriculture and livestock husbandry. The urban site was in the metropolitan area of Milan. The NH3 concentrations observed at the rural site were about 5 times higher than those at the urban location, generating higher levels of secondary inorganic aerosol (ΣSIA) at Bertonico (16.6 ± 6.33 μg m−3) than at Milan 12.6 ± 4.93 μg m−3. The oxidative potential measured with the ascorbic acid assay (OPAAV) was almost triple in Milan than at Bertonico, namely 1.48 ± 1.08 nmol min−1 m−3 and 0.44 ± 0.23 nmol min−1 m−3, respectively, while the measured OPDTTV responses were similar at both sites, close to ∼ 0.5 ± 0.3 nmol min−1 m−3. These results suggested that the SIA components don't significantly contribute to the PM10 oxidative reactivity, although they account for most of the PM10 mass. Despite such an OP-inactivity, the SIA components resulted significantly correlated with both OPAAV and OPDTTV responses. This may be likely due to their inter-correlation with other redox-active components, such as the secondary organic species, which are synergically produced along with the SIA formation. In addition, an increase in the metals reactivity towards the OP assays, may be associated with the PM10 acidic environment produced by enhanced HNO3 and H2SO4 levels. Therefore, the contribution of the SIA to PM oxidative toxicity cannot be ignored in assessing health risk associated with PM exposure.

Measurement report: Dust and anthropogenic aerosols' vertical distributions over northern China dense aerosols gathered at the top of the mixing layer

Abstract. Over the past decades, northern China has been suffering from persistent air pollution caused by both fine and coarse atmospheric particles. Although there are plenty of theoretical and observational studies on aerosols in northern China, most of them only consider total aerosol concentrations and focus on heavy pollution episodes; the long-term vertical distributions of dust (coarse) and anthropogenic aerosols (fine) and their relationships with the mixing layer height (MLH) have not been revealed. In this study, the dust and anthropogenic aerosols' mass concentration and the MLH were retrieved by polarization Raman lidar over Beijing from May 2019 to February 2022. We found that large amounts of anthropogenic aerosols accumulate at the top of the mixing layer, which is most noticeable in summer, with monthly mean mass concentration up to 57 µg m−3. It is mainly influenced by the southward transport in the upper air, where the atmosphere is relatively stable and moist, favoring hygroscopic growth of particles. Dust mass concentration is discontinuous in the vertical direction, not only on the ground but also in lofted layers that reach up to several kilometers. The heights of these lofted dust layers exhibited apparent seasonal dependence, with the height of the main dust layer gradually ascending from 1.1 km to about 2.5 km from April to June and below 3 km from October to December. In addition, there is a significant negative correlation between bottom anthropogenic aerosols' mass concentration and the MLH, and an inverse function fit is more suitable to characterize this relationship, while the relationship between bottom dust mass concentration and the MLH is insignificant. These results will enhance our understanding of the sophisticated interactions between dust and anthropogenic aerosols, the MLH, and regional transport in northern China. It will also help to refine atmospheric chemistry models and improve surface prediction capabilities.

Acidity in rainwater and airborne suspended particles in the southwestern coast of the East Sea (Sea of Japan): Their potential impact on seawater total alkalinity

Our understanding of the impact of atmospheric acid deposition on marine carbonate system remains limited, largely due to a lack of data regarding acidity present in atmospheric particles and precipitation. Previous research has relied on the electroneutrality-based ion balance method for indirect estimation of atmospheric acidity. In this study, atmospheric samples collected at a coastal site of South Korea were mixed with seawater to measure the change in seawater total alkalinity (ΔTAAPL) associated with atmospheric proton loading. For the precipitation samples, the measured ΔTAAPL and electroneutrality-based estimates showed a significant correlation. However, we did not observe similar results for the atmospheric particle samples. Furthermore, the decrease in oceanic TA due to ΔTAAPL was substantially smaller than that in dissolved inorganic carbon from concurrent nitrogen fertilization. Consequently, the adverse impact of acid deposition on ocean acidification or air-sea exchange of CO2 appears to be insignificant on a short-term scale.

Dehazing in hyperspectral images: the GRANHHADA database.

In this study, we present an analysis of dehazing techniques for hyperspectral images in outdoor scenes. The aim of our research is to compare different dehazing approaches for hyperspectral images and introduce a new hyperspectral image database called GRANHHADA (GRANada Hyperspectral HAzy Database) containing 35 scenes with various haze conditions. We conducted three experiments to assess dehazing strategies, using the Multi-Scale Convolutional Neural Network (MS-CNN) algorithm. In the first experiment, we searched for optimal triplets of spectral bands to use as input for dehazing algorithms. The results revealed that certain bands in the near-infrared range showed promise for dehazing. The second experiment involved sRGB dehazing, where we generated sRGB images from hyperspectral data and applied dehazing techniques. While this approach showed improvements in some cases, it did not consistently outperform the spectral band-based approach. In the third experiment, we proposed a novel method that involved dehazing each spectral band individually and then generating an sRGB image. This approach yielded promising results, particularly for images with a high level of atmospheric dust particles. We evaluated the quality of dehazed images using a combination of image quality metrics including reference and non-reference quality scores. Using a reduced set of bands instead of the full spectral image capture can contribute to lower processing time and yields better quality results than sRGB dehazing. If the full spectral data are available, then band-per-band dehazing is a better option than sRGB dehazing. Our findings provide insights into the effectiveness of different dehazing strategies for hyperspectral images, with implications for various applications in remote sensing and image processing.

Improved Configurational Sampling Protocol for Large Atmospheric Molecular Clusters.

The nucleation process leading to the formation of new atmospheric particles plays a crucial role in aerosol research. Quantum chemical (QC) calculations can be used to model the early stages of aerosol formation, where atmospheric vapor molecules interact and form stable molecular clusters. However, QC calculations heavily depend on the chosen computational method, and when dealing with large systems, striking a balance between accuracy and computational cost becomes essential. We benchmarked the binding energies and structures and found the B97-3c method to be a good compromise between the accuracy and computational cost for studying large cluster systems. Further, we carefully assessed configurational sampling procedures for targeting large atmospheric molecular clusters containing up to 30 molecules (approximately 2 nm in diameter) and proposed a funneling approach with highly improved accuracy. We find that several parallel ABCluster explorations lead to better guesses for the cluster global energy minimum structures than one long exploration. This methodology allows us to bridge computational studies of molecular clusters, which typically reach only around 1 nm, with experimental studies that often measure particles larger than 2 nm. By employing this workflow, we searched for low-energy configurations of large sulfuric acid-ammonia and sulfuric acid-dimethylamine clusters. We find that the binding free energies of clusters containing dimethylamine are unequivocally more stable than those of the ammonia-containing clusters. Our improved configurational sampling protocol can in the future be applied to study the growth and dynamics of large clusters of arbitrary compositions.

A comprehensive survey of reference materials for their use in quality assurance for the determination of Np-237 in environmental samples

Neptunium-237 (237Np) is one of the most hazardous radionuclides of public concern due to its radiological toxicity, long half-life and high environmental mobility. Standard reference materials (SRMs) with well characterized 237Np activity concentrations are valuable for method development and validation of 237Np determination in environmental samples. In this study, a comprehensive literature survey of 237Np activity concentrations in 25 SRMs was carried out covering the various matrices of sediment, soil, seawater, atmospheric particles, and biota. After data screening, arithmetic mean of the activity concentrations of 237Np in literatures were calculated as statistical values (SVs). Then, accuracies of different instrument analyses and acid digestion methods were evaluated based on the SVs. Finally, by optimizing the sector field ICP-MS analytical method, 237Np activity concentration in JSAC-0471 soil SRM was measured. The application of SVs provides 237Np activity concentration information in more SRMs. Besides SRMs certified by technically validated procedures, SRMs with SVs and the measurement of JASC-0471 provide more options for suitable selection of SRMs for 237Np determination.

The effect of atmospherically relevant aminium salts on water uptake

Abstract. Atmospheric new particle formation is initiated by clustering of gaseous precursors, such as small acids and bases. The hygroscopic properties of those precursors therefore affect the hygroscopic properties of aerosol particles. In this work, the water uptake of different salts consisting of atmospheric small acids and amines was studied computationally using the conductor-like screening model for real solvents (COSMO-RS). This method allows for the prediction of water activities in atmospherically relevant salts that have not been included in other thermodynamics models. Water activities are reported here for binary aqueous salt solutions, as well as ternary solutions containing proxies for organic aerosol constituents. The order of the studied cation species regarding water activities is similar in sulfate, iodate, and methylsulfonate, as well as in bisulfate and nitrate. Predicted water uptake strengths (in mole fraction) conform to the following orders: tertiary > secondary > primary amines and guanidinos > amino acids. The addition of water-soluble organic to the studied salts generally leads to weaker water uptake compared to pure salts. On the other hand, water-insoluble organic likely phase separates with aqueous salt solutions, leading to minimal effects on water uptake.

Seasonal Disparities of Human Health Risk and Particle-Bound Metal Characteristics Associated with Atmospheric Particles in a Fishery Harbor.

The effects of atmospheric pollution from ship emissions have been considered for several harbors worldwide. The health risk assessment and source apportionment of particle-bound metals in a fishery harbor were investigated in this study. The most abundant metal elements in particulate matter (PM) on all sampling days in three seasons were Fe (280.94 ± 136.93 ng/m3), Al (116.40 ± 71.25 ng/m3), and Zn (110.55 ± 26.70 ng/m3). The ratios of V/Ni were 1.44 ± 0.31, 1.48 ± 0.09 and 1.87 ± 0.06 in PM10, PM2.5, and PM1, respectively. Meanwhile, the ratios higher than 1 indicated that fuel oil combustion from ship emission in fishery harbor. The highest deposits of total particle-bound metals in the human respiratory tract were in the head airway (HA), accounting for 76.77 ± 2.29% of the total particle-bound metal concentration, followed by 5.32 ± 0.13% and 2.53 ± 0.15% in the alveolar region (AR) and tracheobronchial (TB) region, respectively. The total cancer risk (CR) of inhalation exposure to local residents exceeded 10-6. Mean total CR values followed the sequence: autumn (1.24 × 10-4) > winter (8.53 × 10-5) > spring (2.77 × 10-6). Source apportionment of related metal emissions was mobile pollution emissions (vehicle/boat) (37.10-48.92%), metal fumes of arc welding exhaust (19.68-34.42%), spray-painting process (12.34-16.24%), combustion emissions (6.32-13.12%), and metal machining processes (9.04-16.31%) in Singda fishing harbor. These results suggest that proper control of heavy metals from each potential source in fishing harbor areas should be carried out to reduce the carcinogenic risk of adverse health effects.

Conditionally Background Level of Aerosol Pollution of Near-Surface Air in Moscow and One of Its Suburbs: Seasonal Variations

The data of continuous observations of aerosol composition in the near-surface atmosphere in Moscow (in the city center) and in Moscow region (near Zvenigorod, Moscow region) for three years, from autumn 2019 to the end of 2022, are analyzed. The obtained data were compared with the results of observations on the Moscow network stations “Mosecomonitoring”. The concept of conditionally background aerosol pollution of the atmosphere in Moscow is introduced for those days when the average daily concentration of PM10 is less than the MPC value (60 µg/m3). Previously, the authors found that all episodes of increased aerosol pollution in Moscow with daily average PM10 concentration higher than the MPC value, are associated either with the presence of a close local source in the city itself, or with the long-range transport of fire aerosols and/or dust from other territories to the Moscow region. The average daily PM2.5 concentration in the city and the suburb is lower than the MPC (35 µg/m3) all year round. The days corresponding to the introduced conditional background make up more than 91% over three years in the center of Moscow. Such a conditional background is formed by both natural and anthropogenic sources of aerosols, and not only of local, but also of remote origin. It implicitly takes into account the influence of meteorological conditions on sources and sinks of aerosols, as well as advective air mass transport of aerosol to and from the city. Seasonal variations in mass concentration of PM10, PM2.5 particles and individual chemical elements, as well as in the distribution of chemical elements by the size of aerosol particles in near-surface atmosphere under conditionally background pollution are analyzed. The emphasis is placed on the similarity and difference in the conditionally background near-surface aerosol for the city and the suburb in different seasons.

Chemical Characterization of Rural Organic Aerosol in the North China Plain Using Ultrahigh-Resolution Mass Spectrometry

Atmospheric organic aerosol (OA) affects air quality and human health. However, compared with urban areas, the chemical composition and temporal distribution of OA in rural regions are still not well understood. In this study, one-year atmospheric particles with an aerodynamic equivalent diameter of ≤2.5 μm (PM2.5) were collected at a rural site in Quzhou County, the North China Plain (NCP), from August 2020 to July 2021. OA in PM2.5 samples were analyzed with an ultrahigh-performance liquid chromatograph (UHPLC) coupled to an ultrahigh-resolution Orbitrap mass spectrometer in negative mode (ESI−). The results show that the chemical composition and properties of OA varied in different seasons. According to the hierarchical cluster analysis, the molecular formulas of winter OA were close to those in spring, whereas the chemical composition of OA in summer and autumn was similar. The O/C ratio of summer OA was the highest at 1.21, followed by that in autumn (0.92) and spring (0.87), while the winter OA had the lowest O/C ratio of 0.64. It indicates that, compared to the other three seasons, OA underwent more intense oxidation processes in the summer. Moreover, winter OA contained more aromatic compounds with a relative peak abundance fraction of 40%, which may be related to anthropogenic sources (e.g., coal burning) in the winter in the NCP. In addition, biomass burning is considered an important source of OA in the rural region of Quzhou County, the NCP, in all seasons.