Ab initio infra-red spectra of iron-polycyclic aromatic hydrocarbon compounds: a model case

C₁₀H₆-Fe⁺ complexes were observed by Fourier transform mass spectrometry by Marty et al. (Chem. Phys. Lett. 256 (1996) 669). In this article, we present the infra-red (IR) spectra of the two isomers calculated by ab initio methods of quantum chemistry. In the past, the same approach has predicted successfully unexpected features of the IR spectra of polycyclic aromatic hydrocarbon (PAH) cations which were confirmed by measurements in matrices (J. Phys. Chem. 98 (1994) 9187). The C₁₀H₆-Fe⁺ systems are models for larger PAHs-Fe⁺ complexes, which are believed to play a key rôle in space chemistry.     

Assessing degradation capability of aerobic indigenous microflora in PAH-contaminated brackish sediments

A study was conducted to determine polycyclic aromatic hydrocarbons (PAHs) distribution and microbial population changes in brackish sediments from an Italian lagoon included in the Ramsar List of Wetlands of International Importance. The presence and level of PAH-degrading bacteria were estimated by the most probable number (MPN) enumeration technique, whereas degradation capability towards target compounds was checked against loss of spiked PAHs (Phenanthrene, Anthracene and Fluoranthene) in MPN tubes after incubation in optimal conditions. Chemical analyses and microbiological counts suggested a potential for PAHs biodegradation by natural occurring populations of sediment microorganisms, thus indicating an "optimal range" in sediment PAHs concentrations, outside of which the natural selection of the indigenous microflora did not occur. The MPN procedure here described, provided an effective and reliable way to simultaneously determine microbial population densities and subsequent confirmation of the biodegradation capability of sediment indigenous microflora when exposed to laboratory and environmental concentrations of PAHs.     

Fatal attraction: synthetic musk fragrances compromise multixenobiotic defense systems in mussels

We studied interactions of nitromusk compounds musk ketone and musk xylene and polycyclic musks Galaxolide trade mark (HHCB), Celestolide trade mark (ADBI), Tetralide trade mark (AHTN), and Traseolide trade mark (AITI) with multixenobiotic resistance (mxr) transporters in gill tissue of the marine mussel Mytilus californianus (Conrad, 1837). A competitive substrate transport test with rhodamine B was used to assay modulation of transport activity by musks. All tested musks inhibited the transport activity in the low microm range as indicated by increased accumulation of rhodamine B in the tissue. Compared to known substrates of mxr transporters, the effective concentration range was similar to quinidine and about 100 times higher than verapamil. Musk ketone and musk xylene also inhibited efflux of rhodamine B from gill tissue which was loaded with the dye and subsequently incubated with these compounds. Synthetic musk compounds are persistent environmental pollutants in aquatic environments with a high potential to bioaccumulate. As potent inhibitors of mxr transporters they may also play a role as chemosensitizers that enable toxic mxr substrates to accumulate in cells of aquatic organisms.     

The impact of salt water inflows on the distribution of polycyclic aromatic hydrocarbons in the deep water of the Baltic Sea

Salt-water inflows into the Baltic Sea are important events for renewing the deep and bottom waters of the deep basins of the Baltic Sea. These events occur only at irregular intervals. The last strong event was in January 1993 followed by minor inflows in winter 1993/1994. As a result of these inflows, the deep water of the central Baltic basins was completely renewed.Based on extensive observations of polycyclic aromatic hydrocarbons (PAHs) in water, fluffy layer material and surface sediments between 1992 and 1998, the transformation of PAHs and the modification of their distribution in the Baltic deep water is discussed in connection with the spreading of the inflowing highly saline and oxygen-rich water along its pathway from the sills into the central basins. In the course of the inflows in 1993/1994, the PAH concentration in the deep water of the different basins increased significantly. The concentrations were elevated, at least by a factor of 2 and as much as seven to eight times (for the four-ring PAHs) compared to the previous and the following years. Two hypotheses for the causes were discussed: the inflowing salt water may have entrained more highly polluted surface water in the western Baltic Sea, or it may have entrained contaminated fluffy layer material or sediment particles along the route of transport.     

Polycyclic aromatic hydrocarbons in water, seston and copepods in a harbour area in the Western Mediterranean (Ligurian Sea)

Polycyclic aromatic hydrocarbons (PAHs) are widespread carcinogenic, mutagenic and teratogenic pollutants that can significantly affect ecosystems and exert an influence on marine planktonic and benthic communities as well as on higher organisms such as fish and mammals, including humans. In this paper the concentrations of six PAHs in water, seston and copepods were examined in a harbour zone of the Genova Gulf (Ligurian Sea) from November 1997 to June 1998. The importance of freshwater inputs coming from a polluted stream and the influence of seasonal and atmospheric factors were also considered. Highest PAH values were recorded during spring. Fluoranthene, Benzo[b]fluoranthene and Benzo[k]fluoranthene were the most abundant PAHs either in water, seston or copepods. The concentration of total PAHs in seawater was often lower than the detection limit: recorded values ranged between 0.001 and 0.06 ppb. In seston, total PAHs ranged between 0.033 and 6.26 ng·g^?1 and in copepods between 0.01 and 2.34 ng·g^?1. With this study, PAH contamination in the harbour zone of Genova Sestri‐Ponente and the importance of inputs of organic pollutants coming from land and freshwaters have been emphasized.     

A reassessment of models for hydrocarbon generation in the Khibiny nepheline syenite complex, Kola Peninsula, Russia

Although hydrocarbon-bearing fluids have been known from the alkaline igneous rocks of the Khibiny intrusion for many years, their origin remains enigmatic. A recently proposed model of post-magmatic hydrocarbon (HC) generation through Fischer-Tropsch (FT) type reactions suggests the hydration of Fe-bearing phases and release of H₂ which reacts with magmatically derived CO₂ to form CH₄ and higher HCs. However, new petrographic, microthermometric, laser Raman, bulk gas and isotope data are presented and discussed in the context of previously published work in order to reassess models of HC generation. The gas phase is dominated by CH₄ with only minor proportions of higher hydrocarbons. No remnants of the proposed primary CO₂-rich fluid are found in the complex. The majority of the fluid inclusions are of secondary nature and trapped in healed microfractures. This indicates a high fluid flux after magma crystallisation. Entrapment conditions for fluid inclusions are 450–550 °C at 2.8–4.5 kbar. These temperatures are too high for hydrocarbon gas generation through the FT reaction. Chemical analyses of rims of Fe-rich phases suggest that they are not the result of alteration but instead represent changes in magma composition during crystallisation. Furthermore, there is no clear relationship between the presence of Fe-rich minerals and the abundance of fluid inclusion planes (FIPs) as reported elsewhere. δ¹³C values for methane range from − 22.4‰ to − 5.4‰, confirming a largely abiogenic origin for the gas. The presence of primary CH₄-dominated fluid inclusions and melt inclusions, which contain a methane-rich gas phase, indicates a magmatic origin of the HCs. An increase in methane content, together with a decrease in δ¹³C isotope values towards the intrusion margin suggests that magmatically derived abiogenic hydrocarbons may have mixed with biogenic hydrocarbons derived from the surrounding country rocks.     

MODELING THE FATE AND TRANSPORT OF HYDROPHOBIC ORGANIC COMPOUNDS IN AN UNSTEADY RIVER-ESTUARINE SYSTEM

1 INTRODUCTION Extensive literature (Brown et al., 1985; Sawhney et al., 1981; Bierman and Swain, 1982; Connolly, 1980; Lopez-Avila and Hites, 1980; O扖onnor, 1988) described lots of sorbed pollutants or toxic substances in bed sediments of rivers, even after the effluent was halted for a long time. This is particularly true for hydrophobic organic compounds that can be sorbed on the particles and accumulated in the river bed sediments (Karickhoff et al., 1979). Pollution events of…     

Diagenetic history and porosity evolution of Upper Carboniferous sandstones from the Spring Valley #1 well, Maritimes Basin, Canada–implications for reservoir development

Eighty-two core samples were collected from the Spring Valley #1 well which penetrates the Upper Carboniferous strata in the Late Devonian–Early Permian Maritimes Basin. The strata consist of alternating sandstones and mudstones deposited in a continental environment. The objective of this study is to characterize the relationship of sandstone porosity with depth, and to investigate the diagenetic processes related to the porosity evolution. Porosity values estimated from point counting range from 0% to 27.8%, but are mostly between 5% and 20%. Except samples that are significantly cemented by calcite, porosity values clearly decrease with depth. Two phases of calcite cement were distinguished based on Cathodoluminescence, with the early phase being largely dissolved and preserved as minor relicts in the later phase. Feldspar dissolution was extensive and contributed significantly to the development of secondary porosity. Quartz cementation was widespread and increased with depth. Fluid inclusions recorded in calcite and quartz cements indicate that interstitial fluids in the upper part of the stratigraphic column were dominated by waters with salinity lower than that of seawater, the middle part was first dominated by low-salinity waters, then invaded by brines, and the lower part was dominated by brines. Homogenization temperatures of fluid inclusions generally increase with depth and suggest a paleogeothermal gradient of 25 °C/km, which is broadly consistent with that indicated by vitrinite reflectance data. An erosion of 1.1–2.4 (mean 1.75) km of strata is inferred to have taken place above the stratigraphic column. δ¹⁸O values of calcite cements (mainly from the late phase) decrease with depth, implying increasing temperatures of formation, as also suggested by fluid-inclusion data. δ¹³C values of calcite cements range from −13.4‰ to −5.7‰, suggesting that organic matter was an important carbon source for calcite cements. A comparison of the porosity data with a theoretical compaction curve indicates that the upper and middle parts of the stratigraphic column show higher-than-normal porosity values, which are related to significant calcite and feldspar dissolution. Meteoric incursion and carboxylic acids generated from organic maturation were probably responsible for the abundant dissolution events.     

Evidence of early generation of liquid hydrocarbon from suberinite as visible under the microscope

The early generation of liquid hydrocarbons from suberinite can be clearly observed under the microscope. The generation of this oil-like material, mainly in the form of exsudatinite, from the maceral suberinite occurs at a maturity level of about 0.4% vitrinite reflectance. Hydrocarbons appear to be naturally expelled from coal initially through sweating and agglomeration of suberinite which subsequently forms exsudatinite. It is suggested that extensive expulsion of exsudatinite causes cracks to develop in vitrinite whereas limited expulsion of exsudatinite will only impregnate the vitrinite matrix. If cracks are formed, it is possible they could progressively develop to form an exsudatinite-crack network. The formation of such a network is believed to represent an effective way of hydrocarbon expulsion from coal source rocks.