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Accurate assessment of the mechanical properties of organic matter, clay matrix, and bulk shale during maturation remains a challenge. Here, we aim to assess the mechanical properties of organic-rich shale during maturation using a combination of nanoindentation methods and various geochemical analyses, i.e., mineral composition, mass loss rate, chemical structure of organic matter, and Rock-Eval analyses. Results show that the evolution of mechanical properties of organic matter in shale during maturation can be divided into: the main oil-generation stage, and the condensate oil and gas generation stage. The stiffening of organic matter in the shale is mainly due to increased aromaticity and condensation of aromatic groups. The clay matrix experiences a slight decrease in hardness and Young's modulus at low maturity levels due to the generation of liquid hydrocarbons. However, overall, the clay matrix becomes stiffer as the shale matures due to shale dehydration, expulsion or cracking of liquid hydrocarbons, transformation of clay minerals, and hardening of organic matter. The Young's modulus and hardness of bulk shale generally increase with increasing maturity. This is closely related to the hardening of organic matter and clay matrix, as well as the development of the more compact and dense microstructure in the shale. [ABSTRACT FROM AUTHOR]

Polymetallic enrichment layers are commonly found at the base of the Lower Cambrian and extensively distributed across the Upper Yangtze Platform, yet their genetic models remain controversial. This study systematically collected samples from a typical section in the southeastern Chongqing region for mineral, organic, and inorganic analyses. It investigates the relationship between the abundance of various trace metal elements and organic matter at the base of the Niutitang Formation, as well as the vertical distribution characteristics of organic carbon isotopes and organic matter features. The results indicate that the Niutitang Formation shale exhibits a distinct three-part structure from bottom to top. Various metal elements are enriched in the lower interval, showing a close correlation between the abundance of polymetallic elements and the carbon isotopes of shale organic matter. The middle interval contains the highest TOC value and the lowest Ti/Al ratio, while the upper interval shows a significant decrease in organic matter abundance, with a clear positive correlation between the excess silicon content and Ti/Al ratio. Additionally, the mixing effect of deep-sea upwelling is the primary control on the formation of polymetallic enrichment layers in the lower interval, followed by the adsorption of organic matter under anoxic conditions. The sedimentary environment of the upper interval of the Niutitang Formation trends toward oxidation, with paleoclimate shifting toward colder and drier conditions, exhibiting aeolian sedimentary features that are unfavorable for the enrichment of trace metal elements. Consequently, upwelling is a key factor in the enrichment and mineralization of trace metal elements at the base of the Lower Cambrian in the Upper Yangtze region. [ABSTRACT FROM AUTHOR]

While aqueous-phase processing is known to contribute to the formation of nitrogen-containing organic compounds (NOCs), the specific pathways involved remain poorly understood. In this study, we aimed to characterize the NOCs present in both pre-fog aerosols and fog water collected at a suburban site in northern China. Fourier-transform ion cyclotron resonance mass spectrometry was utilized to analyze the molecular composition of NOCs in both negative and positive modes of electrospray ionization (ESI - and ESI +). In both pre-fog aerosols and fog water samples, NOCs constituted a significant portion, accounting for over 60 % of all assigned formulas in ESI - and more than 80 % in ESI +. By comparing the molecular composition of NOCs originating from biomass burning, coal combustion, and vehicle emissions, we identified that 72.3 % of NOCs in pre-fog aerosols were attributed to primary anthropogenic sources (pNOCs), while the remaining NOCs were categorized as secondary NOCs formed within the aerosols (saNOCs). Unique NOCs found in fog water were classified as secondary NOCs formed within the fog water (sfNOCs). Through a comprehensive "precursor–product pair" screening involving 39 reaction pathways, we observed that the nitration reaction, the amine pathway, and the intramolecular N-heterocycle pathway of NH 3 addition reactions contributed 43.6 %, 22.1 %, and 11.6 % of saNOCs, respectively. In contrast, these pathways contributed 26.8 %, 28.4 %, and 29.7 % of sfNOCs, respectively. This disparity in formation pathways is likely influenced by the diverse precursors, the aqueous acidity, and the gas-phase species partitioning. Correspondingly, saNOCs were found to contain a higher abundance of carbohydrate-like and highly oxygenated compounds with two nitrogen atoms compared to pNOCs. Conversely, sfNOCs exhibited a higher content of lipid-like compounds with fewer oxygen atoms. These results underscore the distinct secondary processes contributing to the diversity of NOCs in aerosols and fog water, which may lead to their different climate effects. [ABSTRACT FROM AUTHOR]

Halogenated aromatic compounds (HACs) exhibit environmental ubiquity, persistence, bioaccumulation, and diverse toxic effects, prompting widespread concern about their pollution and potential risks. This study investigated four categories of typical HACs in fish samples from five common species in South China. Results showed that the mean±standard deviation (range) of toxic equivalent quantity (TEQ) of polychlorinated dibenzo-p-dioxins/ furans (PCDD/Fs), dioxins-like polychlorinated biphenyls (DL-PCBs), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs), and total dioxins (dioxins) were (0.0680±0.3230) pg⋅g-1(0 ~2.21 pg⋅g-1), (0.118±0.124) pg⋅g-1 (0.000451 ~0.528 pg⋅g-1), (0.139±0.164) pg⋅g-1 (0.00882 ~0.917 pg⋅g-1), and (0.325±0.366) pg⋅g-1 (0.0409 ~ 2.30 pg⋅g-1) (based on wet weight), respectively. All values were below the specified TEQ limit set by the European Union (EU) for dioxins in fish. Among the five fish species, mandarin fish exhibited the highest total TEQ and intake risk, followed by eel and catfish, while perch had the lowest. However, no statistical differences were observed in the TEQ among these five fish species. In comparison to global data, the concentrations of polybromodiphenyl ethers (PBDEs) in these fish samples (0.347±0.297) ng⋅g-1(0.0191 ~ 1.40 ng⋅g-1) (based on wet weight) were at moderate or low levels with a changing trend among species: salmon>eel>perch>mandarin fish>catfish. The PCDD/Fs in these fish samples were predominantly high-chlorinated, possibly originating from PCDD/Fs-polluted feed and the use of pentachlorophenol/pentachlorophenol sodium. PCB-118 and PCB-105 were the dominant congeners of DL-PCBs in these samples, primarily sourced from commercial PCB products and various metal smelting processes. The sources of PBDEs in these fishes included commercial PBDE mixtures and the debromination of high-brominated PBDEs. PBDD/Fs showed dominance in high-brominated PBDFs, and their pollution was closely associated with PBDEs. The intake carcinogenic and non-carcinogenic risk values of these four HACs via fish consumption ranged from 6.56x 10-6 to 2.87x 10-5 and 0.0314 to 0.114, respectively, for the residents from South China, with higher values for children compared to teenagers and adults. PBDD/Fs contributed significantly higher total TEQ and intake risks (45.6% on average) than the other HACs, emphasizing the ongoing need for continuous attention to their pollution in biota and associated risks. [ABSTRACT FROM AUTHOR]

The formation process of in‐cloud aqueous‐phase secondary organic matter (aqSOM) and its characteristics are unclear. Herein, water‐soluble inorganic ions, oxalate, and water‐soluble organic carbon (WSOC) were determined in cloud water and aerosol (PM2.5) samples simultaneously collected at a remote mountain site in southern China during spring 2018 and winter 2020. The molecular compositions of water‐soluble organic matter (WSOM) in cloud water and aerosols were analyzed by a Fourier transform ion cyclotron resonance mass spectrometer in negative electrospray ionization (ESI‐) mode. The results showed that the mean concentration of WSOC was 6.27–8.54 mg C L−1 in cloud water and 0.60–1.37 μg C m−3 in aerosols. The strong correlation observed between WSOM and aqueous secondary matter (e.g., NO3− and oxalate), the positive matrix factorization results, and the elevated WSOM/K+ ratios observed in cloud water suggested enhanced aqSOM formation in cloud water. According to random forest analysis, the factors related to in‐cloud WSOM variation mainly included secondary ions, K+, cloud water pH, and atmospheric NOx. Additionally, 37 characteristic in‐cloud aqSOM molecules, classified as ‐Ox, ‐NOx, ‐N2Ox, and ‐N1‐2OxS, mainly consisting of dicarboxylic acids, nitrophenols, and dinitrophenols, were identified using linear discriminant analysis effect size (LefSe). The characteristic N‐ and S‐containing molecules in in‐cloud aqSOM with carbon numbers >10 had low or extremely low volatility; therefore, they might contribute to secondary organic aerosol formation after droplet evaporation. The results revealed the modifying effects of in‐cloud processes on aerosol organic composition at the molecular level and could improve our understanding of aerosol–cloud interactions. Plain Language Summary: In this study, we determined the water‐soluble ion, water‐soluble organic matter (WSOM) and organic molecular composition of cloud water and aerosol samples collected at a remote mountain site in southern China. The results indicated the formation of secondary organic matter (SOM) in cloud water, the proportion of which in total WSOM was >50%. In addition, the characteristic molecules of SOM in cloud water were identified, some of which had low or extremely low volatility and might remain in the particulate phase after droplet evaporation. This work advanced our understanding of secondary organic aerosol formation in cloud water and its implications for the climate and the environment. Key Points: The proportion of in‐cloud aqueous‐phase secondary organic matter in WSOM was >50%Some molecules, for example, diacids and dinitrophenols, were identified as characteristic molecules of in‐cloud secondary organic matterMolecules with C numbers >10 formed by in‐cloud processes had low volatility [ABSTRACT FROM AUTHOR]

Humic-like substances (HULIS) encompass a continuum of molecular weight (MW) ranges, yet our understanding of how HULIS characteristics vary with MW is still limited and not well established. In this study, a combination of ultrafiltration and solid-phase extraction protocols was employed to fractionate the high MW (HMW; > 1 kDa) and low MW (LMW; < 1 kDa) HULIS fractions from ambient aerosols collected during summer and winter at a rural site. Subsequently, comprehensive characterization using total organic carbon, high-performance size exclusion chromatography (HPSEC), UV-visible (UV-vis) and fluorescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), and negative electrospray ionization high-resolution mass spectrometry (ESI–HRMS) were conducted. The results revealed that HMW HULIS were dominated by larger-sized chromophores, substantially constituting a higher fraction of total organic carbon and UV absorption at 254 nm than LMW HULIS. While both HMW and LMW HULIS shared similar fluorophore types and functional groups, the former exhibited higher levels of humification and a greater presence of polar functional groups (e.g., - COOH; > C = O). HRMS analysis further unveiled that molecular formulas within HMW HULIS generally featured smaller sizes but higher degrees of unsaturation and aromaticity compared to those within LMW HULIS fractions. This observation suggests the possibility of small molecules assembling to form the HMW HULIS through intermolecular weak forces. Moreover, HMW HULIS contained a higher proportion of CHON but fewer CHO compounds than LMW HULIS. In both HMW and LMW HULIS, the unique molecular formulas were primarily characterized by lignin-like species, yet the former displayed a prevalence of N-enriched and highly aromatic species. Additionally, HMW HULIS contained more unique lipid-like compounds, while LMW HULIS exhibited a distinct presence of tannin-like compounds. These findings provide valuable insights into the distribution, optical properties, and molecular-level characteristics of HULIS in atmospheric aerosols, thereby advancing our understanding of their sources, composition, and environmental implications. [ABSTRACT FROM AUTHOR]

While aqueous-phase processing contributes to the formation of nitrogen-containing organic compounds (NOCs), the detailed pathways are not well understood. In this study, the molecular composition of NOCs in both pre-fog aerosols and fog water collected at a suburban site in northern China was characterized using Fourier-transform ion cyclotron resonance mass spectrometry in both negative and positive modes of electrospray ionization (ESI- and ESI+). In both pre-fog aerosols and fog water, NOCs account for number fractions of more than 60 % in all assigned formulas in ESI- mode and more than 80 % in ESI+ mode. By comparing the molecular composition of biomass burning, coal combustion, and vehicle emissions, 72.3 % of NOCs in pre-fog aerosols were assigned as originating from these primary anthropogenic sources (pNOCs), while the remaining NOCs were regarded as secondary NOCs formed in aerosol (saNOCs). On the other hand, the unique NOCs in fog water were regarded as secondary NOCs formed in fog (sfNOCs). According to "precursor-product pair" screening involving 39 reaction pathways, we found that the nitration reaction, the amine pathway and the intramolecular N-heterocycle pathway of NH3 addition reactions contribute to 43.6 %, 22.1 %, and 11.6 % of saNOCs, but 26.8 %, 28.4 %, and 29.7 % of sfNOCs, respectively. Such distinct formation pathways are most likely attributed to the diverse precursors and the aqueous acidity. Correspondingly, saNOCs contain more abundant carbohydrates-like and highly oxygenated compounds with two nitrogen atoms compared to pNOCs, whereas sfNOCs contain more lipids-like with fewer oxygen atoms. The results reveal the disparity in secondary processes that contribute to the richness of NOCs in aerosols and fog water. The findings are valuable for understanding the formation and control of organic nitrogen pollution. [ABSTRACT FROM AUTHOR]

Humic-like Substances (HULIS) encompass a continuum of molecular weight (MW) ranges, yet our understanding of how HULIS characteristics vary with MW is still limited and not well-established. In this study, a combination of ultrafiltration and solid-phase extraction protocols was employed to fractionate the high MW (HMW, >1 kDa) and low MW (LMW, < 1kDa) HULIS fractions from ambient aerosols collected during summer and winter at a rural site. Subsequently, comprehensive characterization by using total organic carbon, high-performance size exclusion chromatography (HPSEC), UV-vis and fluorescence spectroscopy, Fourier-transform infrared spectroscopy (FTIR), negative electrospray ionization high resolution mass spectrometry (ESI- HRMS) were conducted. The results revealed that HMW HULIS were dominated by larger-sized chromophores, substantially constituting a higher fraction of total organic carbon and UV absorption at 254 nm than LMW HULIS. While both HMW and LMW HULIS shared similar fluorophore types and functional groups, the former exhibited higher levels of humification and a greater presence of polar functional groups (e.g., -COOH, >C=O). HRMS analysis further unveiled that molecular formulas within HMW HULIS generally featured smaller sizes but higher degrees of unsaturation and aromaticity compared to those within LMW HULIS fractions. This observation suggests the possibility of small molecules assembling to form the HMW HULIS through intermolecular weak forces. Moreover, HMW HULIS contained a higher proportion of CHON but fewer CHO compounds than LMW HULIS. In both HMW and LMW HULIS, the unique molecular formulas were primarily characterized by lignin-like species, yet the former displayed a prevalence of N-enriched and highly aromatic species. Additionally, HMW HULIS contained more unique lipids-like compounds, while LMW HULIS exhibited a distinct presence of tannin-like compounds. These findings provide valuable insights into the distribution, optical properties, and molecular-level characteristics of HULIS in atmospheric aerosols, thereby advancing our understanding of their sources, composition, and environmental implications. [ABSTRACT FROM AUTHOR]

The accurate identification of elemental carbon (EC) sources in aerosol based on radiocarbon (14 C) depends on the method of EC isolation. The lack of aerosol EC reference materials with "true" 14 C values makes it impossible to evaluate the accuracy of various methods for the analysis of 14 C-EC in aerosols. In this study, EC isolation methods were evaluated by using samples of mixed biomass burning, vehicle exhaust, and coal combustion. The results show that 14 C-EC was not only related to the isolation method but also to the types and proportions of biomass sources in the sample. The hydropyrolysis (Hypy) method, which can be used to isolate a highly stable portion of EC Hypy and avoid charring, is a more effective and stable approach for the matrix-independent 14 C quantification of EC in aerosols. The 13 C-EC Hypy and non-fossil EC Hypy values of Standard Reference Material (SRM) 1649b were -24.9 ‰ and 11 %, respectively. [ABSTRACT FROM AUTHOR]

Rheological deformation of coal could severely jeopardize the extraction performance during deep coal mining and coalbed methane development by causing instability, shrinkage and collapse of drilling boreholes in the long run. Standard macroscale creep test could only reveal the bulk properties of coal while neglecting the high heterogeneity nature of coal mainly composed of various organic macerals. This study took a low-rank (0.39% Ro) humic coal as research object, and employed nanoindentation technique to study its mechanical and rheological heterogeneity from the particle level. The results showed that mechanical heterogeneity within the humic coal is manifested as inertinite being much harder and less likely to undergo creep than vitrinite. By focusing on vitrinite, both mechanical properties and creep resistance showed negative relationships with loading rate and indentation size. The relationship of creep displacement and time can be best depicted by the model with one spring and two Kelvin–Voigt bodies. To probe into the structure-dependent rheological properties of organic matter in geo-field, carbon stacking structure from X-ray diffraction, creep behavior via nanoindentation and stress distribution simulated by finite-element analysis of coal were compared with another natural carbon aggregation as solid bitumen. The results showed that the coal investigated exhibited a relatively weaker creep resistance than solid bitumen, which is a consequence of its looser stacking manner with small size of crystallites in plane but large layer space inside. The observations here signified the role of chemical structure in determining rheology of organic matter. [ABSTRACT FROM AUTHOR]

Individual hydrocarbons identified to be macrocyclic alkanes in a torbanite from the Sydney Basin (Australia) were successfully isolated from its extracts using preparative gas chromatography and analyzed by NMR. Saturated cyclic structures were confirmed by single peaks in the NMR 1H and 13C spectra indicating single forms of H and C atoms exist in these biomarker molecules. This is consistent with the methylene unit in a ring system assignment of the macrocyclic alkanes and accounts for a formula of (CH2)n. The unusual molecular structures of these compounds are consistent with those that were identified from previous GC retention index data and co-injection with a standard supports the previous research. The mass spectral fragmentation behaviors of representative cyclic alkanes were further investigated by comparing them with the mass spectra of isolated individual macrocyclic alkanes. The characteristic fragment ions in the macrocyclic alkanes of (M–28)+ and base peaks of m/z 97, 111, 125, etc., can be assigned as being generated by simple α-/i-cleavage and hydrogen rearrangement. These fragmentation pathways combined with retention indices should assist in differentiating these compounds from monounsaturated alkenes and alkylated monocyclics having similar mass spectral characteristics in other geological samples. [ABSTRACT FROM AUTHOR]

The accurate identification of elemental carbon (EC) source in aerosol based on radiocarbon (14C) depends on the method of EC isolation. The lack of aerosol EC reference materials with 'true' 14C values makes it impossible to evaluate the accuracy of various methods for the analysis of 14C-EC in aerosols. In this study, EC separation methods were evaluated by using samples of mixed biomass burning, vehicle exhaust and coal-combustion. The results show that 14C-EC was not only related to the separation method but also to the types and proportions of biomass sources in the sample. And the Hydropyrolysis (Hypy) method, which can be used to separate a highly stable portion of ECHypy and avoid charring, is a more effective and stable approach for the matrix-independent 14C quantification of EC in aerosols. The 13C-ECHypy and non-fossil ECHypy values of SRM1649b was 24.9 ‰ and 11 %, respectively. [ABSTRACT FROM AUTHOR]

In traditional kerogen pyrolysis experiments, the effects of minerals and rock fabric on the pyrolysis products were ignored. To further clarify the role of the mineral matrix and rock fabric on hydrocarbon generation and retention, a closed anhydrous pyrolysis experiment was conducted on core plugs, powdered rock and kerogen from a clay-rich sample of Maoming oil shale within a temperature range of 312 °C to 600 °C, at a fixed pressure of 30 Mpa. The experiment's results showed that the yields of heavy hydrocarbons (C14+) generated from the core plugs and powdered rock were obviously lower than that of kerogen, which may be caused by the retention effect of clay minerals in raw shale. The yields of gaseous hydrocarbons generated from core plugs were lower compared with powdered rock due to the retention of C2+ hydrocarbons by the intact rock fabric and the preferential generation of methane. Light hydrocarbon (C6-14) yields generated from the core plugs and powdered rock were higher than kerogen, which may be the consequence of the cleavage of extraction bitumen and the interactions with kerogen. Moreover, the ratios of iso to normal paraffin (iC4/nC4, iC5/nC5) of the core plugs and powdered rock were higher than kerogen. Our experimental results show that kerogen pyrolysis in a confined system may overestimate the hydrocarbon generation potential due to the negligence of the retention effect of minerals and the rock fabric, especially in the source rocks rich in clay minerals. [ABSTRACT FROM AUTHOR]

Three-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy is an important method for the identification of the occurrence, chemical composition, and source of atmospheric chromophores. However, current knowledge on the identification and interpretation of fluorescent components is mainly based on aquatic dissolved organic matter and might not be applicable to atmospheric samples. Therefore, this study comprehensively investigated EEM data of different types of strong light-absorbing organic compounds, water-soluble organic matter (WSOM) in different aerosol samples (combustion source samples and ambient aerosols), soil dust, and purified fulvic and humic acids supplemented by parallel factor (PARAFAC) modeling. The results demonstrated that organic compounds with high aromaticity and strong electron-donating groups generally present strong fluorescence spectra at longer emission wavelengths, whereas organic compounds substituted with electron-withdrawing groups have relatively weaker fluorescence intensity. In particular, aromatic compounds containing nitro groups (i.e., nitrophenols), which show strong absorption and are the major component of atmospheric brown carbon, exhibited no significant fluorescence. The EEM–PARAFAC method identified three fluorescent components (i.e., C1, C2, and C3) in ambient WSOM. Although EEM–PARAFAC-derived C1 (Ex / Em = 235, 270/330 nm) in ambient WSOM is generally considered to be protein-like groups, our findings suggested that it is mainly composed of aromatic acids, phenolic compounds, and their derivatives, with only traces of amino acids. C2 is associated with the atmospheric chemical reaction of biomass burning and/or biogenic organic molecules, with a relatively lower degree of oxidation, which are more abundant in Guangzhou WSOM (56 %–69 %). C3, in contrast, is mainly attributed to highly oxygenated organic molecules derived from soil and atmospheric aging processes and has a relatively higher contribution in Chuzhou WSOM (23 %). These findings provide new insights into the analysis of chemical properties and sources of atmospheric fluorophores using the EEM method. [ABSTRACT FROM AUTHOR]

Water-soluble humic-like substances (HULIS) absorb light in near-UV and visible wavelengths and exert significant influence on the atmospheric environment and climate. However, knowledge on HULIS evolution during haze bloom-decay process is limited. Herein, PM 2.5 samples were obtained during a winter haze event in Guangzhou, China, and the light absorption and molecular composition of HULIS were investigated by UV–Vis spectrophotometry and ultrahigh-resolution mass spectrometry. Compared with HULIS on clean days, the absorption coefficients (Abs 365) of HULIS on haze days were significantly higher but the mass absorption efficiencies (MAE 365) were relatively low, suggesting diverse and dynamic absorption properties of HULIS during haze episodes. The CHO and CHON compounds were the most abundant components in HULIS, followed by CHOS, CHONS, and CHN. Haze HULIS presented comparatively high molecular weight; a lower aromaticity index (AI mod); and higher O/Cw , O/Nw , and O/Sw ratios, indicating that HULIS fractions undergo relatively high oxidation during haze days compared to clean days. Moreover, CHON and CHO compounds with high AI mod were the major potential chromophores in HULIS and significantly contributed to HULIS light absorption. It is worth noting that the proportions of these chromophores decreased during haze events, mainly owing to their higher oxidation during haze episodes. Besides, accumulated contribution of organic compounds emitted from vehicles and formed from reactions of biogenic volatile organic compounds (bio-VOCs) also diluted light-absorbing compounds in haze HULIS. These findings help us to understand HULIS evolution during haze bloom-decay processes in the subtropic region of China. [ABSTRACT FROM AUTHOR]

FTT experiments with water as a hydrogen source and three types of possible carbon sources in the subsurface (diiron nonacarbonyl, siderite and formic acid, representing CO, CO2 and a simple organic acid, respectively) were carried out in this study. Our experimental results showed that n‐alkanes with the highest carbon number of C33 were produced when CO was used as a carbon source (series A); a variety of polycyclic aromatic hydrocarbons (PAHs) were detected in series B with CO2 as a carbon source; gaseous hydrocarbons were also detected with formic acid added (series C). The different products in the three series showed that there were different hydrocarbon generation mechanisms and reaction processes with different carbon sources. The generation of long‐chain n‐alkanes in series A provided experimental support for the formation of abiogenic petroleum underground, which was of significance to early membranes on the Earth. PAHs in series B provide experimental support for the possibility of an abiotic source of reduced carbon on other planets. The carbon isotopes of gaseous hydrocarbons produced by CO exhibited a partial reversed order (δ13C1 < δ13C2 > δ13C3 > δ13C4 > δ13C5), while the gaseous hydrocarbons produced by CO2 and HCOOH showed a positive order (δ13C1 < δ13C2 < δ13C3 < δ13C4 < δ13C5). Based on these, the alkylene mechanism and the carbonyl insertion mechanism were used to reasonably explain these characteristics. [ABSTRACT FROM AUTHOR]

For identifying the occurrence and extent of thermochemical sulfate reduction (TSR) reaction of natural gas and better understanding the chemical and carbon isotopic variations in natural gas reservoirs, high-pressure hydro-pyrolysis with a special designed apparatus was performed using natural gas and various amounts of MgSO4·7H2O at up to 360 °C. The yields, chemical and isotopic compositions of the gases produced during TSR and thermal cracking were measured. As the extent of TSR reaction increased, the concentrations of CH4, CO2 and H2S increased in a nonlinear way, while those of C2H6 and C3H8 decreased. According to the variation of gas content, the TSR reaction of alkane gases can be divided into an uncatalyzed and a catalyzed stage, which is different from previous studies that treated the TSR reaction of alkane gases as a non-autocatalytic reduction process. As the concentration of MgSO4·7H2O increased, the rate of TSR reaction with hydrocarbon gases increased. The concentrations of HSO4− and volume of aqueous phase could be responsible for the different TSR reaction rates in the catalyzed stage. The co-variation of ln(C1/C2) and ln(C2/C3) could be related to the TSR reaction of alkane gases. Our study provides clues for understanding the compositional variations in natural conditions. [ABSTRACT FROM AUTHOR]

The lower Cambrian Niutitang/Qiongzhusi shale gas in the Middle-Upper Yangtz Block had been regarded as a very promising unconventional natural gas resource due to its high total organic carbon, great thickness, and large areal distribution. However, no commercial shale gas fields have yet been reported. From the northwest to the southeast there are considerable differences in the sedimentary environments, lithology, and erosive nature of the underlying interval (the floor interval) of the Niutitang shale. However, systematic research on whether and how these regional differences influence shale petrophysical properties and shale gas preservation in the Niutitang shale is lacking. A comparison of Niutitang shale reservoirs as influenced by different sedimentary and tectonic backgrounds is necessary. Samples were selected from both the overmature Niutitang shales and the floor interval. These samples cover the late Ediacaran and early Cambrian, with sedimentary environments varying from carbonate platform and carbonate platform marginal zone facies to continental shelf/slope. Previously published data on the lower Cambrian samples from Kaiyang (carbonate platform), Youyang (carbonate platform marginal zone) and Cen'gong (continental shelf/slope) sections were integrated and compared. The results indicate that the petrophysical properties of the floor interval can affect not only the preservation conditions (sealing capacity) of the shale gas, but also the petrophysical properties (pore volume, porosity, specific surface area and permeability) and methane content of the Niutitang shale. From the carbonate platform face to the continental shelf/slope the sealing capacity of the floor interval gradually improves because the latter gradually passes from high permeability dolostone (the Dengying Formation) to low permeability dense chert (the Liuchapo Formation). In addition, in contrast with several unconformities that occur in the carbonate platform face in the northern Guizhou depression, no unconformity contact occurs between the Niutitang shale and the floor interval on the continental shelf/slope developed in eastern Chongqing Province and northwestern Hunan Province. Such regional differences in floor interval could lead to significant differences in hydrocarbon expulsion behaviour and the development of organic pores within the Niutitang shale. Therefore, shale gas prospects in the Niutitang shales deposited on the continental shelf/slope should be significantly better than those of shales deposited on the carbonate platform face. [ABSTRACT FROM AUTHOR]

Atmospheric brown carbon (BrC) makes a substantial contribution to aerosol light absorption and thus global radiative forcing. Although BrC may change the lifetime of the clouds and ultimately affect precipitation, little is known regarding the optical properties and formation of BrC in the clouds. In the present study, the light-absorption properties of cloud droplet residual (cloud RES) were measured by coupled a ground-based counterflow virtual impactor (GCVI) and an aethalometer (AE-33), in addition to the cloud interstitial (cloud INT) and ambient (cloud-free) particles by PM 2.5 inlet-AE-33 at Mt. Tianjing (1690 m a.s.l.), a remote mountain site in southern China, from November to December 2020. Meanwhile, the light-absorption and fluorescence properties of water-soluble organic carbon (WSOC) in the collected cloud water and PM 2.5 samples were also obtained, associated with the concentration of water-soluble ions. The mean light-absorption coefficient (Abs 370) of the cloud RES, cloud INT, and cloud-free particles were 0.25 ± 0.15, 1.16 ± 1.14, and 1.47 ± 1.23 Mm -1 , respectively. The Abs 365 of WSOC was 0.11 ± 0.08 Mm -1 in cloud water and 0.40 ± 0.31 Mm -1 in PM 2.5 , and the corresponding mass absorption efficiency (MAE 365) was 0.17 ± 0.07 and 0.31 ± 0.21 m 2 g -1 , respectively. A comparison of the light-absorption coefficient between BrC in cloud RES and cloud INT particles, and WSOC in cloud water and PM 2.5 indicates a considerable contribution (48 %–75 %) of water-insoluble BrC to total BrC light absorption. Secondary BrC estimated by minimum R squared (MRS) method dominated the total BrC in cloud RES (67 %–85 %), rather than in the cloud-free (11 %–16 %) and cloud INT (9 %–23 %) particles. It may indicate the formation of secondary BrC during cloud processing. Supporting evidence includes the enhanced WSOC and dominant contribution of the secondary formation and biomass burning factor (>80 %) to Abs 365 in cloud water provided by positive matrix factorization (PMF) analysis. In addition, we showed that the light absorption of BrC in cloud water was closely related to humic-like substances and tyrosine-like and/or protein-like substances (r>0.63 , p<0.01), whereas only humic-like substances for PM 2.5 , as identified by excitation-emission matrix fluorescence spectroscopy. [ABSTRACT FROM AUTHOR]

Atmospheric brown carbon (BrC) makes a substantial contribution to aerosol light-absorbing and thus the global radiative forcing. Although BrC may change the lifetime of the cloud and ultimately affect precipitation, little is known regarding the optical properties and formation of BrC in the cloud. In the present study, the light-absorption properties of cloud droplet residual (cloud RES) were measured by coupled a ground-based counterflow virtual impactor (GCVI) and an Aethalometer (AE-33), in addition to the cloud interstitial (cloud INT) and ambient (cloud-free) particles by PM2.5 inlet-AE-33, at Mt. Tianjing (1690 m a.s.l.), a remote mountain site in southern China, from November to December 2020. Meanwhile, the light-absorption and fluorescence properties of water-soluble organic carbon (WSOC) in the collected cloud water and PM2.5 samples were also obtained, associated with the concentration of water-soluble ions. The mean light-absorption coefficient (Abs370) of the cloud RES, cloud INT, and cloud-free particles were 0.25 ± 0.15, 1.16 ± 1.14, and 1.47 ± 1.23 Mm−1, respectively. The Abs365 of WSOC was 0.11 ± 0.08 Mm−1 in cloud water and 0.40 ± 0.31 Mm−1 in PM2.5, and the corresponding mass absorption efficiency (MAE365) was 0.17 ± 0.07 and 0.31 ± 0.21 m2·g−1, respectively. A comparison of the light-absorption coefficient between BrC in the cloud RES/cloud INT and WSOC in cloud water/PM2.5 indicates a considerable contribution (48-75 %) of water-insoluble BrC to total BrC light-absorption. Secondary BrC estimated by minimum R squared (MRS) method dominated the total BrC in cloud RES (67-85 %), rather than in the cloud-free (11-16 %) and cloud INT (9-23 %) particles. It may indicate the formation of secondary BrC during cloud processing. Supporting evidence includes the enhanced WSOC and dominant contribution of secondary formation/biomass burning factor (> 80 %) to Abs365 in cloud water provided by Positive Matrix Factorization (PMF) analysis. In addition, we showed that the light-absorption of BrC in cloud water was closely related to humic-like substances and tyrosine/proteins-like substances (r > 0.63, p < 0.01), whereas only humic-like substances for PM2.5, as identified by excitation-emission matrix fluorescence spectroscopy. [ABSTRACT FROM AUTHOR]

Characterizing the molecular composition of cloud water could provide unique insights into aqueous chemistry. Field measurements were conducted at Mt. Tianjing in southern China in May, 2018. There are thousands of formulas (C5–30 H4–55 O1–15 N0–2 S0–2) identified in cloud water by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). CHON formulas (formulas containing C, H, O, and N elements; the same is true for CHO and CHOS) represent the dominant component (43.6 %–65.3 % of relative abundance), followed by CHO (13.8 %–52.1%). S-containing formulas constitute ∼ 5 %–20 % of all assigned formulas. Cloud water has a relative-abundance-weighted average O/C of 0.45–0.56, and the double bond equivalent of 5.10–5.70. Most of the formulas (>85 %) are assigned as aliphatic and olefinic species. No statistical difference in the oxidation state is observed between cloud water and interstitial PM2.5. CHON with aromatic structures are abundant in cloud water, suggesting their enhanced in-cloud formation. Other organics in cloud water are mainly from biomass burning and oxidation of biogenic volatile organic compounds. The cloud water contains more abundant CHON and CHOS at night, which are primarily contributed by -N2 O5 function and organosulfates, demonstrating the enhanced formation in dark aqueous or multi-phase reactions. While more abundant CHO is observed during the daytime, likely due to the photochemical oxidation and photolysis of N- or S-containing formulas. The results provide an improved understanding of the in-cloud aqueous-phase reactions. [ABSTRACT FROM AUTHOR]

Biomass burning (BB) and coal combustion (CC) are important sources of brown carbon (BrC) in ambient aerosols. In this study, six biomass materials and five types of coal were combusted to generate fine smoke particles. The BrC fractions, including water-soluble organic carbon (WSOC), humic-like substance carbon (HULIS-C), and methanol-soluble organic carbon (MSOC), were subsequently fractionated, and their optical properties and chemical structures were then comprehensively investigated using UV–visible spectroscopy, proton nuclear magnetic resonance spectroscopy (1 H NMR), and fluorescence excitation–emission matrix (EEM) spectroscopy combined with parallel factor (PARAFAC) analysis. In addition, the oxidative potential (OP) of BB and CC BrC was measured with the dithiothreitol (DTT) method. The results showed that WSOC, HULIS-C, and MSOC accounted for 2.3 %–22 %, 0.5 %–10 %, and 6.4 %–73 % of the total mass of combustion-derived smoke PM 2.5 , respectively, with MSOC extracting the highest concentrations of organic compounds. The MSOC fractions had the highest light absorption capacity (mass absorption efficiency at 365 nm (MAE 365): 1.0–2.7 m 2 /gC) for both BB and CC smoke, indicating that MSOC contained more of the strong light-absorbing components. Therefore, MSOC may represent the total BrC better than the water-soluble fractions. Some significant differences were observed between the BrC fractions emitted from BB and CC with more water-soluble BrC fractions with higher MAE 365 and lower absorption Ångström exponent values detected in smoke emitted from BB than from CC. EEM-PARAFAC identified four fluorophores: two protein-like, one humic-like, and one polyphenol-like fluorophores. The protein-like substances were the dominant components of WSOC (47 %–80 %), HULIS-C (44 %–87 %), and MSOC (42 %–70 %). The 1 H-NMR results suggested that BB BrC contained more oxygenated aliphatic functional groups (H-C-O), whereas CC BrC contained more unsaturated fractions (H-C-C= and Ar-H). The DTT assays indicated that BB BrC generally had a stronger oxidative potential (DTT m , 2.6–85 pmol/min/ µ g) than CC BrC (DTT m , 0.4–11 pmol/min/ µ g), with MSOC having a stronger OP than WSOC and HULIS-C. In addition, HULIS-C contributed more than half of the DTT activity of WSOC (63.1 % ± 15.5 %), highlighting that HULIS was a major contributor of reactive oxygen species (ROS) production in WSOC. Furthermore, the principal component analysis and Pearson correlation coefficients indicated that highly oxygenated humic-like fluorophore C4 may be the important DTT active substances in BrC. [ABSTRACT FROM AUTHOR]

Characterizing the molecular composition of cloud water could provide unique insight into the aqueous chemistry. Field measurement was conducted at Mt. Tianjing in southern China during May' 2018. Thousands of formulas (C5.30H4.55O1. I[SUB 5]N[SUB 0].[SUB 2]S[SUB 0].2) were identified in cloud water by Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). CHON represents the dominant component (43.6-65.3% of relative abundance)' followed by CHO (13.8-52.1%). S-containing formulas constitute the remaining ~10-20%. Molecules have O/C of 0.45-0.56 and the double-bond equivalent of 5.10-5.70. More than 90% are assigned as aliphatic and olefinic species. No statistical difference of oxidation state is observed between cloud water and interstitial PM2.5. CHON with aromatic structures are abundant in cloud water' suggesting their enhanced in- cloud formation. Other organics in cloud water are mainly from biomass burning and oxidation of biogenic volatile organic compounds. The cloud water contains more abundant CHON and CHOS at night' which are mainly contributed by -N2O5 function and organosulfates' demonstrating the enhanced formation in dark aqueous or multi-phase reactions. While more abundant CHO are observed during the daytime' likely due to the photochemical oxidation and photolysis of N-/S-containing formulas. The results provide an improved understanding on the in-cloud aqueous-phase reactions. [ABSTRACT FROM AUTHOR]

Size and effective density (ρe) are important properties of aerosol particles and are related to their influences on human health and the global climate. The volume equivalent diameter (Dve) is an intrinsic property that is used to evaluate particle size. Three definitions of ρe are generally used to characterize the physical property of a particle as an alternative to particle density, in which only the ρeII , defined as the ratio of particle density (ρp) to a dynamic shape factor (χ), has the characteristic of being independent of particle size. However, it is still challenging to simultaneously characterize the Dve and ρeII of aspherical particles. Here, we present a novel system that classifies particles with their aerodynamic diameter (Da) by aerodynamic aerosol classifier (AAC) and determines their vacuum aerodynamic diameter (Dva) by single-particle aerosol mass spectrometry (SPAMS) to achieve a measurement of Dve and ρeII. The reliability of the AAC-SPAMS system for accurately obtaining Dve and ρeII is verified based on the result that the deviation between the measured and theoretical values is less than 6 % for the size-resolved spherical polystyrene latex (PSL). The AAC-SPAMS system was applied to characterize the Dve and ρeII of (NH 4) 2 SO 4 and NaNO 3 particles, suggesting that these particles are aspherical and their ρeII is independent of particle size. Finally, the AAC-SPAMS system was deployed in a field measurement, showing that it is a powerful technique to characterize the chemically resolved Dve and ρeII of particles in real time. [ABSTRACT FROM AUTHOR]

Organic acids are important agents in the alteration of deep reservoirs. It is difficult, however, to assess the impact of organic acid alteration on deep reservoirs because different dissolution processes may occur during diagenesis. This study simulated the dissolution of three different types of reservoir rocks by acetic acid in a closed system and compared the mineral and elemental composition, surface morphology, pore structure, and water chemistry variations of the initial and altered samples. The study demonstrated that both micrite and sucrosic dolostone are strongly dissolved, losing about 20%–30% of their initial rock sample weights. Observation under SEM showed that the limestone dissolved homogenously, whereas the dolostone showed honeycomb-like dissolution. Both carbonate samples showed the development of large voids, including holes and cavities of micrometer scale, but nanopores of various sizes were blocked. In contrast, lithic arkose was heterogeneously altered, losing a weight proportion of about 13% by dissolution of calcite cement. These micrometer-scale microfissures were developed, but those nanometer-scale pores just varied in a narrow range of sizes. The volume increase in all three reservoir types is mainly attributed to the dissolution of carbonate minerals. In deep reservoirs, in situ generated organic acids can enlarge existing cavities in carbonates and develop microfissures in sandstones. The microfissure porosity in sandstone is limited but can increase through other geological processes such as overpressure. More importantly, these acids can maintain the acidity of pore waters, inhibit the precipitation of dissolved minerals, and help to preserve reservoir porosity. Although temperature plays an insignificant role in laboratory simulations, it influences both the generation and destruction processes of organic acids in deep reservoirs on geologic time scales and, thus, warrants further attention. The results provide a basis for recognizing the typical patterns of organic acid dissolution on different reservoir rocks and further suggest the potential role of organic acids in the formation and preservation of secondary porosity in deeply buried reservoirs. [ABSTRACT FROM AUTHOR]

Modification of nanoscale zero-valent iron (nZVI) with reducing sulfur compounds has proven to improve the reactivity of nZVI towards recalcitrant halogenated organic contaminants. In this study, we develop a novel method for the preparation of sulfidated nZVI (S-nZVI) with S0 (a low cost and available reducing sulfur agent) dissolved in ethanol under mild conditions and apply it for the transformation of tetrabromobisphenol A (TBBPA), a potential persistent organic pollutant. Surface analysis shows that S0 dissolved in ethanol has been successfully doped into nZVI via a reaction with Fe0 to form a relatively homogeneous layer of FeS/FeS2 on the nZVI surface. The H2 production test and the electrochemical analysis show that the FeS/FeS2 layer not only slows the H2 evolution reaction but also enhances the electron transfer. Debromination kinetics indicate that the resulting S-nZVI with a S/Fe ratio of 0.015–0.05 possesses higher debromination activity for TBBPA and its debromination products (i.e., tri-BBPA, di-BBPA, mono-BBPA and BPA) in comparison with nZVI. Among them, S-nZVI at a S/Fe of 0.025 (S-nZVIS-0.025) has the greatest debromination rate constant (kobs) of 1.19 ± 0.071 h−1 for TBBPA. It debrominates TBBPA at a faster rate than other conventional S-nZVI made from Na2S and Na2S2O4 and has been successfully applied in the treatment of TBBPA-spiked environmental water samples (including river water, groundwater, and tap water). The results suggest that the modification of nZVI with S0 dissolved in ethanol is a simple, safe, inexpensive, and effective sulfidation technique, which can be applied for the large-scale production of S-nZVI for treating contaminated water. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are toxic compounds in the atmosphere and have adverse effects on public health, especially through the inhalation of particulate matter (PM). At present, there is limited understanding of the size distribution of particulate-bound PAHs and their health risks on a continental scale. In this study, we carried out a PM campaign from October 2012 to September 2013 at 12 sampling sites simultaneously, including urban, suburban and remote sites in different regions of China. Size-segregated PAHs and typical tracers of coal combustion (picene), biomass burning (levoglucosan) and vehicle exhaust (hopanes) were measured. The annual averages of the 24 total measured PAHs (∑24 PAHs) and benzo[a]pyrene (BaP) carcinogenic equivalent concentration (BaP eq) ranged from 7.56 to 205 ng/m 3 with a mean of 53.5 ng/m 3 and from 0.21 to 22.2 ng/m 3 with a mean of 5.02 ng/m 3 , respectively. At all the sites, ∑24 PAHs and BaP eq were dominant in the ultrafine particles with aerodynamic diameter < 1.1 µ m, followed by those in the size ranges of 1.1–3.3 µ m and > 3.3 µ m. Compared with southern China, northern China witnessed much higher ∑24 PAHs (87.36 vs. 17.56 ng/m 3) , BaP eq (8.48 vs. 1.34 ng/m 3) and PAHs' inhalation cancer risk (7.4 × 10 -4 vs. 1.2 × 10 -4). Nationwide increases in both PAH levels and inhalation cancer risk occurred in winter. The unfavorable meteorological conditions and enhanced emissions of coal combustion and biomass burning together led to severe PAHs' pollution and high cancer risk in the atmosphere of northern China, especially during winter. Coal combustion is the major source of BaP eq in all size particles at most sampling sites. Our results suggested that the reduction of coal and biofuel consumption in the residential sector could be crucial and effective in lowering PAH concentrations and their inhalation cancer risk in China. [ABSTRACT FROM AUTHOR]

The source of marine oils from the deep Tarim Basin is still in debate due to several alteration processes of source indicators. A series of trimethyl-alkylbenzenes has been detected in marine oils from this old, composite basin, besides the reported aryl isoprenoids with 2,3,6-trimethyl substitution (AIPs). They are characterized by regular gas chromatography elution pattern, which is similar to that of n-alkylbenzenes, and suggest a strong possibility of n-alkyl side chains. C15 trimethyl-n-alkylbenzenes were synthesized by Friedel–Crafts acylation of trimethylbenzene isomers to determine their structures. Based on the chromatography and mass spectra data and the coinjection of synthesized compounds, this series of compounds has been assigned as the 2,4,5-trimethyl-n-alkylbenzenes that coeluted with 2,3,5-trimethyl-n-alkylbenzenes, and other trimethyl-n-alkylbenzene isomers were also detected. This series of trimethyl-n-alkylbenzene (AAs) shows much higher relative abundances in light and waxy oils than in normal and heavy oils, which is opposite to the variation in relative abundances of aryl isoprenoids. The ratios of these trimethyl-n-alkylbenzenes to the aryl isoprenoids (AA/AIP ratio) generally show a good correlation with the maturity indicators for most of studied oils despite of some outliers (mainly condensates). The pyrolysis of asphaltenes has confirmed these trends. These results support an important control of thermal stress on the molecular compositions of marine oils from the deep Tarim Basin, besides other secondary alteration processes (such as oil mixing and migration fractionation, among others). These factors should be given a full consideration for the source determination of deep and ultradeep oils. [ABSTRACT FROM AUTHOR]

The composition, morphology, and mixing structure of individual cloud residues (RES) and interstitial particles (INT) at a mountaintop site were investigated. Eight types of particles were identified, including sulfate-rich (S-rich), S-organic matter (OM), aged soot, aged mineral dust, aged fly ash, aged metal, refractory, and aged refractory mixture. A shift of dominant particle types from S-rich (29 %) and aged soot (27 %) in the INT to aged refractory mixture (23 %) and S-OM (22 %) in the RES is observed. In particular, particles with organic shells are enriched in the RES (27 %) relative to the INT (12 %). Our results highlight that the formation of more oxidized organic matter in the cloud contributes to the existence of organic shells after cloud processing. The fractal dimension (Df), a morphologic parameter to represent the branching degree of particles, for soot particles in the RES (1.82 ± 0.12) is lower than that in the INT (2.11 ± 0.09), which indicates that in-cloud processes may result in less compact soot. This research emphasizes the role of in-cloud processes in the chemistry and microphysical properties of individual particles. Given that organic coatings may determine the particle hygroscopicity, activation ability, and heterogeneous chemical reactivity, the increase of OM-shelled particles upon in-cloud processes should have considerable implications. [ABSTRACT FROM AUTHOR]

Size and effective density (ρe) are important properties of aerosol particles and are related to their influences on human health and the global climate. The volume equivalent diameter (Dve) is an intrinsic property that is used to evaluate particle size. ρe, defined as the ratio of particle density to a dynamic shape factor (χ), is used to characterize the physical property of a particle as an alternative to particle density. However, it is still challenging to simultaneously characterize the Dve and ρe of particles. Here, we present a novel system that classifying particles with their aerodynamic diameter (Da) by aerodynamic aerosol classifiers (AAC) and determining their vacuum aerodynamic diameter (Dva) by single particle aerosol mass spectrometry (SPAMS) to achieve a measurement of Dve and ρe. The reliability of the AAC-SPAMS system for accurately obtaining Dve and ρe is verified based on the results that the deviation between the measured values and the theoretical values is less than 4 % for the size-resolved spherical polystyrene latex (PSL). The AAC-SPAMS system is applied to characterize the Dve and ρe of (NH4)2SO4 and NaNO3 particles, suggesting that these particles are aspherical and their ρe are independent of particle size. Finally, the AAC-SPAMS system is deployed in a field measurement, showing that it is a powerful technique to characterize the chemically-resolved Dve and ρe of particles in real time. [ABSTRACT FROM AUTHOR]

Geochemical studies of crude oil and source rock play an important role in future exploration in Zhanhua Depression. In this study, thirty-one oil samples collected from Shahejie Formation in Zhanhua Depression, Bohai Bay Basin, NE China have been geochemically analyzed and their organic geochemical characteristics have been applied to differentiate groups of oils. These oil samples can be classified into two families based on multiple biomarker proxies and stable carbon isotopic values. Family I is characterized by a low ratio of pristane over phytane (Pr/Ph < 0.7), a relatively high ratio of phytane over n-C18 (Ph/n-C18), varying ratios of gammacerane over C30 hopane (Ga/C30H) and C22/C21 tricyclic terpane, and a low ratio of C19/C23 tricyclic terpane. Family II is marked by a relatively high Pr/Ph ratio (0.7–1.6), relative low ratios of Ph/n-C18 and C22/C21 tricyclic terpane, and avarying ratio of C19/C23 tricyclic terpane. Both families I and II within these crude oils can be subdivided into two families based on different values of stable carbon isotopic composition of individual n-alkanes. Moreover, the potential source rocks of oil samples in Family I and Family II were likely derived from the upper Es4 member and Es3 member, respectively, based on the correlation of organic geochemical characteristics of the oils and source rocks. The results of oil–source rock correlation provide insight into the process from oil generation to migration and to final accumulation, providing a better understanding of factors controlling oil–gas distribution for prediction of sweet spots. [ABSTRACT FROM AUTHOR]

Photochemistry plays an important role in the evolution of atmospheric water-soluble organic carbon (WSOC), which dissolves into clouds, fogs, and aerosol liquid water. In this study, we tentatively examined the molecular composition and evolution of a WSOC mixture extracted from field-collected wheat straw burning aerosol (WSBA) samples upon photolysis, using direct infusion electrospray ionisation (ESI) coupled to high-resolution mass spectrometry (HRMS) and liquid chromatography (LC) coupled with HRMS. For comparison, two typical phenolic compounds (i.e. phenol and guaiacol) emitted from lignin pyrolysis in combination with hydrogen peroxide (H2O2) as a typical OH radical precursor were simultaneously exposed to simulated sunlight irradiation. Their photochemical products such as phenolic dimers (e.g. m/z 185.0608 for phenol dimer and m/z 245.0823 for guaiacol dimer) or their isomers, were also observed in field-collected WSBA samples, suggesting that the aqueous-phase reactions might contribute to the formation of emitted biomass burning aerosols. The aqueous photochemistry of both the phenols (photooxidation) and WSBA extracts (direct photolysis) could produce a series of highly oxygenated compounds, which in turn increases the oxidation degree of organic composition and acidity of the bulk solution. In particular, the LC/ESI-HRMS technique revealed significant photochemical evolution of the WSOC composition in WSBA samples, e.g. the photodegradation of low oxygenated species and the formation of highly oxygenated products. We also tentatively compared the mass spectra of photolytic time-profile WSBA extracts with each other for a more comprehensive description of the photolytic evolution. The calculated average oxygen-to-carbon ratio (O/C) of oxygenated compounds in bulk extract increases from 0.38±0.02 to 0.44±0.02 (mean ± standard deviation), while the intensity (S/N)-weighted average O/C (O/Cw) increases from 0.45±0.03 to 0.53±0.06 as the time of irradiation extends from 0 to 12 h. These findings indicate that the water-soluble organic fraction of combustion-derived aerosols has the potential to form more oxidised organic matter, contributing to the highly oxygenated nature of atmospheric organic aerosols. [ABSTRACT FROM AUTHOR]

Biomass burning (BB) emits large amounts of brown carbon (BrC); however, the evolutionary behavior of BrC in BB emissions (BB BrC) resulting from complex atmospheric processes is poorly understood. In this study, the transformation of contents and the chromophoric characteristics of BrC in smoke particles emitted by the burning of rice straw (RS), corn straw (CS), and pinewood (PW) under O3 aging are investigated. The O3 aging induced the reduction of light absorption and fluorescence for the BB BrC, suggesting the decomposition of chromophores and fluorophores. These changes were accompanied by a decrease in aromaticity, average molecular weight, and the light absorption capacity for the chromophores, as well as an increase in humification for the fluorophores. The excitation emission matrix combined with a parallel factor analysis revealed that protein-like components (C3) were predominantly decomposed by O3 aging, while the relative distribution of a humic-like component with highly oxygenated chromophores (C4) gradually increased. In general, the humic-like substances (C1 + C2 + C4) were transformed to be the most abundant fluorophores for all the BB BrC samples, which accounted for 84 %–87 % of the total fluorophores in final O3 -aged BB BrC. Two-dimensional correlation spectroscopy (2D-COS) was performed on the synchronous fluorescence, which suggested that the RS and CS BrC exhibits the same susceptible fluorophores changes upon O3 aging. It showed that O3 firstly reacted with protein-like fractions (263–289 nm) and then with fulvic-like fractions (333–340 nm). In comparison, the changing sequence of susceptible fluorophores in the PW BrC to O3 was in the order of fulvic-like fluorophores with shorter wavelengths (309 nm), protein-like fluorophores (276 nm), and fulvic-like fluorophores with longer wavelengths (358 nm). The 2D-FTIR-COS (2D-COS combined with FTIR) analysis showed conjugated C=O and aromatic C=C and C=O groups were the most susceptible functional groups to O3 aging for all BB BrC. Moreover, it also revealed a consistent sequential change, which is in the order of aromatic OH; conjugated C=O groups and aromatic C=O ; aromatic COO- ; and finally lignin-derived C–C, C–H, and C–O groups. Our results provide new insights into the evolutionary behavior of the chromophoric and fluorescent properties of BB BrC during O3 aging, which are of great significance for better understanding the heterogeneous oxidation pathways of BB-derived BrC in the atmospheric environment. [ABSTRACT FROM AUTHOR]

Isotopic rollover refers to that δ13C value of a gas component decreases with maturity. Its occurrence is closely related to high productivity of shale gas. Isothermal confined pyrolysis experiments (gold capsules) were performed to simulate this phenomenon on whole rock Lucaogou and kerogens Saergan, Wuerhe and Fengcheng in the absence (anhydrous) and presence of added water (hydrous) at 50 MPa, 372 °C and heating duration 0–672 h, corresponding to 0.96–1.85 EASY%Ro. For kerogen Saergan isolated from source rock with hydrogen index (HI) 159 mg/g TOC and 1.10–1.30% Ro equivalent, none of δ13C1, δ13C2 and δ13C3 showed any rollover in both anhydrous and hydrous experiments. For Lucaogou whole rock with HI 856 mg/g TOC and 0.50–0.60%Ro, both δ13C2 and δ13C3 showed rollover in anhydrous experiments while all δ13C1, δ13C2 and δ13C3 showed rollover with greater magnitude in hydrous experiments starting at 1.49–1.64 EASY%Ro. For kerogens Wuerhe and Fengcheng isolated from source rocks with HI of 550 and 741 mg/g TOC, and 1.18 and 0.96%Ro respectively, both δ13C2 and δ13C3 demonstrated rollover in anhydrous experiments while only δ13C2 showed rollover with minor magnitude in hydrous experiments starting at 1.47–1.53 EASY%Ro. The different effects of water on isotopic rollover among samples Lucaogou, Wuerhe and Fengcheng can be ascribed to rate related isotopic fractionation. Higher generation rate leads to minor isotopic fractionation and rollover magnitude. It was suggested that isotopic rollover likely occurs in a source rock having higher amount of initial retained oil prior to bulk oil cracking and currently within the major stage of oil-cracking to gas (1.50–2.00%Ro). [ABSTRACT FROM AUTHOR]

Arsenic decontamination from groundwater is an urgent but still challenging task. Polystyrene-based hydrated ferric oxide (denoted as D201-HFO) nanocomposite is a new emerging current adsorbent for efficient arsenate removal in natural waters; the resulting materials can interact with arsenate, mainly driven by inner complexation and static interaction and the existing HA effects on adsorption was well investigated. Results reveals that low concentrations of HA (below 25 mg/L) coexistence led to negligible effects on As(V) removal, but high levels of HA (100 mg/L) exerted outstanding sorption competition to As(V) removal; kinetics results revealed the HA additions brought about the diffusion prolonging and capacity decline, due to the large molecule structure of HA. Column experiments further showed the slight decrease application capacity of 810 BV by HA additions, with satisfactory saturation capacity; significantly, the presence of HA also exerted negligible influences on regeneration performances. All the sorbents with or without HA could be well regenerated by binary alkaline and salt mixture. [ABSTRACT FROM AUTHOR]

Type I and II kerogens, isolated from outcrop shales in the Songliao Basin, were performed a programed sealed-heating kinetic process. Both carbon isotope values of pyrolysis-residual kerogens and those of asphaltene extractions present gradual enrichments dependence on increasing Easy %Ro and biomarker maturity ratios. The carbon isotope (δ13C) values are used for the first time to analyze a close relationship between these kerogens and asphaltenes at the same level of thermal maturation, and identification oil–source rock correlation studies in theory. Such validity of the model was further tested by δ13C of asphaltenes and biomarker ratios in crude oils. [ABSTRACT FROM AUTHOR]

Brown carbon (BrC) plays an essential impact on radiative forcing due to its ability to absorb sunlight. In this study, the optical properties and molecular characteristics of water-soluble and methanol-soluble organic carbon (OC; MSOC) emitted from the simulated combustion of biomass and coal fuels and vehicle emissions were investigated using ultraviolet–visible (UV–vis) spectroscopy, excitation–emission matrix (EEM) spectroscopy, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with electrospray ionization (ESI). The results showed that these smoke aerosol samples from biomass burning (BB) and coal combustion (CC) had a higher mass absorption efficiency at 365 nm (MAE 365) than vehicle emission samples. A stronger MAE 365 value was also found in MSOC than water-soluble organic carbon (WSOC), indicating low polar compounds would possess a higher light absorption capacity. Parallel factor (PARAFAC) analysis identified six types of fluorophores (P1–6) in WSOC including two humic-like substances (HULIS-1) (P1 and P6), three protein-like substances (PLOM) (P2, P3, and P5), and one undefined substance (P4). HULIS-1 was mainly from aging vehicle exhaust particles; P2 was only abundant in BB aerosols; P3 was ubiquitous in all tested aerosols; P4 was abundant in fossil burning aerosols; and P5 was more intense in fresh vehicle exhaust particles. The MSOC chromophores (six components; C1–6) exhibited consistent characteristics with WSOC, suggesting the method could be used to indicate the origins of chromophores. FT-ICR mass spectra showed that CHO and CHON were the most abundant components of WSOC, but S-containing compounds appeared in a higher abundance in CC aerosols and vehicle emissions than BB aerosols, while considerably fewer S-containing compounds largely with CHO and CHON were detected in MSOC. The unique formulas of different sources in the van Krevelen (VK) diagram presented different molecular distributions. To be specific, BB aerosols with largely CHO and CHON had a medium H/C and low O/C ratio, while CC aerosols and vehicle emissions largely with S-containing compounds had an opposite H/C and O/C ratio. Moreover, the light absorption capacity of WSOC and MSOC was positively associated with the unsaturation degree and molecular weight in the source aerosols. The above results are potentially applicable to further studies on the EEM-based or molecular-characteristic-based source apportionment of chromophores in atmospheric aerosols. [ABSTRACT FROM AUTHOR]

Rationale: Compound‐specific stable isotope analysis (CSIA) is a powerful tool for the source apportionment and characterization of environmental transformation processes, especially for new emerging contaminants. In this study, we have developed an effective method for determination of the stable carbon isotope ratios of hexabromocyclododecane diastereoisomers. Methods: Three diastereoisomers of hexabromocyclododecane (HBCD), α‐, β‐, and γ‐HBCD, were separated on a preparative high‐performance liquid chromatography (HPLC) system. Their carbon isotope ratios were determined using gas chromatography/isotope ratio mass spectrometry (GC/IRMS), and compared with data obtained by elemental analyzer/isotope ratio mass spectrometry (EA/IRMS). Results: α‐, β‐, and γ‐HBCD were well separated by the preparative HPLC system. Method validation results indicated excellent precision and reproducibility. For a series of injection volumes (0.5 to 3 μL), the average carbon isotope ratios for α‐HBCD, β‐HBCD, and γ‐HBCD were −26.42‰, −26.88‰, and −26.43‰, respectively, and their deviations from those of the HBCD standard (−26.52‰) were all lower than the analytical uncertainty of 0.5‰. Relative standard deviations of intra‐day and inter‐day injections of HBCD were in the ranges 0.35–0.64% and 0.37–0.76%, respectively. Comparison with EA/IRMS further verified the accuracy of the HBCD stable carbon isotope ratio measured by GC/IRMS. Conclusions: This work offers a novel approach to separate and concentrate the three major isomers of HBCD and to determine their stable carbon isotope ratios. This permits analysis of their carbon isotope ratios in environmental samples in order to elucidate the sources and abiotic or biological transformation processes of HBCD in the environment. [ABSTRACT FROM AUTHOR]

The effects of the chemical composition and size of sea-salt-containing particles on their cloud condensation nuclei (CCN) activity are incompletely understood. We used a ground-based counterflow virtual impactor (GCVI) coupled with a single-particle aerosol mass spectrometer (SPAMS) to characterize chemical composition of submicron (dry diameter of 0.2–1.0 µm) and supermicron (1.0–2.0 µm) sea-salt-containing cloud residues (dried cloud droplets) at Mount Nanling, southern China. Seven cut sizes (7.5–14 µm) of cloud droplets were set in the GCVI system. The highest number fraction of sea-salt-containing particles was observed at the cut size of 7.5 µm (26 %, by number), followed by 14 µm (17 %) and the other cut sizes (3 %–5 %). The submicron sea-salt-containing cloud residues contributed approximately 20 % (by number) at the cut size of 7.5 µm , which was significantly higher than the percentages at the cut sizes of 8–14 µm (below 2 %). This difference was likely involved in the change in the chemical composition. At the cut size of 7.5 µm , nitrate was internally mixed with over 90 % of the submicron sea-salt-containing cloud residues, which was higher than sulfate (20 %), ammonium (below 1 %), amines (6 %), hydrocarbon organic species (2 %), and organic acids (4 %). However, at the cut sizes of 8–14 µm , nitrate, sulfate, ammonium, amines, hydrocarbon organic species, and organic acids were internally mixed with > 90 %, > 80 %, 39 %–84 %, 71 %–86 %, 52 %–90 %, and 32 %–77 % of the submicron sea-salt-containing cloud residues. The proportion of sea-salt-containing particles in the supermicron cloud residues generally increased as a function of cut size, and their CCN activity was less influenced by chemical composition. This study provided a significant contribution towards a comprehensive understanding of sea-salt CCN activity. [ABSTRACT FROM AUTHOR]

The discipline of "Bio-Organic Geochemistry" is a cross research field between biogeochemistry and traditional organic geochemistry, which focuses on geochemical processes related to the biosynthesis of organic molecules (particularly lipids) by (micro) organisms, organic matter production by primary producers, degradation of organic matter by microbial processes recorded by retainable lipid biomarkers, and organic proxies for studies of paleo-climate, paleo-environments, paleoecology and Earth evolution. This field aims to go beyond the traditional petroleum-oriented Organic Geochemistry by integrating with biogeochemical concepts concerned mostly with biomolecules from cellular material such as DNA and lipids. A formal Chinese organization in Bio-Organic Geochemistry was established in 2012 when the first conference was held in Guangzhou. This organization has witnessed rapid growth over the past six years with focused research addressing organic proxies in paleoclimate and paleoenvironmental applications, with particular rapid development in glycerol dialkyl glycerol tetraethers-derived proxies. Most progresses in China so far are made following or paralleling the international trend in biogeochemical studies. Things have begun to change with China's ambitious initiatives in several bio-geo programs such as the Ocean Deep Drilling Program of China, the Microbial Hydrosphere Program, the Deep Carbon Observatory, and the Microbiome Program. Looking forward in the 21st Century, the growing Chinese research community in Bio-Organic Geochemistry faces grand opportunities and challenges as Chinese scientists propel themselves toward global research frontiers. [ABSTRACT FROM AUTHOR]

Reliable quantifications of brominated flame retardants (BFRs) not only ensure compliance with laws and regulations on the use of BFRs in commercial products, but also is key for accurate risk assessments of BFRs. Acetone is a common solvent widely used in the analytical procedure of BFRs, but our recent study found that acetone can react with some BFRs. It is highly likely that such reactions can negatively affect the quantifications of BFRs in environmental samples. In this study, the effects of acetone on the extraction yields of three representative BFRs [i.e., decabrominated diphenyl ether (decaBDE), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA)] were evaluated in the Soxhlet extraction (SE) system. The results showed that acetone-based SE procedure had no measureable effect for the recovery efficiencies of decaBDE but could substantially lower the extraction yields for both TBBPA and HBCD. After 24 h of extraction, the recovery efficiencies of TBBPA and HBCD by SE were 93 and 78% with acetone, 47 and 70% with 3:1 acetone:n-hexane, and 82 and 94% with 1:1 acetone:n-hexane, respectively. After 72 h of extraction, the extraction efficiencies of TBBPA and HBCD decreased to 68 and 55% with acetone, 0 and 5% with 3:1 acetone/n-hexane mixtures, and 0 and 13% with 1:1 acetone/n-hexane mixtures, respectively. The study suggested that the use of acetone alone or acetone-based mixtures should be restricted in the quantitative analysis of HBCD and TBBPA. We further evaluated nine alternative solvents for the extraction of the three BFRs. The result showed that diethyl ether might be reactive with HBCD and may not be considered as the alternative to acetone used solvents for the extraction of HBCD. [ABSTRACT FROM AUTHOR]

Organic carbon (OC) burial in nondeltaic continental shelves is an important part of the global carbon cycle. Of these, the Taiwan Strait (TWS) is a typical, nondeltaic shelf region that is influenced by a variety of factors including strong ocean currents, coastal upwelling, and small river inputs. To better understand how these factors influence OC burial in the TWS, we measured total organic carbon and total nitrogen contents as well as the stable carbon isotopes of sedimentary organic matter (δ13Corg) from the TWS. We also measured glycerol dialkyl glycerol tetraethers in surface sediments collected from the TWS. The concentrations of sedimentary total organic carbon and total nitrogen along the coast were high but decreased in areas more central to the TWS. This gradient was controlled by both hydrological conditions and coastal upwelling. The calculated accumulation rate of organic carbon ranged from 1.9 to 47.2 g C/m2/year and was comparable to other areas of the Chinese marginal seas. The source contribution calculated from the three‐end‐member model revealed that mostly marine OC was buried in the upwelling regions. In comparison, OC derived from terrestrial plant and soil was buried in the estuaries. Collectively, these results showed that the TWS may serve as a CO2 sink in the global carbon cycle. This is due to the preservation of the labile portions of the OC derived from plant and marine source, which formed the main component of the buried OC in the TWS. Plain Language Summary: Organic carbon (OC) burial in nondeltaic continental shelves is an important part of the global carbon cycle. Of these, the Taiwan Strait is a typical, nondeltaic shelf region that is influenced by a variety of factors including strong ocean currents, coastal upwelling, and small river inputs. This study addressed what control the distribution of OC and where different sources of OC (e.g., soil, plant, and marine) are buried. We demonstrated that the distribution of burial of OC was controlled by both hydrological conditions and coastal upwelling. Also, since the easily degradable marine OC formed the main component of the buried OC, we revealed that the Taiwan Strait may serve as a CO2 sink in the global carbon cycle. Key Points: A multiproxy analysis of sedimentary OC in the Taiwan Strait was discussedHydrological conditions controlled OC spatial distribution in the Taiwan StraitThe Taiwan Strait may serve as a CO2 sink in the global carbon cycle [ABSTRACT FROM AUTHOR]

For assessing the density and viscosity of tight oil and their geochemical controls, 47 tight oil samples across the Ordos Basin were analyzed. The oil density and viscosity lay in the ranges of 0.81-0.88 g/ml and 1.9-13.36 mPa·s, which are low in overall. The average saturated hydrocarbon content is higher than 80%. The molecular compositions suggest a source dominated organic matter by lacustrine type I/II with minor input of terrestrial type III kerogen. The oils were mainly generated at relatively high maturities. Fractionation during the oil expulsion may also result in the depletion of heavy-ends compounds. These are the main controlling factors for the overall good quality of the Ordos tight oil. [ABSTRACT FROM AUTHOR]

Hexabromocyclododecane (HBCD) stereoisomers may exhibit substantial differences in physicochemical, biological, and toxicological properties. However, there remains a lack of knowledge about stereoisomer-specific toxicity, metabolism, and environmental fate of HBCD. In this study, the biotransformation of (±)α-, (±)β-, and (±)γ-HBCD contained in technical HBCD by a mixed culture containing the organohalide-respiring bacterium Dehalococcoides mccartyi strain 195 was investigated. Results showed that the mixed culture was able to efficiently biotransform the technical HBCD mixture, with 75% of the initial HBCD (∼12 μM) in the growth medium being removed within 42 days. Based on the metabolites analysis, HBCD might be sequentially debrominated via dibromo elimination reaction to form tetrabromocyclododecene, dibromocyclododecadiene, and 1,5,9-cyclododecatriene. The biotransformation of the technical HBCD was likely diastereoisomer-specific. The transformation rates of α-, β-, and γ-HBCD were in the following order: α-HBCD > β-HBCD > γ-HBCD. The enantiomer fractions of (±)α-, (±)β-, and (±)γ-HBCD were maintained at about 0.5 during the 28 days of incubation, indicating a lack of enantioselective biotransformation of these diastereoisomers. Additionally, the amendment of another halogenated substrate tetrachloroethene (PCE), which supports the growth of strain 195, had a negligible impact on the transformation patterns of HBCD diastereoisomers and enantiomers. This study provided new insights into the stereoisomer-specific transformation patterns of HBCD by anaerobic microbes and has important implications for microbial remediation of anoxic environments contaminated by HBCD using the mixed culture containing Dehalococcoides. [ABSTRACT FROM AUTHOR]

Four samples from a Permian reservoir in the Ordos Basin of North China were separated into twelve fractions in grain sizes of <0.5, 0.5-1 and 1-2 μm. Using the 40Ar-39Ar step-heating method, all of the fractions essentially yielded plateau ages ranging from 172.5 to 217.1 Ma. These scattered plateau ages might not have been obtained from pure diagenetic illites but from mixed clay minerals, although the samples were disaggregated using a gentle freeze-thaw cycle to free them of non-clay minerals. A regional thermal event, as suggested by several proxies, led to intensive illitization as a distinct diagenetic process when the Yanshanian Movement triggered magmatism around the entire North China Block during the Jurassic to Cretaceous. Thermal illites formed during a short time period, whereas detrital illites came from various sources. The scattered plateau ages could have resulted from mixed degassing of thermal and detrital illites. Within one sample, the plateau ages decrease with the diminution of grain sizes, but it is difficult to extrapolate to the detrital-illite-free ages. Because the plateau age is a mixture of ages for thermal and detrital illites, this regression analysis studies the dependence of the plateau ages on the synthetic values of contents and ages of detrital illites instead of on the grain sizes. Comparing the samples to one another, the plateau ages show the same trend among the different grain sizes. Weighted by the contents and ages of detrital illites, linear regression analysis revealed the relationship between the plateau ages and the relative weight proportions. Based on iterated calculations, a thermal event age and a set of weight proportions were derived. The regressed thermal event age is 163.3±1.6 Ma, which coincides with regional thermal activities and links to gas accumulation. [ABSTRACT FROM AUTHOR]

Two biomarkers, 5,9-dimethyl-6-isopropyl-2-decanone ( 1) and 4,9,11-trimethyl-6-isopropyl-2-dodecanone ( 2), were isolated from Chinese Maoming oil shale by silica gel column chromatography and preparative gas chromatography. Their structures were elucidated by using spectroscopic techniques. [ABSTRACT FROM AUTHOR]

RATIONALE: Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. METHODS: One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ13 C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. RESULTS: The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. CONCLUSIONS: This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oi-source' correlations. [ABSTRACT FROM AUTHOR]

This study investigated polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo- p-dioxins/furans (PBDD/Fs), and dechlorane plus (DP) in air around three concentrated vehicle parking areas (underground, indoor, and outdoor) in a metropolitan of South China. The parking areas showed higher concentrations of PBDEs, PBDD/Fs, and DP than their adjacent urban area or distinct congener/isomer profiles, which indicate their local emission sources. The highest PBDE and DP concentrations were found in the outdoor parking lot, which might be related to the heating effect of direct sunlight exposure. Multi-linear regression analysis results suggest that deca-BDEs without noticeable transformation contributed most to airborne PBDEs in all studied areas, followed by penta-BDEs. The statistically lower anti-DP fractions in the urban area than that of commercial product signified its degradation/transformation during transportation. Neither PBDEs nor vehicle exhaust contributed much to airborne PBDD/Fs in the parking areas. There were 68.1-100 % of PBDEs, PBDD/Fs, and DP associated with particles. Logarithms of gas-particle distribution coefficients ( Ks) of PBDEs were significantly linear-correlated with those of their sub-cooled vapor pressures ( ps) and octanol-air partition coefficients ( Ks) in all studied areas. The daily inhalation doses of PBDEs, DP, and PBDD/Fs were individually estimated as 89.7-10,741, 2.05-39.4, and 0.12-4.17 pg kg day for employees in the parking areas via Monte Carlo simulation. [ABSTRACT FROM AUTHOR]