Light-absorption and fluorescence fingerprinting characteristics of water and methanol soluble organic compounds in PM2.5 in cold regions of Northeast China.

High-performance liquid chromatography-size exclusion chromatography and excitation-emission matrix (EEM) fluorescence spectroscopy were used to analyze the seasonal variations and potential sources of molecular weight (MW) separated light-absorbing chromophores and fluorophores of water-soluble organic compounds (WSOC) and methanol-soluble organic compounds (MSOC) in PM2.5 in cold areas of northern China. The results showed that the light-absorbing organics in MSOC had larger weight-average MW (Mw) (3.19 kDa) and number-average MW (Mn) (1.13 kDa) compared with WSOC (Mw: 1.41 kDa, Mn: 0.692 kDa). The light-absorption of organics showed a trend of winter>spring>autumn>summer and increased on air pollution days. Three fluorescent components including humic-like, protein-like, and terrestrial humic-like components in WSOC were extracted by parallel factor analysis (PARAFAC). Fluorophores in WSOC were dominated by humic-like and terrestrial humic-like components (67.7%). Three fluorescent components extracted from MSOC were low oxidation humic-like, polycyclic aromatic hydrocarbon (PAH)-like, and protein-like components respectively. It is worth noting that compared with WSOC, MSOC may have a higher human health risk due to the presence of PAH-like components. The combination of PARAFAC and self-organizing map had the potential to identify potential sources of fluorophores. It provided a new perspective for comprehensively exploring the characteristics of fluorophores in aerosols. This study provided a reference for further understanding the chemical composition and optical properties of organic aerosols in the cold regions of northern China.

Changes in antibiotic resistance genotypes and phenotypes after two typical sewage disposal processes.

Antibiotic resistome is a growing concern around the world. Wastewater treatment plants (WWTPs) have been identified as hotspots for antibiotic resistance gene (ARG) research. However, the distribution of antibiotic resistance genotypes and phenotypes in biofilm wastewater treatment system is poorly understood. In this study, the abundance and fate of antibiotic resistance genotypes and phenotypes in two typical wastewater treatment processes [biological aerated filter (BAF), anaerobic-oxic (A/O)] were quantitatively studied. The average removal rate of total ARGs was greater than 90%. In the biological treatment unit, the abundance of ARGs increased in the A/O unit and decreased in the biofilm unit. In addition, the resistance of tetracycline resistant bacteria changed after sewage disposal, which was closely related to the evolution of bacterial community. In total, the removal rate of resistance bacteria in A/O system was lower than that in BAF system. Genotypes were the basis of determining the phenotypes of microbial resistance. But it is necessary to pay close attention to antibiotic resistance phenotype due to its high variability. More specifically, antibiotic resistance mitigation in WWTPs should focus more on removing bacterial hosts to reduce the release of ARGs into the environment.

Theoretical insights into the gas/heterogeneous phase reactions of hydroxyl radicals with chlorophenols: Mechanism, kinetic and toxicity assessment.

Emission of 2-chlorophenols (2-CPs) can cause serious air pollution and health problems. Here, the reaction kinetics and products of key radicals in 2-CPs photo-oxidation are explored in both gaseous and heterogeneous reactions. Quantum chemical calculations show that •OH-addition pathways are more preferable than H-abstraction pathways in gas phase, while that is opposite in heterogeneous phase. At 298 K, the overall rate coefficients of the title reactions in gas and heterogeneous phases are 3.48 × 10-13 and 2.37 × 10-13 cm3 molecule-1 s-1 with half-lives of 55.3 h and 81.2 h, respectively. The strong H-bonds between linear Si3O2(OH)8 and 2-CPs change the energy barriers of initial •OH-addition and H-abstraction reactions, resulting in the competition between heterogeneous reactions and gas phase reactions. The products in heterogeneous reactions are chloroquinone and HONO, which can cause atmospheric acid deposition and eco-toxicity. In gas phase, self-cyclization of alkoxy radical (RO•) leads to formation of •HO2 and highly­oxygenated molecules, which cause formation of secondary organic aerosol. It is emphasized that oxidation of 2-CPs by •OH leads to formation of more toxic products for aquatic organisms. Therefore, more attention should be focused on the products originated from •OH-initiated reactions of (2-)CPs in gaseous and heterogeneous reactions.

A new insight into the ARG association with antibiotics and non-antibiotic agents-antibiotic resistance and toxicity.

Although concerns have been raised about co-selection for antibiotic resistance and various antibiotics and non-antibiotic agents, the data on their association in urban sludge is still limited. In addition, antibiotic contamination can result in not only the toxicity but also the antibiotic resistance. In this study, the first large-scale identification of antibiotics and non-antibiotic agents concern for co-selection of resistance against antibiotics was conducted in urban sludge. Co-occurrence analysis showed that antibiotic resistance genes (ARGs) had no significant correlation with the corresponding antibiotics. Therefore, the results of co-occurrence analysis based on antibiotic concentration and ARG abundance were always ambiguous and difficult to interpret. However, antibiotic resistance was positively correlated with highly toxic compounds such as diclofenac, enrofloxacin and nicotine, suggesting that environmental contaminants might influence antibiotic resistance while exerting toxicity through mechanisms such as changes in microbial community and enzyme activity. The close correlation between class 1 integrase gene (intI1) and diclofenac/enrofloxacin indicated that the co-selection scenario between environmental contaminants and ARGs was likely mediated via intI1. In total, the derived co-occurrence patterns improve our understanding of the co-selection between ARGs, antibiotics and non-antibiotic agents, and also reaffirm the importance of potential role of non-antibiotic agents in the global spread of antibiotic resistance.

Effects of Atmospheric Fine Particulate Matter and Its Carrier Microbes on Pulmonary Microecology in Patients with COPD.

Objective: The aim of this paper was to analyse the influence of atmospheric fine particulate matter (AFPM) and atmospheric microorganisms on the pulmonary microecology of chronic obstructive pulmonary disease (COPD) patients in northeast China. Methods: Collected bronchoalveolar lavage fluid (BALF) of COPD patients in the high-risk period (group A) and low-risk period (group B) of AFPM inhalation and samples of AFPM in the same time range (group C) were collected. DNA sample sequencing, the bacterial abundance, and diversity bioinformatics of BALFs were performed by methods of Illumina MiSeq™ platform and Mothur and Uclust. Results: A total of 58 samples were sequenced, including 22 samples from group A, 26 samples from group B and 10 samples from group C. A total of 2,005,790 bacterial sequences and 34,256 bacterial numbers were detected. Group B had the highest bacterial diversity of the three groups. Group B also had the highest bacterial abundance index value. There were differences in the classification of bacterial colonies for the three groups at the genus level. The types of bacteria in group C were more numerous than other groups, and group B was higher than group A, which indicates that there were more bacteria in BALF during the high-risk period of AFPM inhalation. The detection rates of Streptococcus, Mycoplasma, Roche, Pushia, Chlamydia trachomatis and Brucella for group C were significantly higher than group A. The COG and KEGG databases' difference analysis results for the bacterial gene function abundance of group A and group B were 40.7% in group A and 38.9% in group B (R=0.098, P=0.006). The human disease abundance in group A and group B was 1.16% and 1.12%, respectively (P>0.05). Conclusion: The increase in the concentration of AFPM can increase the diversity and abundance of bacteria in the BALF of stable COPD patients. Clinical Trial Registration Number: 2020XS04-02.

Assessing the emission sources and reduction potential of atmospheric ammonia at an urban site in Northeast China.

Atmospheric ammonium and ammonia have brought negative environmental impacts and adverse health effects. However, ammonia emissions are generally less regulated worldwide. This study analyzed ammonium pollution character, quantified the dominant ammonia emission sources, and assessed ammonia reduction potential in urban Harbin (China). The results showed that ammonium recorded low concentration in the non-heating season (1.34 ± 1.57 µg/m3), and recorded sharply increased concentration (6.50 ± 7.02 µg/m3) and relative abundance in the heating season. It was closely correlated with vehicle-related pollutants (CO) in non-heating season, while with biomass burning-related pollutants (K+, Cl-) in the heating season. Bayesian Mixing Model emphasized the increasing contribution of biomass burning and decreasing contribution of fertilizer as the pollution levels escalate. The results from the thermodynamic equilibrium model showed that a 50%-60% ammonium decrease could bring marketable decrements of the aerosol pH, aerosol water content, ammonium nitrate concentration, and inorganic ion mass. The results of this study would provide scientific bases for ammonia emission reduction and haze pollution control in urban Harbin.

Long-term characteristics of criteria air pollutants in megacities of Harbin-Changchun megalopolis, Northeast China: Spatiotemporal variations, source analysis, and meteorological effects.

The hourly concentration of six criteria air pollutants in the Harbin-Changchun region were used to investigate the status and spatiotemporal variation of target air pollutants and their relationships with meteorological factors. The annual concentrations of particulate matters during 2013-2017 were two times higher than the Chinese Ambient Air Quality Standards (CAAQS) Grade Ⅱ. The annual O3 concentration increased by two times during 2013-2018 in Harbin. The concentration of PM, SO2, NO2, and CO depicted a similar seasonal trend with an order of winter > autumn > spring > summer. The consistent interannual variation trends of PM2.5/CO, NO2 and SO2 indicated that the formation of secondary inorganic aerosols in the annual scale was dominated by the concentrations of NO2 and SO2. The interannual variations of the individual meteorological factors causing on PM2.5 and O3 during 2013-2018 varied significantly in seasonal scale. The interannual variations were stable in annual scale indicating that the continuous decline of PM2.5 during 2014-2018 can be attributed to the comprehensive and strict prohibition of small coal-fired boilers and straw burning in the study area. Meanwhile, the increase in O3 during 2013-2018 in the study area were mainly attributed to the rapid growth of the emission of its precursor (VOCs and NOx). The influence of meteorology on PM2.5 and ozone were the most stable and strongest in winter than that in the other three seasons.

Seasonal characteristic composition of inorganic elements and polycyclic aromatic hydrocarbons in atmospheric fine particulate matter and bronchoalveolar lavage fluid of COPD patients in Northeast China.

OBJECTIVE: To explore the composition characteristics of atmospheric fine particulate matter (PM2.5) and bronchoalveolar lavage fluid (BALF), and their impact on the development of chronic obstructive pulmonary disease (COPD). METHODS: The atmospheric PM2.5 samples and BALF samples from COPD patients were collected from June 2, 2017 to October 30, 2018, and allocated into a high-risk of PM2.5 inhalation group and a low-risk PM2.5 inhalation group according to the heating season in Harbin. Inorganic elements were detected by ICP-MS, and polycyclic aromatic hydrocarbons (PAHs) were detected by GC/MS. RESULTS: Twenty-six inorganic elements were found in 54 BALF specimens. There was a high correspondence in inorganic elements between BALF and atmospheric PM2.5. Trace elements Cr, Mn, V, and Co, and toxic trace elements Al, Pb, Cd, As, and Ag were above the upper limit of normal blood. There were significant higher K, Ti, Fe, Co, Cu, Se, Rb, Ag, and Sb in BALF of the high-risk PM2.5 inhalation group (p < 0.05). Sixteen PAHs were detected in 32 BALF samples. The main components of BALF and atmospheric PM2.5 were the high molecular weight PAHs, and the species and concentration of PAHs in BALF and atmospheric PM2.5 are highly consistent. CONCLUSION: The types and concentrations of inorganic elements and PAHs in BALF of COPD patients are highly consistent with those of atmospheric PM2.5. The sustained high concentrations of Benzo(a)anthracene, Chrysene, Benzo(b)Fluoranthene, Benzo(k)Fluoranthene, Indeno(123-c,d)Pyrene, and Benzo(a)Pyrene in BALF of COPD patients may have long-term adverse effects on COPD patients.

Exploring the disparity of inhalable bacterial communities and antibiotic resistance genes between hazy days and non-hazy days in a cold megacity in Northeast China.

The physicochemical properties of inhalable particles during hazy days have been extensively studied, but their biological health threats have not been well-explored. This study aimed to explore the impacts of haze pollution on airborne bacteria and antibiotic-resistance genes (ARGs) by conducting a comparative study of the bacterial community structure and functions, pathogenic compositions, and ARGs between hazy days and non-hazy days in a cold megacity in Northeast China. The results suggested that bacterial communities were shaped by local weather and customs. In this study, cold-resistant and Chinese sauerkraut-related bacterial compositions were identified as predominant genera. In the comparative analysis, higher proportions of gram-negative bacteria and pathogens were detected on hazy days than on non-hazy days. Pollutants on hazy days provided more nutrients (sulfate, nitrate and ammonium) for bacterial metabolism but also caused more bacterial cell damage and death than on non-hazy days. This study also detected increases in the sub-types and average absolute abundance of airborne resistance genes on hazy days compared to non-hazy days. The results of this study revealed that particle pollution promotes the dissemination and exchange of pathogenic bacteria and ARGs among large urban populations, which leads to a higher potential for human inhalation exposure.

Occurrence, composition profiles and risk assessment of polycyclic aromatic hydrocarbons in municipal sewage sludge in China.

A nationwide survey, including 75 sludge samples and 18 wastewater samples taken from different wastewater treatment plants (WWTPs) from 23 cities, was carried out to investigate the occurrence and composition profiles of polycyclic aromatic hydrocarbons (PAHs) in China. In total, the concentrations of ∑16PAHs in sludge ranged from 565 to 280,000 ng/g (mean: 9340 ng/g) which was at a moderate level in the world. The composition profiles of PAHs were characterized by 3- and 4-ring PAHs in textile dyeing sludge and 4- and 5-ring PAHs in domestic sludge. Significant variations in regional distribution of PAHs were observed. Both the principal components analysis and diagnostic ratios revealed that vehicle exhaust, coal and natural gas combustion were the main sources of PAHs in China. The estimated concentrations of PAHs were 3820 ng/L and 1120 ng/L in influents and effluents of the WWTPs, respectively. The high toxic equivalent quantity (TEQ) values of PAHs are ascribed to the high PAH levels. Risk quotient values (RQs) in sludge indicated that there was low potential risk to soil ecosystem after sludge had been applied one year except for indeno [1,2,3-cd]pyrene (IcdP) detected in Huaibei, Anhui province.

Distribution features and controls of heavy metals in surface sediments from the riverbed of the Ningxia-Inner Mongolian reaches, Yellow River, China.

Fifty-six riverbed surface sediment (RSS) samples were collected along the Ningxia-Inner Mongolian reaches of the Yellow River (NIMYR). These samples were analyzed to determine their heavy metal concentrations (Co, Cr, Ni, Cu, V and Zn), grain sizes, sediment sources and the causes of their heavy metal contamination. The cumulative distribution functions of the heavy metals in RSS of these reaches are plotted to identify the geochemical baseline level (GBL) of each element and determine the average background concentration of each heavy metal. Principal component analysis and hierarchical cluster analysis are conducted based on the grain sizes of RSS, and the samples are classified into two groups: coarse grained samples (CGS) and fine grained samples (FGS). The degree of heavy metal contamination for each sample is identified by its enrichment factor (EF). The results reveal that the coarse particle component (medium sand and coarse sand) in the bed materials is chiefly from the bordering deserts along the Yellow River. The clay and silt in the bed materials chiefly originate from the upper reaches of the Yellow River, and the fine sand is identified as a hybrid sediment derived from the upper reaches of the Yellow River and the bordering deserts. The CGS primarily appear in the reaches bordering deserts, and the sites are near the confluence of gullies and the Yellow River. The FGS are located adjacent to cities with especially strong industrial activity such as Wuhai, Bayan Nur, Baotou and Togtoh. The Cr, Ni, Cu, V and Zn concentrations (mg kg(-1)) are 84.34 ± 49.46, 30.21 ± 7.90, 25.01 ± 7.61, 73.17 ± 18.92 and 55.62 ± 18.93 in the FGS and 65.07 ± 19.51, 23.86 ± 6.84, 18.04 ± 3.8, 53.47 ± 10.57 and 34.89 ± 9.19 in the CGS respectively, and the concentrations of Co in the CGS (213.40 ± 69.71) are notably higher than in the FGS (112.02 ± 48.87) and greater than the Co GBL (210). The most contaminated samples in the NIMYR are adjacent to the cities of Wuhai (EF(Cr) = 5.19; EF(Ni) = 1.96), Bayan Nur (EF(Cr) = 5.88; EF(Ni )= 2.08) and Baotou (EF(Cu) = 1.55; EF(Zn) = 1.68) where the Cr, Ni, Cu, V and Zn concentrations are above the correlated GBLs (85, 34, 27, 75 and 62 mg kg(-1), respectively), which are mostly affected by industrial processes, and samples that are only moderately contaminated by heavy metals are found in the reaches bordering desert (Wuhai-Baotou) because contaminated sediments are diluted by uncontaminated desert sand. In contrast, all of the Cu, Cr, Ni, V and Zn concentrations in RSS of the Qingtongxia-Wuhai reach are lower than the correlated GBLs of elements.