Organic geochemistry of water and bottom sediments during a seasonal flood in 2006 in the North Dvina River estuary

Heavy contaminant load released into the Northern Dvina River during flooding increased the concentrations of aliphatic (AHC) and polcyclic aromatic (PAH) hydrocarbons in water and bottom sediments. The composition of hydrocarbons was different from that of the summer low flow season. The concentrations of dissolved and particulate AHC ranged from 12 to 106 and from 192 to 599 µg/l, respectively, and bottom sediments contained from 26.2 to 329 µg/g AHC and 4 to 1785 ng/g PAH. As the transformation of AHC occurred at low spring temperatures, the alkane composition was shown to be dominated by terrigenous compounds, whereas more stable PAH showed elevated contents of petrogenic and pyrogenic compounds. It was also shown that the Northern Dvina-Dvina Bay geochemical barrier prevents contaminant input into the White Sea, i.e., acts as a marginal filter.

Sources and distribution of aliphatic and polyaromatic hydrocarbons in sediments of Jiaozhou Bay, Qingdao, China

The composition and distribution of aliphatic (n-alkanes) and polyaromatic hydrocarbons (PAHs) were measured for the surface sediments collected at 25 sites from Jiaozhou Bay, Qingdao, China. Total n-alkanes and PAH concentrations ranged from 0.5 to 8.2 mu g/gdw and 0.02 to 2.2 mu g/gdw, respectively, and the distribution of both n-alkanes and PAHs showed large spatial variations in the bay. The distribution of PAHs in the sediments was predominated by the three or more ring compounds. High hydrocarbon levels were generally found in the areas associated with high anthropogenic impact and port activities in the bay. The calculated hydrocarbon indexes suggest that petroleum contamination was the main source of n-alkanes, while both pyrolytic and petrogenic sources contributed PAHs to the surface sediments of Jiaozhou Bay. In comparison to other polluted coastal sediments, the level of contamination from both aliphatic hydrocarbons and PAHs in Jiaozhou Bay sediments is relatively low at the present time. (c) 2005 Elsevier Ltd. All rights reserved.

Phase and partitioning behavior of phenols and polycyclic aromatic hydrocarbons in offshore oil and gas produced water

Produced water constitutes the largest volume of waste from offshore oil and gas operations and is composed of a wide range of organic and inorganic compounds. Although treatment processes have to meet strict oil in water regulations, the definition of “oil” is a function of the analysis process and may include aliphatic hydrocarbons which have limited environmental impact due to degradability whilst ignoring problematic dissolved petroleum species. This thesis presents the partitioning behavior of oil in produced water as a function of temperature and salinity to identify compounds of environmental concern. Phenol, p-cresol, and 4-tert-butylphenol were studied because of their xenoestrogenic power; other compounds studied are polycyclic aromatic hydrocarbon PAHs which include naphthalene, fluorene, phenanthrene, and pyrene. Partitioning experiments were carried out in an Innova incubator for 48 hours, temperature was varied from 4ﾟC to 70ﾟC, and two salinity levels of 46.8‰ and 66.8‰ were studied. Results obtained showed that the dispersed oil concentration in the water reduces with settling time and equilibrium was attained at 48 h settling time. Polycyclic aromatic hydrocarbons (PAHs) partitions based on dispersed oil concentration whereas phenols are not significantly affected by dispersed oil concentration. Higher temperature favors partitioning of PAHs into the water phase. Salinity has negligible effect on partitioning pattern of phenols and PAHs studied. Simulation results obtained from the Aspen HYSYS model shows that temperature and oil droplet distribution greatly influences the efficiency of produced water treatment system.

Characterization of complex hydrocarbons in cigarette smoke condensate by gas chromatography-mass spectrometry and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry

Gas chromatography-mass spectrometry with electron ionization and positive-ion chemical ionization and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC x GC-TOF-MS) were applied for the characterization of the chemical composition of complex hydrocarbons in the non-polar neutral fraction of cigarette smoke condensates. Automated data processing by TOF-MS software combined with structured chromatograms and manual review of library hits were used to assign the components from GC x GC-TOF-MS analysis. The distributions of aliphatic hydrocarbons and aromatics were also investigated. Over 100 isoprenoid hydrocarbons were detected, including carotene degradation products, phytadiene isomers and carbocyclic diterpenoids. A total of 1800 hydrocarbons were tentatively identified, including aliphatic hydrocarbons, aromatics, and isoprenoid hydrocarbons. The identified hydrocarbons by GC x GC-TOF-MS were far more than those by GC-MS. (C) 2004 Elsevier B.V. All rights reserved.

Accumulation of petroleum hydrocarbons and heavy metals in clams (Ruditapes philippinarum) in Jiaozhou Bay, China

Accumulation and distributions of aliphatic and polyaromatic hydrocarbons (PAHs) and heavy metals were measured in tissues of the clam Ruditapes philippinarum collected from 5 sites in Jiaozhou Bay, Qingdao, China. The concentrations of total aliphatic hydrocarbon and PAHs ranged from 570 to 2 574 ng/gdw (gram dry weight) and from 276 to 939 ng/gdw, in the most and least polluted sites, respectively. The bio-accumulation of hydrocarbons and PAHs in the clams appeared to be selective. Aliphatic hydrocarbons were predominantly represented by short chain (< nC(23)) n-alkanes, suggesting that petroleum hydrocarbons were likely the major contamination source. The selective uptake of 3 and 4 ring PAHs, such as naphthalene, fluorene, phenanthrene, fluoranthene and pyrene, by the clams was probably related to the physiological and bio-kinetic processes that were energetically favorable for uptake of compounds with fewer rings. Accumulation of the metals Cd, Cu, Zn, Pb, Cr, Hg, and As in the clam tissues also showed high variability, ranging from 0.043 to 87 A mu g/gdw. Among the 7 detected metals, Zn, Cd, Cu, and As had a particularly high potential of accumulation in R. philippinarum. In general, a positive correlation was found between the tissue concentrations and sediment concentrations of hydrocarbons and of some metals. Our study suggests that moderate contamination with polyaromatic hydrocarbons, and low to moderate contamination with metals, currently exists for clam R. philippinarum in Jiaozhou Bay, in comparison with other regional studies. A long-term monitoring program is certainly needed for assessment of the potential ecological influence and toxicity of these contaminants of R. philippinarum in Jiaozhou Bay.

Novel supramolecular network in tri- and mono-nuclear oxovanadium(V)-salicyl-hydroximate: Synthesis, structure and catalytic oxidation of hydrocarbons using H2O2 as terminal oxidant

oxovanadium(V) salicylhydroximate complexes, [VO(SHA)(H2O)]center dot 1.58H(2)O (1) and [V3O3(CSHA)(3) (H2O)(3)]center dot 3CH(3)COCH(3) (2) have been synthesized by reaction of VO43- with N-salicyl hydroxamic acid (SHAHS) and N-(5-chlorosalicyl) hydroxamic acid (CSHAH(3)), respectively, in methanol medium. Compound 1 on reaction with pyridine 2,6-dicarboxylic acid (PyDCH2) yields mononuclear complex [VO(SHAH(2))(PyDC)] (3). Treatment of compound 3 with hydrogen peroxide at low pH (2-3) and low temperature (0-5 degrees C) yields a stable oxoperoxovanadium(V) complex H[VO(O-2)(PyDC)(H2O)]center dot 2.5H(2)O (4). All four complexes (1-4) have been characterized by spectroscopic (IR, UV-Vis, V-51 NMR) and single crystal X-ray analyses. Intermolecular hydrogen bonds link complex 1 into hexanuclear clusters consisting of six {VNO5} octahedra surrounded by twelve {VNO5} octahedra to form an annular ring. While the molecular packing in 2 generates a two-dimensional framework hydrogen bonds involving the solvent acetone molecules, the mononuclear complexes 3 and 4 exhibit three-dimensional supramolecular architecture. The compounds 1 and 2 behave as good catalysts for oxygenation of benzylic, aromatic, carbocyclic and aliphatic hydrocarbons to their corresponding hydroxylated and oxygenated products using H2O2 as terminal oxidant; the process affords very good yield and turnover number. The catalysis work shows that cyclohexane is a very easily oxidizable substrate giving the highest turnover number (TON) while n-hexane and n-heptane show limited yield, longer time involvement and lesser TON than other hydrocarbons. (C) 2008 Elsevier Ltd. All rights reserved.

Identification of polycyclic aromatic hydrocarbons in sugar cane soot by gas chromatography mass spectrometry

Fly soot samples collected in the sugar cane fields after the process of burning were extracted in a Soxhlet apparatus (methylene chloride:methanol 4:1). The extracts were fractionated on silica gel Sep-Pak cartridges into three fractions. A gas chromatographic-mass spectrometric study of the fly soot extracts allowed the identification of the PAH with mutagenic and carcinogenic properties. Large amounts of aliphatic hydrocarbons, fatty acid esters and some PAHs were identified by GCMS in full scan mode. GC-MS in the selective ion monitoring mode (SIM) was suitable for the determination of many PAHs, which are often present in the burnt biomass. 31 PAHs and 7 thiophens derivatives were identified. The presence of these compounds should be regarded as a caution to workers and the general population to avoid exposure to the fly soot.

Halogenated aliphatic and aromatic aerobic biodegradation via direct metabolism and cometabolism: batch and continuous tests

In this thesis the application of biotechnological processes based on microbial metabolic degradation of halogenated compound has been investigated. Several studies showed that most of these pollutants can be biodegraded by single bacterial strains or mixed microbial population via aerobic direct metabolism or cometabolism using as a growth substrates aromatic or aliphatic hydrocarbons. The enhancement of two specific processes has been here object of study in relation with its own respective scenario described as follow: 1st) the bioremediation via aerobic cometabolism of soil contaminated by a high chlorinated compound using a mixed microbial population and the selection and isolation of consortium specific for the compound. 2nd) the implementation of a treatment technology based on direct metabolism of two pure strains at the exact point source of emission, preventing dilution and contamination of large volumes of waste fluids polluted by several halogenated compound minimizing the environmental impact. In order to verify the effect of these two new biotechnological application to remove halogenated compound and purpose them as a more efficient alternative continuous and batch tests have been set up in the experimental part of this thesis. Results obtained from the continuous tests in the second scenario have been supported by microbial analysis via Fluorescence in situ Hybridisation (FISH) and by a mathematical model of the system. The results showed that both process in its own respective scenario offer an effective solutions for the biological treatment of chlorinate compound pollution.