Sheng Guoying

Polycyclic aromatic hydrocarbons in sediments from the Pearl river and estuary, China : spatial and temporal distribution and sources

Abstract Polycyclic aromatic hydrocarbons (PAHs) were measured in surface sediments and dated core sediments from the Pearl river and estuary, China, to investigate the spatial and temporal variability of anthropogenic pollutants. The sediments from the sampling stations at the Guangzhou channel have the highest concentrations of PAHs, owing to contributions from the large amount of urban/industrial discharges from the city of Guangzhou. The significant decrease of PAHs concentrations in sediments from the Shiziyang channel is mainly attributed to the increasing degradation and desorption of low molecular weight PAHs and alkyl PAHs, and the dilution by less contaminated water and particles from the East river. The PAH contaminants were concentrated on the western side in the Lingding bay of the Pearl river estuary because of the hydrodynamic and sedimentation conditions. Based on the characteristics of the parent compound distributions (PCDs) and the alkyl homologue distributions (AHDs) of PAHs, the potential source of PAHs in sediments from each sampling station was identified. Results indicated that the pyrogenic (combustion) source, characterized by the abundance of parent PAHs, were predominant in the heavily contaminated station (ZB01) near the aging industrial area, and the petrogenic (petroleum- derived) PAHs were more abundant in the stations (ZB02, ZB03) adjacent to the petrochemical plant and shipping harbor. Sediments from Lingding bay show variable distributions of PAH composition and variety in the proportion of combustion and petrogenic sources for the PAHs in different stations. Perylene, a naturally derived PAH, was found to be highly abundant in less contaminated stations. Analysis of the dated sediments (210Pb) indicates that higher PAH concentrations occurred in the sediments deposited after 1980, and higher fluxes of PAHs discharged to the Pearl river are found after 1990.

Synthesis, characterization and photocatalytic property of nano-sized Zn2SnO4

Nano-sized Zn2SnO4 materials have been synthesized using the coprecipitation method. The synthetic conditions and the calcination behaviors of nano-sized Zn2SnO4 materials have been studied. The nano-sized Zn2SnO4 materials have been characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetry and differential thermal analysis (TG-DTA) and specific surface area. As a result, the kinetic grain growth equation for nano-sized Zn2SnO4 can be expressed as D4.78 = 9.12 × 1023t exp(−40.6 × 103/T), with an activation energy for grain growth of Q = 337.9 KJ/mol. The nano-sized Zn2SnO4 materials have been used as photocatalysts to decompose benzene in water solution. The results show that Zn2SnO4 can photocatalytically decompose benzene, and the photocatalytic capacity for Zn2SnO4 relates to the grain size, which is discussed in terms of the surface effect and the quantum size effect.

Biodegradability of di(2-ethylhexyl) phthalate by Pseudomonas fluorescens FS1

Di(2-ethylhexyl)phthalate (DEHP), one of high-molecular weightphthalate esters (PAEs), is used in the manufacturing of polyvinylchloride (PVC) resins, polyvinyl acetate, cellulosics,and polyurethanes, and contributes to environmental pollution. In this article, the characteristics of DEHP biodegradation by aneffective degradation bacterium, Pseudomonasfluorescens FS1 that isolated from the activated sludge at a petrochemicalfactory, was capable of using phthalate esters as the sole carbonand energy source, were investigated. Experimental results showedthat the biodegradation of DEHP by P. fluorescens FS1 could be described by the first-order reaction model, whichcould be expressed as: lnC = –0.0688t + A, and the half-life ofDEHP biodegradation was 10.07 d when the initial concentrations of DEHP were less than 50 mg L-1. The inhibition effects ofDEHP as a substrate had become predominant above the concentration of 50 mg L-1. The PAEs-degrading enzyme of P. fluorescens FS1, mainly located in the soluble part andthe particle of cytoplasm, was an intracellular enzyme. The metabolites of DEHP degradation by P. fluorescens FS1, which monoester, phthalic acid, benzonic acid, phenol, wereextracted using dichloromethane at different time intervals and identified by the GC-MS. The tentative pathway proposed for degradation of DEHP by P. fluorescens FS1 under aerobic condition is monoester in the beginning, further enzymatic degradation of the monoester produces phthalic acid, benzonic acid, phenol and finally CO2 and H2O.

Organochlorinated Compounds in Waters of the Pearl River Delta Region

Samples of river water and sewage water were analysed for ten PCB congeners, chlorobenzenes and chlorinated pesticides (BHCs and DDT) in three cities (Guangzhou, Shenzhen and Zhaoqing) in the Pearl River Delta, The results showed that the sewage water in Shengzhen had the highest concentration of total PCBs at about 10ng/L, and Dasha River (Shengzhen), the lowest at about 1.0ng/L. In general, the sewage waters in the three cities had higher concentrations of PCBs than river waters. Chlorobenzenes were investigated in the water samples. The total concentrations of chlorobenzenes ranged from 0.02~0.13μg/L, the Dasha River had the highest level of chlorobenzenes, and the sewage water in the city of Zhaoqing had the next highest. The result may be related to the discharges from paper production factories nearby the sampling sections of the Dasha River (Shenzhen) and sewage water in Zhaoqing. The concentrations of organochlorinated pesticides (α-BHC, λ-BHC, β-BHC, DDT and DDE) changed little in all water samples except for the sewage water in Guangzhou. It seemed that these pesticides are more a residual signal than a direct discharge from point sources.

Retene in pyrolysates of algal and bacterial organic matter

Abstract Retene, dehydroabietin, and 1,2,3,4-tetrahydroretene have been identified by GC–MS in extractable aromatic hydrocarbon fractions produced by pyrolysis at 200 and 300°C of pure strains of the green alga Chlorella protothecoides and the cyanobacterium Synechocystis sp. The results suggest phytoplankton as a possible source of retene in Recent and ancient sediments.

Geology and geochemistry of bitumen vein deposits at Ghost City, Junggar Basin, northwest China

Veins of solid bitumen occur in Cretaceous sandstones at the northwest margin of the Junggar Basin, China. The bitumen has a low aromaticity and a composition comparable to gilsonite. The bitumen contains abundant steranes and terpanes, and /S-carotane, although most n- and i- alkanes have been removed, which is characteristic of the local crude oil. The sterane and triterpane maturity parameters show that the bitumen, local crude oil, and source rocks are all mature. Bitumen-wallrock relationships suggest that the host sandstone was not completely consolidated at the time of emplacement of the bitumen veins, although bitumen emplacement was a relatively late diagenetic event. The burial history for the northwest Junggar Basin shows that hydrocarbon generation from the assumed upper Permian source rocks commenced in late Triassic/early Jurassic times and suggests that rapid hydrocarbon generation may have resulted in overpressure contributing to the bitumen emplacement.

Characterization of organic matter in total suspended particles by thermodesorption and pyrolysis-gas chromatography-mass spectrometry

The organic matter in tropospheric aerosol plays an important role in atmospheric physical and chemical processes. The bulk of organic matter, representing a significant proportion of the total suspended particulate (TSP) mass, is bound to polymeric material whose structure and properties are largely unknown. Here we used thermodesorption gas chromatography/mass spectrometry (Td-GC/MS) to study organic compounds of low molecular mass and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) to characterize the chemical structure of macromolecules in TSP samples collected in different seasons from different sites in Guangzhou. n-Alkanes, fatty acids and nitriles were the predominant compounds in the thermodesorption products, whereas aromatics, fatty acids, nitriles and n-alkanes/alkenes were the major compounds in the pyrolysates. The results indicated that aromatics were main units in macromolecules. The fatty acids and nitriles formed from carboxylic ammonium salts were detected in both thermodesorption products and pyrolysates at a certain concentration, indicating the importance of these compounds in TSP formation. The TSP source mainly determined the occurrence of compounds in samples from urban, suburban and forest sites, whereas the TSP source and formation process maybe controlled the seasonal variation in compounds detected. High levels of nitriles in summer samples from suburban and forest sites coincide with the release of ammonium from the land and of fatty acids from vegetation at these sites.

Establishment and Application of the Co-analysis Method of PBDD/Fs and PCDD/Fs with Isotope Dilution High Resolution Gas Chromatography-High Resolution Mass Spectrometry in Ambient Air Samples

Abstract It has been known that the polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) share similar or even higher toxicity and bio-accumulativity with polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs). In this study, the co-analysis method of PBDD/Fs and PCDD/Fs with isotope dilution HRGC-HRMS was built based on the U.S. EPA Method 1613 and TO-9A. The samples were extracted and cleaned through acid silica gel bed, multi-layer silica gel column, and Florisil column, respectively. Eight 2,3,7,8-PBDD/Fs congeners and 17 congeners of 2,3,7,8-PCDD/Fs were quantified. The HRGC-HRMS conditions for PBDD/Fs were: EI+ and SIM model with resolution ≥ 10000, electron emission energy of 50 eV, and filament current of 0.75 mA; DB-5 MS fused silica capillary column (30 m × 0.25 mm i.d., 0.1 μm) was used and the temperatures for injection, ion source, and transfer line were 250 °C, 250 °C, and 305 °C, respectively. The carrier gas was helium (1.0 ml min−1). The results showed that the relative standard deviations (RSDs) of parallel blank samples were ≤ 10.3% and the recoveries of PBDD/Fs and PCDD/Fs were in the range of 73%–112%. The average quantified values of the standard reference sample were in accordance with the certified values and the RSDs were ≤ 12.0%. The method detection limits were 0.25–1.5 pg μl−1 for PBDD/Fs and 1.5–5 pg μl−1 for PCDD/Fs. The concentrations of PBDD/Fs and PCDD/Fs were 1.01–2.43 pg per m3 and 6.19–10.8 pg per m3 for particulate samples, and 0.036–0.801 pg per m3 and 1.37–12.1 pg per m3 for gaseous samples of certain area, respectively. Compared with other areas in the world, the atmospheric dioxins pollution of the sampling area was at high level.

Molecular characterization of sulfur compounds in some specieal sulfur-rich Chinese crude oils by FT-ICR MS

Routine GC/MS analysis may apply to the volatilized Low-Molecular-Weight compounds in saturate and aromatic hydrocarbon fractions; thus, relative studies using this technique inevitably bring about some limitations on distribution of miscellaneous sulfur atom. In this article, Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with high resolution is employed to investigate the distribution of organic sulfur compounds (OSCs) in the crude oil typically derived from the Eogene carbonate-evaporite sediments with further chemical compositional characterization in molecular level by miscellaneous atomic type, carbon number, and double bond equivalent (DBE). A variety of miscellaneous atomic types with S1, S2, S3, OS, OS2, O2S, O2S2, NS, and NOS etc. (S1 means those OSCs with one sulfur atom in a molecule) were identified in OSCs in these oil samples. High levels of alkyl thioether series compounds with one ring structure were presented mainly in the crude oil in the Jianghan Basin whereas high amounts of benzothiophene, dibenzothiophene etc. compounds with higher values in DBE and carbon number range occurred in the sulfur-rich heavy oil in the Jinxian Sag. Although carbonate-evaporite sediments deposited in the saline lacustrine facies in the Eogene basin both occurred in the Jinxian Sag and Jianghan Basin, obviously, they possess different chemical diagenetic pathway of sulfur under various microbial reactions, leading to diverse distributional characteristics on biomarkers, OSCs, and even different hydrocarbon generation mechanism of immature crude oil.

Identification and formation of sulfur-containing steroids in sulfur-rich heavy oils in the Jinxian Sag, Bohai Bay Basin, North China

High abundant sulfur-containing steroids were identified and detected in saturate hydrocarbon fractions of heavy oil with a high sulfur content in the Jinxian Sag, Bohai Bay Basin, North China. These sulfur-containing steroids were structurally merged into the D-ring of steroid nucleus with thiophene ring and/or combined into the C-22 in the side-chain. Based on the previous reports of sulfur-containing steroids with methylthio-teroids and intra-molecular form, four formation mechanisms of sulfur-containing steroids and diagenetic pathway of steroids under S-rich conditions were proposed in this paper according to the double bond positions in the sterene compounds. Hydrogenation and sulfurization both occurred in the diagenetic processes of olefinic bond in the side-chain of steroids: abiogenic chemical hydrogenation of H2S and HS− leads to the formation of regular steranes; a successful sulfurization process leads to the formation of the side-chain sulfur-containing steroids whereas unsuccessful cyclization and/or sulfurization result in the generation of short-chain steranes. This kind of mechanism of hydrogenation/sulfurization of side-chain olefinic bond provides a potential genesis clue for the occurrence of high abundance of short-chain steranes (higher than the common regular steroids, phytane and n-alkanes) in S-rich heavy oils and source rocks in the Jinxian Sag, Bohai Bay Basin, North China.