Evaluation of laboratory and environmental exposure systems for protein modification upon gas pollutants and environmental factors.

Chemical modifications of proteins induced by ambient ozone (O3) and nitrogen oxides (NOx) are of public health concerns due to their potential to trigger respiratory diseases. The laboratory and environmental exposure systems have been widely used to investigate their relevant mechanism in the atmosphere. Using bovine serum albumin (BSA) as a model protein, we evaluated the two systems and aimed to reduce the uncertainties of both the reactants and products in the corresponding kinetic study. In the laboratory simulation system, the generated gaseous pollutants showed negligible losses. Ten layers of BSA were coated on the flow tube with protein extraction recovery of 87.4%. For environmental exposure experiment, quartz fiber filter was selected as the upper filter with low gaseous O3 (8.0%) and NO2 (1.7%) losses, and cellulose acetate filter was appropriate for the lower filter with protein extraction efficiency of 95.2%. The protein degradation process was observed without the exposure to atmospheric oxidants and contributed to the loss of protein monomer mass fractions, while environmental factors (e.g., molecular oxygen and ultraviolet) may cause greater protein monomer losses. Based on the evaluation, the study exemplarily applied the two systems to protein modification and both showed that O3 promotes the protein oligomerization and nitration, while increased temperature can accelerate the oligomerization and increased relative humidity can inhibit the nitration in the environmental exposure samples. The developed laboratory and environmental systems are suitable for studying protein modifications formed under different atmospheric conditions. A combination of the two will further reveal the actual mechanism of protein modifications.

Aerosol Proteinaceous Matter in Coastal Okinawa, Japan: Influence of Long-Range Transport and Photochemical Degradation.

The characteristics, sources, and atmospheric oxidation processes of marine aerosol proteinaceous matter (APM), including total proteins and free amino acids (FAAs), were investigated using a set of 1 year total suspended particulate (TSP) samples collected in the coastal area of Okinawa Island in the western North Pacific rim. The concentrations of APM at this site (total proteins: 0.16 ± 0.10 µg m-3 and total FAAs: 9.7 ± 5.6 ng m-3, annual average) are comparable to those of marine APM. The major FAA species of APM are also similar to previously reported marine APM with glycine as the dominant species (31%). Based on the different seasonal trends and weak correlations of total proteins and FAAs, we found that they were contributed by different sources, especially with the influence of long-range transport from the Asian continent of northern China and Mongolia and the oceanic area of the Bohai Sea, Yellow Sea, and East China Sea. The photochemical oxidation processes of high-molecular-weight proteins releasing FAAs (especially glycine) were also considered as an important factor influencing the characteristics of APM at this site. In addition, we propose a degradation process based on the correlation with ozone and ultraviolet radiation, emphasizing their roles in the degradation of proteins. Our findings help to deepen the understanding of atmospheric photochemical reaction processes of organic aerosols.

Ambient volatile organic compounds at a receptor site in the Pearl River Delta region: Variations, source apportionment and effects on ozone formation.

We present the continuously measurements of volatile organic compounds (VOCs) at a receptor site (Wan Qing Sha, WQS) in the Pearl River Delta (PRD) region from September to November of 2017. The average mixing ratios of total VOCs (TVOCs) was 36.3 ± 27.9 ppbv with the dominant contribution from alkanes (55.5%), followed by aromatics (33.3%). The diurnal variation of TVOCs showed a strong photochemical consumption during daytime, resulting in the formation of ozone (O3). Five VOC sources were resolved by the positive matrix factorization (PMF) model, including solvent usage (28.6%), liquid petroleum gas (LPG) usage (24.4%), vehicle exhaust (21.0%), industrial emissions (13.2%) and gasoline evaporation (12.9%). The regional transport air masses from the upwind cities of south China can result in the elevated concentrations of TVOCs. Low ratios of TVOCs/NOx (1.53 ± 0.88) suggested that the O3 formation regime at WQS site was VOC-limited, which also confirmed by a photochemical box model with the master chemical mechanism (PBM-MCM). Furthermore, the observation on high-O3 episode days revealed that frequent O3 outbreaks at WQS were mainly caused by the regional transport of anthropogenic VOCs especially for aromatics and the subsequent photochemical reactions. This study provides valuable information for policymakers to propose the effective control strategies on photochemical pollution in a regional perspective.

The behaviors of Microcystis aeruginosa and microcystins during the Fe2+/persulfate (PS) preoxidation-coagulation and flocs storage period.

The frequent occurrence of toxin-producing cyanobacteria blooms driven by anthropogenic eutrophication has become a major threat to aquaculture ecosystems worldwide. In this study, the behavior of M. aeruginosa cells during flocs storage period of 6 days was first investigated after pre-oxidation and coagulation of Fe2+/PS. Fe2+/PS achieved a superior removal efficiency of 90.7% for OD680 and 90.4% for chl-a. The contents of extracellular MCs in the pre-oxidation and coagulation system were significantly (P < 0.05) lower than those in the control. A significant (P < 0.05) difference in intracellular protein between the control and the coagulated systems was observed. Three-dimensional fluorescence excitation emission matrix (EEM) was employed to investigate the variations in extracellular organic matter (EOM) during flocs storage. The results indicated the presence of four peaks, representing protein-like substances, intermediate dissolved microbial metabolites, fulvic and humic-like compounds in the Fe2+/PS process. And the intensities of four peaks were all decreased in the Fe2+/PS system compared to those in the control. A low level of accumulated residual Fe of 0.28 mg/L was observed without posing potential environmental risk. The results showed that the M. aeruginosa cells were under stressful conditions after 3-d storage due to the decomposition of extracellular polymeric substances (EPSs) and the insufficient supply of nutrients. However, SEM results indicated that no significant alteration in cell morphology was observed. Therefore, with high removal of M. aeruginosa, low MCs concentrations, and trivial cell damage, the Fe2+/PS preoxidation-coagulation was proved to be an environmental-friendly method for cyanobacteria removal without yielding serious secondary pollution. This work will contribute to better understanding and managing the cyanobacteria-laden aquaculture water after pre-oxidation and coagulation.

Occurrence of Aerosol Proteinaceous Matter in Urban Beijing: An Investigation on Composition, Sources, and Atmospheric Processes During the "APEC Blue" Period.

Aerosol proteinaceous matter is comprised of a substantial fraction of bioaerosols. Its origins and interactions in the atmosphere remain poorly understood. We present observations of total proteins, combined, and free amino acids (CAAs and FAAs) in fine particulate matter (PM2.5) samples in urban Beijing before and during the 2014 Asia-Pacific Economic Cooperation (APEC) summit. The decreases in proteins, CAAs and FAAs levels were observed after the implementation of restrictive emission controls. Significant changes were observed for the composition profiles in FAAs with the predominance of valine before the APEC and glycine during the APEC, respectively. These variations could be attributed to the influence of sources, atmospheric processes, and meteorological conditions. FAAs (especially valine and glycine) were suggested to be released by the degradation of high molecular weight proteins/polypeptides by atmospheric oxidants (i.e., ozone and free radicals) and nitrogen dioxide. Besides daytime reactions, nighttime chemistry was found to play an important role in the atmospheric formation of valine during the nights, suggesting the possible influence of NO3 radicals. Our findings provide new insights into the significant impacts of atmospheric oxidation capacity on the occurrence and transformation of aerosol proteinaceous matter which may affect its environmental, climate and health effects.

Atmospheric protein chemistry influenced by anthropogenic air pollutants: nitration and oligomerization upon exposure to ozone and nitrogen dioxide.

The allergenic potential of airborne proteins may be enhanced via post-translational modification induced by air pollutants like ozone (O3) and nitrogen dioxide (NO2). The molecular mechanisms and kinetics of the chemical modifications that enhance the allergenicity of proteins, however, are still not fully understood. Here, protein tyrosine nitration and oligomerization upon simultaneous exposure of O3 and NO2 were studied in coated-wall flow-tube and bulk solution experiments under varying atmospherically relevant conditions (5-200 ppb O3, 5-200 ppb NO2, 45-96% RH), using bovine serum albumin as a model protein. Generally, more tyrosine residues were found to react via the nitration pathway than via the oligomerization pathway. Depending on reaction conditions, oligomer mass fractions and nitration degrees were in the ranges of 2.5-25% and 0.5-7%, respectively. The experimental results were well reproduced by the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). The extent of nitration and oligomerization strongly depends on relative humidity (RH) due to moisture-induced phase transition of proteins, highlighting the importance of cloud processing conditions for accelerated protein chemistry. Dimeric and nitrated species were major products in the liquid phase, while protein oligomerization was observed to a greater extent for the solid and semi-solid phase states of proteins. Our results show that the rate of both processes was sensitive towards ambient ozone concentration, but rather insensitive towards different NO2 levels. An increase of tropospheric ozone concentrations in the Anthropocene may thus promote pro-allergic protein modifications and contribute to the observed increase of allergies over the past decades.

Organophosphate Esters in Air, Snow, and Seawater in the North Atlantic and the Arctic.

The concentrations of eight organophosphate esters (OPEs) have been investigated in air, snow and seawater samples collected during the cruise of ARK-XXVIII/2 from sixth June to third July 2014 across the North Atlantic and the Arctic. The sum of gaseous and particle concentrations (ΣOPE) ranged from 35 to 343 pg/m3. The three chlorinated OPEs accounted for 88 ± 5% of the ΣOPE. The most abundant OPE was tris(2-chloroethyl) phosphate (TCEP), with concentrations ranging from 30 to 227 pg/m3, followed by three major OPEs, such as tris(1-chloro-2-propyl) phosphate (TCPP, 0.8 to 82 pg/m3), tri-n-butyl phosphate (TnBP, 2 to 19 pg/m3), and tri-iso-butyl phosphate (TiBP, 0.3 to 14 pg/m3). The ΣOPE concentrations in snow and seawater ranged from 4356 to 10561 pg/L and from 348 to 8396 pg/L, respectively. The atmospheric particle-bound dry depositions of TCEP ranged from 2 to 12 ng/m2/day. The air-seawater gas exchange fluxes were dominated by net volatilization from seawater to air for TCEP (mean, 146 ± 239 ng/m2/day), TCPP (mean, 1670 ± 3031 ng/m2/day), TiBP (mean, 537 ± 581 ng/m2/day) and TnBP (mean, 230 ± 254 ng/m2/day). This study highlighted that OPEs are subject to long-range transport via both air and seawater from the European continent and seas to the North Atlantic and the Arctic.

Proteins and Amino Acids in Fine Particulate Matter in Rural Guangzhou, Southern China: Seasonal Cycles, Sources, and Atmospheric Processes.

Water-soluble proteinaceous matter including proteins and free amino acids (FAAs) as well as some other chemical components was analyzed in fine particulate matter (PM2.5) samples collected over a period of one year in rural Guangzhou. Annual averaged protein and total FAAs concentrations were 0.79 ± 0.47 µg m-3 and 0.13 ± 0.05 µg m-3, accounting for 1.9 ± 0.7% and 0.3 ± 0.1% of PM2.5, respectively. Among FAAs, glycine was the most abundant species (19.9%), followed by valine (18.5%), methionine (16.1%), and phenylalanine (13.5%). Both proteins and FAAs exhibited distinct seasonal variations with higher concentrations in autumn and winter than those in spring and summer. Correlation analysis suggests that aerosol proteinaceous matter was mainly derived from intensive agricultural activities, biomass burning, and fugitive dust/soil resuspension. Significant correlations between proteins/FAAs and atmospheric oxidant (O3) indicate that proteins/FAAs may be involved in O3 related atmospheric processes. Our observation confirms that ambient FAAs could be degraded from proteins under the influence of O3, and the stoichiometric coefficients of the reactions were estimated for FAAs and glycine. This finding provides a possible pathway for the production of aerosol FAAs in the atmosphere, which will improve the current understanding on atmospheric processes of proteinaceous matter.

Air Pollution and Climate Change Effects on Allergies in the Anthropocene: Abundance, Interaction, and Modification of Allergens and Adjuvants.

Air pollution and climate change are potential drivers for the increasing burden of allergic diseases. The molecular mechanisms by which air pollutants and climate parameters may influence allergic diseases, however, are complex and elusive. This article provides an overview of physical, chemical and biological interactions between air pollution, climate change, allergens, adjuvants and the immune system, addressing how these interactions may promote the development of allergies. We reviewed and synthesized key findings from atmospheric, climate, and biomedical research. The current state of knowledge, open questions, and future research perspectives are outlined and discussed. The Anthropocene, as the present era of globally pervasive anthropogenic influence on planet Earth and, thus, on the human environment, is characterized by a strong increase of carbon dioxide, ozone, nitrogen oxides, and combustion- or traffic-related particulate matter in the atmosphere. These environmental factors can enhance the abundance and induce chemical modifications of allergens, increase oxidative stress in the human body, and skew the immune system toward allergic reactions. In particular, air pollutants can act as adjuvants and alter the immunogenicity of allergenic proteins, while climate change affects the atmospheric abundance and human exposure to bioaerosols and aeroallergens. To fully understand and effectively mitigate the adverse effects of air pollution and climate change on allergic diseases, several challenges remain to be resolved. Among these are the identification and quantification of immunochemical reaction pathways involving allergens and adjuvants under relevant environmental and physiological conditions.

Release of free amino acids upon oxidation of peptides and proteins by hydroxyl radicals.

Hydroxyl radical-induced oxidation of proteins and peptides can lead to the cleavage of the peptide, leading to a release of fragments. Here, we used high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) and pre-column online ortho-phthalaldehyde (OPA) derivatization-based amino acid analysis by HPLC with diode array detection and fluorescence detection to identify and quantify free amino acids released upon oxidation of proteins and peptides by hydroxyl radicals. Bovine serum albumin (BSA), ovalbumin (OVA) as model proteins, and synthetic tripeptides (comprised of varying compositions of the amino acids Gly, Ala, Ser, and Met) were used for reactions with hydroxyl radicals, which were generated by the Fenton reaction of iron ions and hydrogen peroxide. The molar yields of free glycine, aspartic acid, asparagine, and alanine per peptide or protein varied between 4 and 55%. For protein oxidation reactions, the molar yields of Gly (∼32-55% for BSA, ∼10-21% for OVA) were substantially higher than those for the other identified amino acids (∼5-12% for BSA, ∼4-6% for OVA). Upon oxidation of tripeptides with Gly in C-terminal, mid-chain, or N-terminal positions, Gly was preferentially released when it was located at the C-terminal site. Overall, we observe evidence for a site-selective formation of free amino acids in the OH radical-induced oxidation of peptides and proteins, which may be due to a reaction pathway involving nitrogen-centered radicals.

Metaproteomic analysis of atmospheric aerosol samples.

Metaproteomic analysis of air particulate matter provides information about the abundance and properties of bioaerosols in the atmosphere and their influence on climate and public health. We developed and applied efficient methods for the extraction and analysis of proteins from glass fiber filter samples of total, coarse, and fine particulate matter. Size exclusion chromatography was applied to remove matrix components, and sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) was applied for protein fractionation according to molecular size, followed by in-gel digestion and LC-MS/MS analysis of peptides using a hybrid Quadrupole-Orbitrap MS. Maxquant software and the Swiss-Prot database were used for protein identification. In samples collected at a suburban location in central Europe, we found proteins that originated mainly from plants, fungi, and bacteria, which constitute a major fraction of primary biological aerosol particles (PBAP) in the atmosphere. Allergenic proteins were found in coarse and fine particle samples, and indications for atmospheric degradation of proteins were observed. Graphical abstract Workflow for the metaproteomic analysis of atmospheric aerosol samples.

Exposure assessment, chemical characterization and source identification of PM2.5 for school children and industrial downwind residents in Guangzhou, China.

To assess the exposure doses of PM(2.5) and to investigate its chemical components for the subpopulation (i.e., school children and industrial downwind residents), simultaneous sampling of indoor and outdoor PM(2.5) was conducted at an elementary school close to traffic arteries and a residence located in the downwind area of a steel plant in metropolitan Guangzhou in 2010. Chemical components, i.e., organic carbon, elemental carbon and 6 water soluble ions were analyzed in PM(2.5). A survey was also conducted to investigate the time-activity patterns of the school children and the industrial downwind residents. Indoor and outdoor PM(2.5) were 63.2 ± 20.1 and (76.7 ± 35.8) µg/m(3) at the school, and 118.8 ± 44.7 and 125.7 ± 57.1 µg/m(3) in the community, respectively. Indoor PM(2.5) was found to be highly related to outdoor sources, and stationary sources were the significant contributors to PM(2.5) at both sites. The daily average doses of PM(2.5) for the school children at the school (D(children)) and the industrial downwind residents in the community (D(residents)) were (7.6 ± 1.9) and (36.1 ± 36.8) µg/kg-day, respectively. The daily average doses of particulate organic mass and SO(4)(2-) were the two most abundant chemical components in PM(2.5). PM(2.5) exposure for the school children was contributed by indoor and outdoor environments by 48.8 and 51.2 %, respectively; for the industrial downwind residents, the contributions were 66.0 and 34.0 %, respectively. Age and body weight were significantly and negatively correlated with D(children), while age, body weight and education level were significantly and negatively correlated with D(residents); gender was not a significant factor at both cases.

Multiphase reactions of proteins in the air: Oligomerization, nitration and degradation of bovine serum albumin upon ambient exposure.

Proteins in atmospheric aerosol can react with atmospheric pollutants such as ozone (O3) and nitrogen dioxide (NO2) in the atmosphere via the reactions of oxidation, nitration, and cross-linking etc. Currently, the reactions have been more thoroughly studied in the laboratory but rarely investigated in the ambient environment. In this study, we used bovine serum albumin (BSA) as the model protein to conduct the exposure experiment in the ambient environment in southern China, an area with increasing oxidative capacity, to investigate the reactions of proteins in the atmosphere. We observed the occurrence of oligomerization, nitration and degradation of BSA upon exposure. The mass fraction of BSA monomer decreased by 5.86 ± 1.61% after exposure and those of dimers, trimers and higher oligomers increased by 1.04 ± 0.49%, 1.37 ± 0.74% and 3.40 ± 1.06%, respectively. Simultaneously, the nitration degrees of monomers, dimers, trimers and higher oligomers increased by 0.42 ± 0.15%, 0.53 ± 0.15%, 0.55 ± 0.28% and 2.15 ± 1.01%, respectively. The results show that oligomerization was significantly affected by O3 and temperature and nitration was jointly affected by O3, temperature and relative humidity, indicating the important role of atmospheric oxidants in the atmospheric reactions of protein. Atmospheric degradation of BSA was observed with the release of free amino acids (FAAs) such as glycine, alanine, serine and methionine. Glycine was the dominant FAA with a molar yield ranging from ∼8% to 33% for BSA. The estimated stoichiometric coefficient (α) of glycine is 10-7-10-6 for the degradation of BSA upon O3. Our observation suggests the occurrence of protein reactions in the oxidative ambient environment, leading to the production of nitrated products, oligomers and low molecular weight products such as peptides and FAAs. This study may deepen the current understanding of the atmospheric reaction mechanisms and reveal the influence of environmental factors in the atmosphere.

Characterizing atmospheric biological aerosols at a suburban site in Guangzhou, southern China by airborne microbes, proteins and saccharides.

Bioaerosols in ambient environment can be evaluated using various techniques. However, the results of bioaerosols obtained using different methods are rarely compared. The relationships between different bioaerosol indicators and their behaviors under the influence of environment factors are seldom investigated. Here we used airborne microbial numbers, proteins and saccharides concentrations as the indicators to characterize bioaerosols in two seasons with different source contribution, air pollution situation and meteorological conditions. The observation was conducted at a suburban site in Guangzhou, southern China, during the winter and spring periods of 2021. Airborne microbes were observed with an average of (1.82 ± 1.33) × 106 cells/m3, converted to the mass concentration level of 0.42 ± 0.30 µg/m3, comparable but lower than that of proteins (0.81 ± 0.48 µg/m3). Both of them were much higher than the average concentration of saccharides (19.93 ± 11.53 ng/m3). During the winter period, significant and good correlations were observed between the three components. In spring, a biological outbreak was observed in late March with a strong elevation of airborne microbes followed by elevations of proteins and saccharides. The retardation of proteins and saccharides could be the result of the enhanced release from microorganisms under the influence of atmospheric oxidation processes. Saccharides in PM2.5 were studied to reveal the contribution of specific sources of bioaerosols (e.g. fungi, pollen, plants and soil). Our results show that primary emissions and secondary processes should play their roles in the variations of these biological components. By comparing the results of the three methods, this study provides an insight into the applicability and variability of bioaerosol characterization in the ambient environment with respect to various influences of sources, atmospheric processes and environmental conditions.

Chemical characterization of marine aerosols from two cruises over the South China Sea: Importance of biomass burning and secondary formation.

Total suspended particle (TSP) samples were collected during June-July 2015 in the northern South China Sea (NSCS) and August-September 2016 in the western South China Sea (WSCS). Water-soluble ions (WSIs), organic carbon (OC), elemental carbon (EC), and organic compounds were measured. The average concentrations of WSIs, OC, EC and organic compounds were 19.4 ± 10.9 µg m-3, 2.48 ± 1.54 µgC m-3, 0.31 ± 0.25 µgC m-3 and 789 ± 217 ng m-3 in the NSCS, and were 10.2 ± 4.71 µg m-3, 1.76 ± 1.82 µgC m-3, 0.43 ± 0.32 µgC m-3 and 781 ± 342 ng m-3 in the WSCS. In both cruises, sea salt ions (Na+ and Cl-) and secondary inorganic ions (SO42-, NO3-, and NH4+) were the main species of WSIs, accounting for 54.0 % and 43.6 % in the NSCS, and for 35.0 % and 54.0 % in the WSCS. The secondary products (dicarboxylic acids and aromatic acids) (NSCS: 73.3 %; WSCS: 73.9 %) and saccharides (NSCS: 19.0 %; WSCS: 18.0 %) accounted large fractions of organic compounds in aerosol particles over the SCS. These results suggest sea salt emissions and secondary formation are the main sources of the aerosols over the SCS in summer. The positive correlations between the biomass burning tracers (nss-K+ and levoglucosan) and OC as well as organic compounds indicated that biomass burning from nearby continents was also an important source of organic aerosols over the SCS. Based on back-trajectory analysis and satellite fire spots, Indochina Peninsula and China were proposed as the main continental source areas of non-sea salt WSIs and organic compounds. Our results highlight the significant contribution of continental outflow especially biomass burning and photochemical secondary oxidation to the organic compositions of aerosol particles over the SCS in summertime.

Exposure and health risk assessment of PM2.5-bound polycyclic aromatic hydrocarbons during winter at residential homes: A case study in four Chinese cities.

Residential indoor PM2.5 were concurrently collected in Hong Kong, Guangzhou, Shanghai, and Xi'an during the winter and early spring seasons of 2016-2017, for updating the current knowledge of the spatial variation of indoor air pollution and the potential health risks in China. PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) were characterized, and the associated inhalation cancer risks were assessed by a probabilistic approach. Higher levels of indoor PAHs were identified in Xi'an residences (averaged at 176.27 ng m-3) with those of other cities ranging from 3.07 to 15.85 ng m-3. Traffic-related fuel combustion was identified as a common contributor to indoor PAHs through outdoor infiltration for all investigated cities. Indoor PAHs profiles showed city-specific differences, while distinctions between profiles based on indoor activities or ambient air quality were limited. Similar with the total PAHs concentrations, the estimated toxic equivalencies (TEQ) with reference to benzo[a]pyrene in Xi'an residences (median at 18.05 ng m-3) were above the recommended value of 1 ng m-3 and were magnitudes higher than the other investigated cities with estimated median TEQ ranging from 0.27 to 1.55 ng m-3. Incremental lifetime cancer risk (ILCR) due to PAHs inhalation exposure was identified with a descending order of adult (median at 8.42 × 10-8) > adolescent (2.77 × 10-8) > children (2.20 × 10-8) > senior (1.72 × 10-8) for different age groups. Considering the lifetime exposure-associated cancer risk (LCR), potential risks were identified for residents in Xi'an as an LCR level over 1 × 10-6 was identified for half of the adolescent group (median at 8.96 × 10-7), and exceedances were identified for about 90 % of the groups of adults (10th percentile at 8.29 × 10-7) and seniors (10th percentile at 1.02 × 10-6). The associated LCR estimated for other cities were relatively insignificant.

Organophosphate esters in atmospheric particles and surface seawater in the western South China Sea.

Seven organophosphate esters (OPEs) in atmospheric particles and surface seawater were observed during a cruise in the western South China Sea (SCS) in 2014. The median concentrations of ∑OPEs were 688 pg/m3 and 5.55 ng/L for particle and seawater samples, respectively. Total OPEs were dominated by tris(1-chloro-2-propyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP). The spatial distribution of OPEs indicates that the OPEs in particle phase were mainly influenced by the air masses originating from China, Indochina Peninsula and Malay Archipelago, showing the significant contribution of anthropogenic sources from these regions. Significant positive correlations between Tri-n-butylphosphate (TnBP) and organic carbon (P < 0.05) in particle phase over the western SCS suggests that it might be a potential tracer for the source regions of Indochina Peninsula and Malay Archipelago. The spatial distribution of OPEs in seawater was contributed by freshwater inputs associating with variations of human activities as well as salinity. Seawater pollution levels of OPEs in the eastern coast of Vietnam were increased compared to those measured in the northern SCS. The loadings of ∑OPEs transported to the vast area of western SCS vias atmospheric deposition and air-seawater gas exchange were estimated to be 59 tons/year and 105 tons/year, respectively. This work highlights the importance of transport processes and air-seawater interface behavior of OPEs in the oceanic area.

Characterization of airborne bacteria and fungi at a land-sea transition site in Southern China.

Airborne microbe can have impact on regional to global climate as ice nuclei and cloud condensation nuclei. In coastal region, microbial aerosols are simultaneously contributed by terrestrial and marine sources under the influence of land-sea air exchange. We present a study on the characteristics of airborne bacteria and fungi, including their concentrations and communities, at a land-sea transition site in Southern China from December 2019 to December 2020. Seasonal variations of microbial communities were observed with evident profiles in summer, especially for fungal aerosols. The significant enhancement of Basidiomycota abundance in summer was contributed by local biogenic release under the influence of meteorological factors. Terrestrial sources are suggested as the dominant contributors to both bacterial and fungal aerosols rather than marine sources during the whole year period. Source-tracking analysis identified that marine contributions to airborne bacteria and fungi were 3.1-14.2 % and 4-24 %, respectively. It suggests that airborne fungi should be more suitable for long-range transport than airborne bacteria. This study improves the understanding of the conversional contribution of marine and terrestrial sources to airborne microbes in coastal region and the influencing environmental factors under land-sea exchange.

Site location optimization of regional air quality monitoring network in China: methodology and case study.

Regional air quality monitoring networks (RAQMN) are urgently needed in China due to increasing regional air pollution in city clusters, arising from rapid economic development in recent decades. This paper proposes a methodological framework for site location optimization in designing a RAQMN adapting to air quality management practice in China. The framework utilizes synthetic assessment concentrations developed from simulated data from a regional air quality model in order to simplify the optimal process and to reduce costs. On the basis of analyzing various constraints such as cost and budget, terrain conditions, administrative district, population density and spatial coverage, the framework takes the maximum approximate degree as an optimization objective to achieve site location optimization of a RAQMN. An expert judgment approach was incorporated into the framework to help adjust initial optimization results in order to make the network more practical and representative. A case study was used to demonstrate the application of the framework, indicating that it is feasible to conduct site optimization for a RAQMN design in China. The effects of different combinations of primary and secondary pollutants on site location optimization were investigated. It is suggested that the network design considering both primary and secondary pollutants could better represent regional pollution characteristics and more extensively reflect temporal and spatial variations of regional air quality. The work shown in this study can be used as a reference to guide site location optimization of a RAQMN design in China or other regions of the world.

Characterization of fungal aerosol in a landfill and an incineration plants in Guangzhou, Southern China: The link to potential impacts.

To understand the characteristics and potential impacts of fungal aerosols in waste disposal treatments, we performed observations at a landfill and an incineration plants in Guangzhou, Southern China. Size-segregated airborne fungal concentrations were measured based on culture-dependent method, and fungal compositions in PM2.5 were obtained using high-throughput sequencing method. Concentrations of airborne fungi varied from 376 to 9318 CFU/m3 in the landfill plant and from 53 to 8491 CFU/m3 in the incineration plant, respectively. The temporal and spatial variations of fungal aerosols indicate that waste disposal operation, garbage transport, air mixing, and meteorological factors can significantly influence the variations of airborne fungi in the outdoor environment in both plants. Among the meteorological factors, light/moderate rain could significantly increase the airborne fungal concentrations while heavy rain could decrease the concentrations due to wet scavenge. We observed that culturable fungal aerosols predominantly resided in the size range of 2.1-3.3 µm. Different fungal community structures in PM2.5 were found between the landfill and the incineration plants, suggesting the influence of different waste sorts and treatment procedures. We further identified the pathogenic/allergenic fungal taxa (e.g., Alternaria, Epicoccum sp. and Stachybotrys sp.) in the two plants, implying the potential human health risks with long-term exposure for on-site workers and surrounding residents. The fungal genera producing microbial volatile organic compounds (MVOCs, e.g., Cladosporium, Fusarium sp., Penicillium sp. and Candida) were found in both plants. These MVOCs generation related fungal genera could contribute to the odor in the plants and, more importantly, affect the downwind area after aerosolization and transportation.