LC-MS-based serum metabolomics analysis for the screening and monitoring of colorectal cancer.

Background: Colorectal Cancer (CRC) is a prevalent digestive system tumour with significant mortality and recurrence rates. Serum metabolomics, with its high sensitivity and high throughput, has shown potential as a tool to discover biomarkers for clinical screening and monitoring of the CRC patients. Methods: Serum metabolites of 61 sex and age-matched healthy controls and 62 CRC patients (before and after surgical intervention) were analyzed using a ultra-performance liquid chromatography-high resolution mass spectrometer (UPLC-MS). Statistical methods and pathway enrichment analysis were used to identify potential biomarkers and altered metabolic pathways. Results: Our analysis revealed a clear distinction in the serum metabolic profile between CRC patients and healthy controls (HCs). Pathway analysis indicated a significant association with arginine biosynthesis, pyrimidine metabolism, pantothenate, and CoA biosynthesis. Univariate and multivariate statistical analysis showed that 9 metabolites had significant diagnostic value for CRC, among them, Guanosine with Area Under the Curve (AUC) values of 0.951 for the training group and0.998 for the validation group. Furthermore, analysis of four specific metabolites (N-Phenylacetylasparticacid, Tyrosyl-Gamma-glutamate, Tyr-Ser and Sphingosine) in serum samples of CRC patients before and after surgery indicated a return to healthy levels after an intervention. Conclusion: Our results suggest that serum metabolomics may be a valuable tool for the screening and monitoring of CRC patients.

Underestimation of biomass burning contribution to PM2.5 due to its chemical degradation based on hourly measurements of organic tracers: A case study in the Yangtze River Delta (YRD) region, China.

Biomass burning (BB) has significant impacts on air quality and climate change, especially during harvest seasons. In previous studies, levoglucosan was frequently used for the calculation of BB contribution to PM2.5, however, the degradation of levoglucosan (Lev) could lead to large uncertainties. To quantify the influence of the degradation of Lev on the contribution of BB to PM2.5, PM2.5-bound biomass burning-derived markers were measured in Changzhou from November 2020 to March 2021 using the thermal desorption aerosol gas chromatography-mass spectrometry (TAG-GC/MS) system. Temporal variations of three anhydro-sugar BB tracers (e.g., levoglucosan, mannosan (Man), and galactosan (Gal)) were obtained. During the sampling period, the degradation level of air mass (x) was 0.13, indicating that ~87 % of levoglucosan had degraded before sampling in Changzhou. Without considering the degradation of levoglucosan in the atmosphere, the contribution of BB to OC were 7.8 %, 10.2 %, and 9.3 % in the clean period, BB period, and whole period, respectively, which were 2.4-2.6 times lower than those (20.8 %-25.9 %) considered levoglucosan degradation. This illustrated that the relative contribution of BB to OC could be underestimated (~14.9 %) without considering degradation of levoglucosan. Compared to the traditional method (i.e., only using K+ as BB tracer), organic tracers (Lev, Man, Gal) were put into the Positive Matrix Factorization (PMF) model in this study. With the addition of BB organic tracers and replaced K+ with K+BB (the water-soluble potassium produced by biomass burning), the overall contribution of BB to PM2.5 was enhanced by 3.2 % after accounting for levoglucosan degradation based on the PMF analysis. This study provides useful information to better understand the effect of biomass burning on the air quality in the Yangtze River Delta region.

Highly time-resolved measurements of elements in PM2.5 in Changzhou, China: Temporal variation, source identification and health risks.

The temporal variation, sources, and health risks of elemental composition in fine particles (PM2.5) were explored using online measurements of 19 elements with a time resolution of 1 h at an urban location in Changzhou, China, from December 10, 2020 to March 31, 2021. The mass concentration of PM2.5 was 50.1 ±â€¯32.6 µg m-3, with a range of 3-218 µg m-3. The total concentration of 19 elements (2568 ±â€¯1839 ng m-3) accounted for 5.1 % of PM2.5 mass concentration. S, Cl, Si, and Fe were the dominant elementary species, accounting for 90 % of total element mass concentrations during the whole campaign. Positive matrix factorization (PMF) model was applied to identify the major emission sources of elements in PM2.5. Seven factors, named secondary sulfate mixed with coal combustion, Cl-rich, traffic, iron and steel industry, soil dust, fireworks, and shipping, were identified. The major sources for elements were iron and steel industry, followed by soil dust and secondary sulfate mixed with coal combustion, explaining 32.0 %, 23.5 % and 16.7 % of the total source contribution, respectively. The total hazard index (HI) of elements was 3.01 for children and 1.18 for adults, much greater than the admissible level (HI = 1). The total carcinogenic risk (CR) in Changzhou was estimated to be 5.87 × 10-5, which was above the acceptable CR level (1 × 10-6). Among the calculated metal elements, Cr, Co and As have higher carcinogenic risk, and Co was found to trigger the highest noncarcinogenic risk to Children. Our results indicate that industrial emission is the dominant CR contributor, emphasizing the necessity for stringent regulation of industry sources. Overall, our study provides useful information for policymakers to reduce emissions and health risks from elements in the Yangtze River Delta region.

Characteristics and sources of amine-containing particles in the urban atmosphere of Liaocheng, a seriously polluted city in North China during the COVID-19 outbreak.

The Chinese government issued an unprecedentedly strict lockdown policy to control the spread of the novel coronavirus disease 2019 (COVID-19), significantly mitigating air pollution because of the dramatic reduction of industrial and traffic emissions. To explore the impact of COVID-19 lockdown (LCD) on organic aerosols, the mixing states and evolution processes of amine-containing particles were studied using a single particle aerosol mass spectrometer from January to March 2020 in Liaocheng, which is a seriously polluted city in North China. The counts and percentages of amine-containing particles in total obtained particles during the pre-LCD (547832, 29.8 %) were higher than those during the LCD (283983, 20.7 %) and post-LCD (102026, 18.4 %), mainly due to the reduced emission strength of amines and suppressed gas-to-particle partitioning of amines during the LCD and post-LCD. 74(C2H5)2NH2+ was the most abundant amine marker, which accounted for 98.2 %, 98.4 %, and 96.7 % of all amine-containing particles during the pre-LCD, LCD, and post-LCD, respectively. Correlation analysis and temporal variations indicated that the gas-to-particle partitioning of amines was facilitated by the stronger acidic environment and lower temperature, while the effect of RH and aerosol liquid water content was minor. The A-OC particles were the most abundant type (accounting for ~40 %) throughout the observation period. The temporal profiles and correlation analysis suggested that the impact of the increased O3 on the amines and their oxidation products (e.g., trimethylamine oxide) was minor. The identified particle types, correlation analysis, and the potential source contribution function results implied that the amine-containing particles were mainly derived from local and surrounding sources during the LCD, while those were mainly affected by long-range transport during the pre-LCD and post-LCD. Our results could deepen the comprehension of the sources and atmospheric processing of amines in the urban area of North China during the COVID-19 outbreak.

Contrasting compositions and sources of organic aerosol markers in summertime PM2.5 from urban and mountainous regions in the North China Plain.

Although the chemical compositions and sources of organic aerosols (OAs) have been extensively investigated at the summit of Mt. Tai in the North China Plain (NCP), their vertical distributions and characterizations in the Mt. Tai region is not well known. To better understand the vertical variations of OAs in the urban and mountainous atmosphere, PM2.5 samples were collected simultaneously on a daytime/nighttime basis at two sites of different altitudes (Taian urban site: 20 m above ground; the summit of Mt. Tai: 1534 m a.s.l.) during the summer of 2016. The concentrations of all the determined chemical compounds (e.g., OC, EC, inorganic ions, saccharides, n-alkanes, PAHs and hopanes) except for biogenic secondary organic aerosol (BSOA) tracers decreased with the increase in sampling height, indicating the relatively larger contribution of anthropogenic pollutants to OAs at the lower heights. The relatively low concentration levels of biomass burning tracers (e.g., levoglucosan, galactosan and mannosan) and the insignificant correlations of levoglucosan with carbonaceous species demonstrated a negligible effect of biomass burning on the mountaintop atmosphere. The enhanced concentrations of BSOA tracers were observed with the increase of height, largely due to the more intensive secondary oxidation of volatile organic compounds (VOCs) under the stronger radiation conditions at the summit. The daytime concentrations of carbonaceous species, primary sugars, sugar alcohols, PAHs and low molecular weight n-alkanes were significantly higher than those in nighttime at Mt. Tai, suggesting that these chemical compounds at the summit of Mt.Tai aerosols were transported from the ground surface by valley breezes in daytime. There was no correlation between BSOA tracers and relative humidity (RH) or liquid water content (LWC) at both the sites, because both the high RH and LWC can suppress the acid-catalyzed formation of BSOA due to the dilution of the aerosol acidity.

Enhanced photochemical formation of secondary organic aerosols during the COVID-19 lockdown in Northern China.

To eliminate the spread of a novel coronavirus breaking out in the end of 2019 (COVID-19), the Chinese government has implemented a nationwide lockdown policy after the Chinese lunar New Year of 2020, resulting in a sharp reduction in air pollutant emissions. To investigate the impact of the lockdown on aerosol chemistry, the number fraction, size distribution and formation process of oxalic acid (C2) containing particles and its precursors were studied using a single particle aerosol mass spectrometer (SPAMS) at the urban site of Liaocheng in the North China Plain (NCP). Our results showed that five air pollutants (i.e., PM2.5, PM10, SO2, NO2, and CO) decreased by 30.0-59.8% during the lockdown compared to those before the lockdown, while O3 increased by 63.9% during the lockdown mainly due to the inefficient titration effect of O3 via NO reduction. The increased O3 concentration can boost the atmospheric oxidizing capacity and further enhance the formation of secondary organic aerosols, thereby significantly enhancing the C2 particles and its precursors as observed during the lockdown. Before the lockdown, C2 particles were significantly originated from biomass burning emissions and their subsequent aqueous-phase oxidation. The hourly variation patterns and correlation analysis before the lockdown suggested that relative humidity (RH) and aerosol liquid water content (ALWC) played a key role in the formation of C2 particles and the increased aerosol acidity can promote the conversion of precursors such as glyoxal (Gly) and methyglyoxal (mGly) into C2 particles in the aqueous phase. RH and ALWC decreased sharply but O3 concentration and solar radiation increased remarkably during the lockdown, the O3-dominated photochemical pathways played an important role in the formation of C2 particles in which aerosol acidity was ineffective. Our study indicated that air pollution treatment sponges on a joint-control and balanced strategy for controlling numerous pollutants.

[Chemical Compositions and Sources of n-Alkanes and Saccharides in PM2.5 from Taian City During the Summer].

To investigate the variations and sources of n-alkanes and sugars in Taian City during summer, PM2.5 samples were collected from July 22 to August 19, 2016. The identified n-alkane and sugar sources were investigated using a principal component analysis (PCA) multiple linear regression (MLR) model and a backward trajectory model. The results showed that the mass concentrations of PM2.5 during summer were (37.2±11.5) µg·m-3. The mass concentrations of n-alkanes were (83.3±34.7) ng·m-3, the carbon preference index (CPI) was 1.83, and the relative contribution of wax n-alkanes was 34.7%-69.4%, suggesting that contributions from terrestrial plants were more significant in Taian City. The results showed that the mass concentrations of sugars in Taian City during summer were (73.4±46.6) ng·m-3. Levoglucan, galactosan, and mannosan were the main saccharides, accounting for 64.0%, 7.1%, and 6.3% of the total concentrations of sugars, respectively, indicating that biomass burning is much more significant in Taian City. The results of the PCA-MLR model suggested that n-alkanes and sugars in Taian City during summer were mostly from terrestrial plants, coal burning and biomass burning. The backward trajectory model showed that the pollution mostly came from the native sources of Shandong province and the inland cities in the south.

Molecular characteristics and stable carbon isotope compositions of dicarboxylic acids and related compounds in the urban atmosphere of the North China Plain: Implications for aqueous phase formation of SOA during the haze periods.

In the past five years, Chinese government has promulgated stringent measures to mitigate air pollution. However, PM2.5 levels in the China North Plain (NCP), which is one of the regions with the heaviest air pollution in the world, are still far beyond the World Health Organization (WHO) standard. To improve our understanding on the sources and formation mechanisms of haze in the NCP, PM2.5 samples were collected during the winter of 2017 on a day/night basis at the urban site of Liaocheng, which is one of the most polluted cities in the NCP. The samples were determined for molecular distributions and stable carbon isotope compositions of dicarboxylic acids and their precursors (ketocarboxylic acids and α-dicarbonyls), levoglucosan, elemental carbon (EC), organic carbon (OC) and water-soluble organic carbon (WSOC). Our results showed that oxalic acid (C2) is the dominant dicarboxylic acid, followed by succinic acid (C4) and malonic acid (C3), and glyoxylic acid (ωC2) is the most abundant ketocarboxylic acids. Concentrations of C2, glyoxal (Gly) and methylglyoxal (mGly) presented robust correlations with levoglucosan, suggesting that biomass burning is a significant source of PM2.5 in the NCP. Moreover, C2 and Gly and mGly linearly correlated with SO42-, relative humidity (RH), aerosol liquid water content (LWC) as well as particle in-situ pH (pHis), indicating that aqueous-phase oxidation is the major formation pathway of these SOA, and is driven by acid-catalyzed oxidation. Concentrations and relative abundances of secondary species including SNA (SO42-, NO3- and NH4+), dicarboxylic acids, and aerosol LWC in PM2.5 are much higher in the haze periods than in the clean periods, suggesting that aqueous reaction is a vital role in the haze formation. In comparison with those in the clean periods, stable carbon isotopic compositions (δ13C) of major dicarboxylic acids and related SOA and the mass ratios of C2/diacids, C2/Gly and C2/mGly are higher in the haze periods, indicating that haze particles were more aged and enriched in secondary species.

[Diurnal Variations and Source Analysis of Water-soluble Compounds in PM2.5 During the Winter in Liaocheng City].

To investigate the diurnal variations and sources of water-soluble compounds in Liaocheng City, PM2.5 samples were collected between January and February 2017. The PM2.5 samples were analyzed for the compositions, concentrations, and sources of water-soluble inorganic ions, oxalic acid, and levoglucosan. The sources of these chemical compound were investigated using principal component analysis (PCA) and multiple linear regression (MLR) modeling. The results showed that the mass concentrations of PM2.5during the nighttime were higher than those during the daytime, and the average concentrations exceeded the National Ambient Air Quality Standard (GB 3095-2012) by more than 1.8 times. Moreover, atmospheric pollution was worse during the day than during the night. SNA (SO42-, NO3-, and NH4+) were the dominant species among the inorganic ions, the relative abundance of which with respect to the total concentrations of inorganic ions was 73.4% and 77.1% during the daytime and nighttime, respectively. The ratios of anion to cation equivalents (AE/CE) were less than one, suggesting that the PM2.5 was slightly alkaline, and the degree of acidity at night was stronger than during the day. The results of the correlation analyses suggested that aqueous-phase oxidation was the major formation pathway of oxalic acid, which is driven by acid-catalyzed oxidation. The oxalic acid was mainly influenced by biomass burning during the winter in Liaocheng City. The results of the PCA-MLR model suggested that water-soluble compounds in Liaocheng City were mostly from vehicular emissions and secondary oxidation, biomass burning, while the impacts of mineral dust and coal burning were relatively minor.

[Source Analysis and Health Risk Assessment of PAHs in PM2.5 During Winter in Liaocheng City].

To investigate the mass concentrations, sources, and health effects of polycyclic aromatic hydrocarbons (PAHs) in ambient particulate matter (PM) in Liaocheng City during winter, 14 types of PAHs in PM2.5 were determined from January to February of 2017. The sources of the PAHs were analyzed by using diagnostics ratios and the principal component analysis (PCA)-multiple linear regression (MLR) model,and the health risk of PAHs was assessed by BaP equivalent concentrations (BaPeq) and incremental lifetime cancer risk (ILCR). The results showed that the mass concentrations of PAHs in PM2.5 during winter were (64.89±48.23) ng·m-3, Fla, Pyr, and Chry were predominant species, accounting for 15.5%, 12.8%, and 12.7% of the total concentrations of PAHs, respectively. Moreover, the ring distribution of the PAHs was dominated by four-ring PAHs. The pollution during the pre-Spring Festival and firework Ⅱwere the most severe during the sampling period. The results of the PCA-MLR model suggested that PAHs originated mostly from coal burning, biomass burning, and vehicle emissions. The toxicity exposure index (TEQ) in Liaocheng City during winter was (6.37±4.92) ng·m-3. The results of the risk model revealed that the ILCR of adults was higher than that of children, and both groups of ILCR for winter were in the range of the risk threshold. This suggests that a potential risk in terms of inhalation PAH exposure for residents in Liaocheng City.

[Pollution Characteristics and Source Analysis of n-alkanes and Saccharides in PM2.5 During the Winter in Liaocheng City].

To investigate molecular composition, mass concentrations, and sources of n-alkanes and sugars which are adsorbed in ambient particulate matters in Liaocheng City during winter, PM2.5 samples were collected from January 17 to February 15, 2017 at Liaocheng University. 19 kinds (C18-C36) of n-alkanes and 10 kinds of sugars were determined using GC-MS. The identification of n-alkane and sugar sources were investigated using principal component analysis (PCA). The results showed that the mass concentrations of total n-alkanes in PM2.5 during the winter were (456.9±252.5) ng·m-3. During the haze period, the concentrations of n-alkanes were two times higher than those on clear days. Additionally, the concentrations of n-alkanes during fireworks event I and fireworks event Ⅱ were 0.9 times and 1.2 times higher than those on clear days. During the sampling period, the Carbon preference index (CPI) was 1.2±0.1, and the contribution from plant wax concentrations for n-alkanes (% Wax Cn) was between 3.1%~36.0%, indicating that fossil fuels were the major source of n-alkanes in Liaocheng City during the winter. The mass concentrations of saccharides in PM2.5 during the winter were (415.5±213.8) ng·m-3. Levoglucosan was the most abundant species, followed by galactosan and mannosan, which accounted for more than 91.6% of total saccharides, indicating that biomass burning was much more significant in Liaocheng City. PCA further suggested that n-alkane and saccharide compounds in atmospheric aerosol during the winter in Liaocheng City were primarily derived from fossil fuel and biomass burning.