Abiogenic Fischer–Tropsch synthesis of hydrocarbons in alkaline igneous rocks; fluid inclusion, textural and isotopic evidence from the Lovozero complex, N.W. Russia

A detailed fluid inclusion study has been carried out on the hydrocarbon-bearing fluids found in the peralkaline complex, Lovozero. Petrographic, microthermometric, laser Raman and bulk gas data are presented and discussed in context with previously published data from Lovozero and similar hydrocarbon-bearing alkaline complexes in order to further understand the processes which have generated these hydrocarbons. CH₄-dominated inclusions have been identified in all Lovozero samples. They occur predominantly as secondary inclusions trapped along cleavage planes and healed fractures together with rare H₂O-dominant inclusions. They are consistently observed in close association with either arfvedsonite crystals, partially replaced by aegirine, aegirine crystals or areas of zeolitization. The majority of inclusions consist of a low-density fluid with CH₄ homogenisation temperatures between −25 and −120 °C. Those in near-surface hand specimens contain CH₄+H₂ (up to 40 mol%)±higher hydrocarbons. However, inclusions in borehole samples contain CH₄+higher hydrocarbons±H₂ indicating that, at depth, higher hydrocarbons are more likely to form. Estimated entrapment temperatures and pressures for these inclusions are 350 °C and 0.2–0.7 kbar. A population of high-density, liquid, CH₄-dominant inclusions have also been recorded, mainly in the borehole samples, homogenising between −78 and −99 °C. These consist of pure CH₄, trapped between 1.2 and 2.1 kbar and may represent an early CH₄-bearing fluid overprinted by the low-density population. The microthermometric and laser Raman data are in agreement with bulk gas data, which have recorded significant concentrations of H₂ and higher hydrocarbons up to C₆H₁₂ in these samples. These data, combined with published isotopic data for the gases CH₄, C₂H₆, H₂, He and Ar indicate that these hydrocarbons have an abiogenic, crustal origin and were generated during postmagmatic, low temperature, alteration reactions of the mineral assemblage. This would suggest that these data favour a model for formation of hydrocarbons through Fischer–Tropsch type reactions involving an early CO₂-rich fluid and H₂ derived from alteration reactions. This is in contrast to the late-magmatic model suggested for the formation of hydrocarbons in the similar peralkaline intrusion, Ilímaussaq, at temperatures between 400 and 500 °C.     

Do mature hydrocarbons have an influence on acid rock drainage generation?

The generation of acid rock drainage (ARD) is a biogeochemical process that causes severe ecological impacts, threatening human health worldwide. Microbes involved in acid drainage reactions are generally considered autotrophic but heterotrophic and mixotrophic microorganisms have often been identified at ARD sites. This raises questions about the role of organic matter naturally present at these sites, such as mature hydrocarbons, in promoting the microbial processes underpinning ARD generation. To investigate this, aerobic microcosm experiments were carried out using ARD samples collected at a well-characterised site in northern England (Mam Tor, Derbyshire). Organic analyses indicated the presence of substantial amounts of mature, petroleum-derived hydrocarbons and microbial analyses indicated that the sediment hosts acidophilic bacteria with the capability of degrading petroleum-derived compounds. However, the aerobic microcosm experiments indicated that these petroleum-derived hydrocarbons were not used by the bacterial community and, therefore, are not involved in the reactions that ultimately lead to ARD generation. These observations support a primary role for autotrophs in ARD generation.     

Hydrocarbons in the atmosphere

Trace concentrations of highly reactive hydrocarbons of biogenic origin have been proposed for some time as being important in aerosol formation processes in the atmosphere. More recently, assessments of potential photochemical reactions in the troposphere have proposed a role in the atmospheric ozone cycle for hydrocarbons, even for compounds such as methane that had previously been considered nonreactive. An assessment of the atmospheric hydrocarbon reaction system has been limited by a lack of observational information on the nature of conditions in the remote or non-urban atmosphere. Recent data on terpene concentrations and other biogenic hydrocarbon compounds are presented. Data on ethane and acetylene from aircraft samples taken over the north and south Pacific Ocean show concentrations in the 0.5 to 1 /m³ range for ethane and in the 0.05 to 0.3 g/m³ range for acetylene. A concentration gradient is present for these compounds between the northern and southern hemisphere. A rudimentary global concentration pattern for these C₂ compounds has been developed on the basis of recent data.     

Untersuchungen zur adsorptiven Abtrennung von leichtflüchtigen chlorierten Kohlenwasserstoffen (LCKW) aus huminstoffhaltigen Wässern mit neuartigen Adsorberpolymeren

Investigations of the Adsorptive Separation of Volatile Chlorinated Hydrocarbons (VCHC) from Water with Humic Substance by Novel Polymeric Adsorbents and Activated Carbons. Part I: Isotherms and Kinetics of Adsorption The isotherms and kinetics of adsorption of different volatile chlorinated hydrocarbons (VCHC) (1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethene) and a humic substance from water as well as these VCHC from water with humic substance onto novel polymeric adsorbents (WOFATIT EP 63, DOWEX XUS 43493 and XUS 43546, MACRONET MN 100 and MN 200) were studied in comparison to activated carbons (NORIT ROW 0.8 SUPRA, PRECOLITH BKK 3, HYDRAFFIN CG). It was determined that the novel polymeric adsorbents remove the VCHC well and the humic substance in contrast to the activated carbons only a few. The decrease of the equilibrium loading for the VCHC due to the presence of humic substance is at the activated carbons approximately double as high as at the novel polymeric adsorbents, whereas in the kinetics of adsorption no substantial influences of the humic substance on the mass transfer were determined.     

Adsorptive Separation of 1, 2‐Dichloroethane from Model Wastewater by Natural Clinoptilolite

The adsorptive separation of 1, 2‐dichloroethane from model wastewater by different Slovak natural and octadecylammonium‐modified clinoptilolites has been studied. It was found that the 1, 2‐dichloroethane will be adsorbed by natural as well as by surfactant‐modified clinoptilolites; all clinoptilolites have a similar adsorption loading. There was also no remarkable difference between the natural and surfactant‐modified clinoptilolites in respect to the adsorption kinetics.     

Relationships between tissue concentrations of chlorinated hydrocarbons (polychlorinated biphenyls and chlorinated pesticides) and antioxidative responses of marine mussels,Perna viridis

Marine mussels, Perna viridis, were transplanted from a reference site to various polluted sites around Hong Kong. After 30 d of exposure, antioxidative responses in the gills and hepatopancreas and tissue concentrations of chlorinated hydrocarbons [polychlorinated biphenyls (PCBs) and chlorinated pesticides (CPs)] were determined for individual mussels. Glutathione S transferase (GST) and glutathione (GSH) were positively correlated with tissue PCB concentrations. Only one of the enzymatic antioxidants, glutathione peroxidase (GPx), showed significant response to tissue PCB. No significant correlation was found between tissue concentrations of chlorinated hydrocarbons and other enzymatic antioxidants (superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GR) and NADPH DT-diaphorase (DT-d). Oxidative stress, measured as thiobarbituric acid reactive substances, was correlated with chlorinated pesticide concentrations in tissues. This study demonstrated a correlation between GST/GSH and chlorinated hydrocarbons. The apparent lack of correlation between trace organic pollutants and some of the enzymatic antioxidants may be due to the inhibitory effects caused by these chemicals. The above results suggest that more investigations are needed before these enzymes can be used as biomarkers.     

Hydrocarbon contamination in Cartagena Bay, Colombia

This study deals with the levels of aromatic and aliphatic hydrocarbon quantification in sediments and organisms in Cartagena Bay (Colombia), 1996-1997. Sediments (14 stations) and bivalves (2 stations) were monitored at different times of the year. Areas with high values were in the north with concentrations above 100 microg/g with a maximum of 1415 microg/g. Areas with low values were located toward the south, near the outlet of the Canal del Dique and Barú Island, with values below 10 microg/g. In other areas concentrations were between 50 and 100 microg/g. A decrease in sediment concentrations of hydrocarbons has occurred since 1983, but levels in some sectors are still similar to those in polluted areas. Organisms have relatively low values (8-30 microg/g for bivalves, and 10-40 microg/g for fish).     

Hydrocarbons in coastal sediments from the Mediterranean sea (Gulf of Fos area, France)

Sedimentary hydrocarbons have been studied quantitatively and qualitatively in 11 coastal stations located in the Gulf of Fos (French Mediterranean coast). Hydrocarbon levels ranged from 10 to 260 mg kg(-1) sed. dry weight. A new parameter "NAR" (Natural n-alkane ratio) is proposed to evaluate the contribution of terrestrial inputs of hydrocarbons in the sediments. The origins of hydrocarbons are multiple: terrestrial inputs, biogenic, pyrolytic (industry emissions mainly steel and iron industries, ship and road traffic). Generally, the main source of contamination is not petroleum. Several ratios between parent polycyclic aromatic hydrocarbons show that the sources of hydrocarbons in the sediments are generally much more pyrolytic than petrogenic.     

Current Situation and Application in Coal- Generated Hydrocarbons

The characteristics and research methods of terrigenous organic hydrocarbon - generated source rock in coal measures are studied in this thesis. After abundance of organic matters, pyrolysis parameter of rocks and hydrocarbon generated capacity of macerals are basically discussed in coal measures of the Cretaceous Muleng- Chengzihe formation in Suibin depression in Sanjang basin, the hydrocarbon generated grade in coal- generated source rock is ascertained in this depression. At last, we think that it is a main attack prospect in coal - generated hydrocarbons study in the future to research the macerals of coal measures organic source rock and to build a criterion to classify the coal- generated hydrocarbons in Northeast region.     

Magnetite compositions and oxygen fugacities of the Khibina magmatic system

Most titanomagnetite in the Khibina alkaline igneous complex, sampled through 500 m of a vertical cross-section, is represented by Ti-rich varieties. The ulvöspinel component is most commonly around 55 mol%, rarely reaching up to 80 mol%.

We calculated an f_O2–T diagram for magnetite + ilmenite + titanite + clinopyroxene + nepheline + alkali feldspar and magnetite + titanite+ clinopyroxene + nepheline + alkali feldspar phase assemblages at a hedenbergite activity of 0.2. The diagram shows that magnetites with 55 mol% of ulvöspinel crystallized at oxygen fugacities just slightly below the quartz–fayalite–magnetite buffer. More Ti-rich varieties crystallized at higher temperatures and slightly lower ΔQMF values, whereas more Ti-poor magnetites crystallized at or below about 650 °C.

Under the redox conditions estimated for the apatite-bearing intrusion of the Khibina complex (close to the QFM buffer), substantial quantities of methane may only form during cooling below 400 °C in equilibrium with magma. However, even at higher orthomagmatic temperatures and redox conditions corresponding to ΔQMF = 0, the hydrogen content in the early magmatic stage is not negligible. This hydrogen present in the gas phase at magmatic temperatures may migrate to colder parts of a solidifying magma chamber and trigger Fischer-Tropsch-type reactions there. We propose therefore, that methane in peralkaline systems may form in three distinct stages: orthomagmatic and late-magmatic in equilibrium with a melt and — due to Fischer-Tropsch-type reactions — post-magmatic in equilibrium with a local mineral assemblage.