Degradation of crude oils byPseudomonas sp. in enriched seawater medium

Microbial degradation of five crude oils such as Arabian light, Berri, Murban, Khafji and Minas crude oil by a pure bacterial strain,Pseudomonas sp. isolated from the sea water sampled at Kawasaki Harbor in Tokyo Bay, was studied experimentally in the enriched seawater medium.The degradation of crude oils was determined in total residual oil and in four fractions of saturated, aromatics, asphaltene and column residue by use of the column chromatography with activated alumina.The saturated fraction was shown to be most biodegradable. The aromatics followed for all five crude oils examined and the asphaltene was biodegradable to some extent. The column residue was not apparently degraded byPseudomonas sp. within 30 days. Each of Arabian light, Berri or Murban crude oil was degraded from 59 to 63.5 %, Khafji crude oil 49 % and Minas crude oil, solid at room temperature, only 33 %. Degradation rate of the five crude oils was determined to be in a range from 2.88 to 17.3 mg-oil 1^–1 hr^–1 or from 6.0×10^–12 to 1.56×10^–10 mg-oil cell^–1 hr^–1. Relative degradation ofn-paraffins of different carbon numbers in the saturated fraction was found to be similar regardless of carbon number for the five crude oils.     

Photo-oxidative behaviour of crude oils relative to sea pollution: Part II. Photo-induced phase separation

A phase separation appears during the photo-oxidation of a light crude oil (Zarzaitine from Algeria), an aromatic-rich petroleum distillate, and a model mixture. Analysis by steric exclusion chromatography shows that this phenomenon is due to the formation of high molecular weight species which are insoluble in the hydrocarbon mixture. The phenomenon is linked to the radical propagation of the oxidation reaction and mainly involves the aromatic fraction. Its mechanism is discussed on the basis of experimental results.     

Sensitivity of three microalgae to crude oils and fuel oils

Four crude oils and five fuel oils have been tested for toxicity with three microalgae—a blue-green, a green and a diatom. The oils were absorbed on filter paper pads and the pads submerged in the growth medium. The crude oils were less inhibitory than equal amounts of fuel oils. Despite initial growth lags, the crude oils allowed growth at 30 μl/20 ml of culture medium (10⁵ cells/ml) while fuel oils were lethal at 10 μl/20 ml. The toxicity patterns of two of the whole fuel oils were different from that seen with their water soluble fractions (WSF); for example, the Baton Rouge fuel oil sample was very toxic to growth of the three test organisms whereas its WSF was relatively innocuous. Photosynthesis of a sensitive organism Chlorella autotrophica, strain 580 (10⁷ cells/ml), was only temporarily depressed by the crude oils (30 μl/20 ml). Four of the fuel oils inhibited photosynthesis, O₂ output decreasing to zero without recovery. When the fuel oils were heated in a stream of helium they were detoxified. Chemical analyses of two of the toxic fuel oils before and after heating were compared with analyses of the Montana sample, a largely non-toxic fuel oil, in an effort to determine what types of compounds might be involved. Classes of aromatic compounds which were not accountable for the toxicity observed here include naphthalene, methylnaphthalenes, dibenzothiophenes, phenanthrenes and compounds with volatilities greater than methylnaphthalenes. Paraffinic and asphaltic fractions of fuel oil were also non-toxic. The accumulated chemical data suggest that the toxicity of whole fuel oils is due to the less water soluble types of compounds in the higher boiling aromatic fraction.     

Toxicity of Santa Barbara seep oil to starfish embryos: Part 3—influence of parental exposure and the effects of other crude oils

We exposed the bat starfish, Patiria miniata, to the water-soluble fraction (WSF) of oil from a natural seep near Santa Barbara, California, during the first 48 hours of embryological growth. There were no consistent differences among populations whose parents were from areas with differing levels of hydrocarbon exposure. In a second experiment, the order of decreasing toxicity of crude oils to the embryos was: Monterey Zone > Rincon Zone > Prudhoe Bay > Isla Vista Seep. The results are discussed in relation to the effects of natural seeps and oil characteristics.     

Mechanisms of petroleum accumulation in the Bozhong sub-basin, Bohai Bay Basin, China. Part 1: Origin and occurrence of crude oils

The origin of the fourteen major oil fields in the Bozhong sub-basin, Bohai Bay basin was studied based on the results of Rock-Eval pyrolysis on more than 700 samples and biomarker analysis on 61 source rock samples and 87 oil samples. The three possible source rock intervals have different biomarker assemblages and were deposited in different environments. The third member of the Oligocene Dongying Formation (E₃d₃, 32.8–30.3 Ma in age) is characterized mainly by high C₁₉/C₂₃ tricyclic terpane (>0.75), high C₂₄ tetracyclic terpane/C₂₆ tricyclic terpane (>2.5), low gammacerane/αβ C₃₀ hopane (<0.15) and low 4-methyl steranes/ΣC₂₉ steranes (<0.15) ratios, and was deposited in sub-oxic to anoxic environments with significant terrigenous organic matter input. The first (E₂s₁, 35.8–32.8 Ma) and third (E₂s₃, 43.0–38.0 Ma) members of the Eocene Shahejie Formation have low C₁₉/C₂₃ tricyclic terpane and low C₂₄ tetracyclic terpane/C₂₆ tricyclic terpane ratios and were deposited in anoxic environments with minor terrestrial organic matter input, but have different abundances of 4-methyl steranes and gammacerane. The hydrocarbon-generating potential and biomarker associations of these three source rock intervals were controlled by tectonic evolution of the sub-basin and climate changes. Three oil families derived from E₂s₃, E₂s₁ and E₃d, respectively, and three types of mixed oils have been identified. All large oil fields in the Bozhong sub-basin display considerable heterogeneities in biomarker compositions and originated from more than one source rock interval, which suggests that mixing of oils derived from multiple source rock intervals or multiple generative kitchens, and/or focusing of oils originated from a large area of a generative kitchen, is essential for the formation of large oil fields in the Bozhong sub-basin. E₂s₃- and E₂s₁-derived oils experienced relatively long-distance lateral migration and accumulated in traps away from the generative kitchen. E₃d₃-derived oils had migrated short distances and accumulated in traps closer to the generative kitchen. Such a petroleum distribution pattern has important implications for future exploration. There is considerable exploration potential for Dongying-derived oils in the Bozhong sub-basin, and traps close to or within the generative kitchens have better chance to contain oils generated from the Dongying Formation.     

Geochemistry and charge history of oils from the Yuqi area of Tarim Basin,NW China

The geochemistry, origin and charge history of oils from the Yuqi area of Tarim Basin have been investigated, through GC, GC-MS and fluid inclusion microthermometry analysis. The Yuqi oils accumulated mainly in three intervals: (1) in the Lower-Middle Ordovician Yingshan Formation (O_1-2y) carbonate reservoirs; (2) in the overlying Upper Triassic Halahatang Formation (T₃h); and (3) in the Lower Cretaceous Yageliemu Formation (K₁y) sandstones. Oils from different reservoirs have distinct physical properties, varying from extra-heavy (O_1-2y), heavy (T₃h), to light oils (T₃h and K₁y). However, their geochemical compositions show a high degree of similarity, which indicates that they derive from the same source rock. Abundant tricyclic terpanes, gammacerane, dibenzothiophene and C₂₁C₂₂steranes, together with a low level of diasteranes, indicate an anoxic marine source rock for oils in the Yuqi area. Oil-oil correlation shows that Yuqi oils derive from the same source bed as Tahe oils. The co-occurrence of intact n-alkanes and 25-norhopanes in all the samples supports the proposition that there is a mixture of an early filled severely biodegraded oil and a late filled fresh oil.In this study, charge history is examined on the basis of integration of fluid inclusion homogenization temperature data with 1D burial-thermal history models. Two episodes of oil charging are identified in the O_1-2y reservoir (well YQX1-1) at around 436-420 Ma (Middle-Late Silurian) and 10-3 Ma (Miocene to Pliocene), respectively. For the samples from the T₃h and K₁y intervals, only one episode of oil charge is indicated by the homogenization temperatures of coexisting aqueous inclusions with an inferred timing around 10-3 Ma. The T₃h heavy oil reservoir is assumed to be a secondary hydrocarbon pool, which accumulated by re-migration and re-distribution of hydrocarbons from O_1-2y hydrocarbon pools. The few early biodegraded oils in the K₁y light oils were probably picked up along the migration pathway during the late fresh oil charging.     

LPS-induced NO inhibition and antioxidant activities of ethanol extracts and their solvent partitioned fractions from four brown seaweeds

The nitric oxide inhibitory (NOI) and antioxidant (ABTS and DPPH radical scavenging effects with reducing power) activities of the ethanol (EtOH) extracts and solvent partitioned fractions from Scytosiphon lomentaria, Chorda filum, Agarum cribrosum, and Desmarestia viridis were investigated, and the correlation between biological activity and total phenolic (TP) and phlorotannin (TPT) content was determined by PCA analysis. The yield of EtOH extracts from four brown seaweeds ranged from 2.6 to 6.6% with the highest yield from D. viridis, and the predominant compounds in their solvent partitioned fractions had medium and/or less polarity. The TP and TPT content of the EtOH extracts were in the ranges of 25.0–44.1 mg GAE/g sample and 0.2–4.6 mg PG/g sample, respectively, which were mostly included in the organic solvent partitioned fractions. Strong NOI activity was observed in the EtOH extracts and their solvent partitioned fractions from D. viridis and C. filum. In addition, the EtOH extract and its solvent partitioned fractions of D. viridis exhibited little cytotoxicity to Raw 264.7 cells. The most potent ABTS and DPPH radical scavenging capacity was shown in the EtOH extracts and their solvent partitioned fractions from S. lomentaria and C. filum, and both also exhibited strong reducing ability. In the PCA analysis the content of TPT had a good correlation with DPPH (r = 0.62), ABTS (r = 0.69) and reducing power (r = 0.65), however, an unfair correlation was observed between the contents of TP and TPT and NOI, suggesting that the phlorotannins might be responsible for the DPPH and ABTS radical scavenging activities.     

Effects of Prudhoe bay crude oil on primary production and zooplankton in arctic tundra thaw ponds

The effects of Prudhoe Bay, Alaska, crude oil on the indigenous phytoplankton and zooplankton of tundra thaw ponds were studied under controlled conditions in situ during the summer of 1976. These effects were compared with uncontrolled oil spills on Pond Omega (a year previously) and Pond E (six years previously). In the uncontrolled spills, the phytoplankton species composition of both ponds remained appreciably different compared with control Pond C, although phytoplankton biomass did not differ greatly. Primary production remained low in Pond Omega but had recovered to control levels in Pond E. In controlled subpond experiments, oil caused a decrease of about 90–100% in primary production in five days but recovered to 40–50% of the control level within fifteen days. During that time, phytoplankton biomass decreased initially but recovered within fifteen days. Oil caused a shift in phytoplankton species composition from a predominance of cryptophytes to chrysophytes. Subponds containing two Daphnia middendorffiana and one Brachinecta paludosa per litre of pondwater were also affected by oil, causing zooplankton death within three or four days. After that time, changes in the phytoplankton species composition were similar to control subponds without zooplankton. Oil toxicity to zooplankton or experimental removal resulted in a loss of grazing pressure which caused the elimination of the cryptophyte Rhodomonas sp. This species was still absent from Pond Omega, but was seen in Pond E for the first time, when zooplankton also reappeared after six years. Oil perturbation of tundra thaw ponds causes a loss of zooplankton and a reduction in primary production. Phytoplankton primary production recovers somewhat but algal species composition remains changed because of the loss of zooplankton grazing pressure and the selective effects of oil.     

The role of iron chelates in the NAD(P)H-dependent oxidation of 2-keto-4-thiomethylbutyric acid (KMBA) by rainbow trout and pacific salmon microsomal fractions

Uninduced microsomes from three different species of the genus Oncorhynchus catalyzed a NAD(P)H-dependent oxidation of the radical scavenging agent 2-keto-4-thiomethylbutyric acid (KMBA). This reaction was stimulated by the addition of iron-EDTA, hemoglobin and myoblobin but inhibited by catalase and benzoate. Superoxide dismutase (SOD) did not substantially inhibit the oxidation in the presence of iron-EDTA. This hydroxyl radical (·OH)-generating system was mainly NADH-dependent which is similar to observations in aquatic invertebrates but in contrast to mammalian systems. This study demonstrates that this radical-generating activity is wide ranging and requires consideration in evaluating xenobiotic metabolism.     

Exposure of phytoplankton to ekofisk crude oil

Solutions of Ekofisk crude oil in sea water were prepared by slow stirring for 21h in a closed system. Headspace and GC/MS techniques were applied to establish dose composition and levels. The standardized test medium produced in a closed system contained approximately 14 mg oil per litre and was dominated by low molecular weight aromatic hydrocarbons and phenols.The toxicity of the standarized oil-containing medium to three marine diatoms was studied in a cage culture turbidostat and by conventional batch culture technique. The three algal species differed in sensitivity to the oil compounds, but showed identical ranking in both test systems.Standardized test medium diluted to 50% with respect to oil content stopped the growth of the most sensitive alga, Skeletonema costatum. For comparison naphthalene was applied and gave 50 % growth reduction at a concentration of 400 μg litre^?1. The growth of Chaetoceros ceratosporum was only slighty affected by the full strength standard test medium, which had no influence on the growth of Phaeodactylum tricornutum, the least sensitive organism. The presence of an oil layer on the surface of the standard test medium during the growth test greatly increased its toxicity and blocked completely the photosynthesis even of P. tricornutum after 4 days.     

Characteristics and origin of carbon isotopes of n-alkanes in crude oils from the western Pearl River Mouth Basin,South China sea

The quantitative characterization of carbon isotopes of n-alkanes is commonly carried out in organic geochemical studies. Possible controls on carbon isotopes include source organic matter, maturity, fractionation during oil expulsion and migration, and the mixing of different oils. In this study of the origin of crude oils in the western Pearl River Mouth Basin, the influences of all of these factors have been considered in reaching a conclusion. Carbon isotopes of n-alkanes in the crude oils, and the extracts of the two effective source rocks (the Wenchang and Enping formations) in the basin, exhibit clear differences. The Wenchang source rocks have heavy δ¹³C values that remain almost constant or become slightly heavier with increasing carbon number. The Enping source rocks have light δ¹³C values that become lighter with increasing carbon number. Two groups of oils in this area were identified based on the carbon isotopes of the n-alkanes; groupIoils are similar to extracts of the Wenchang source rocks. However, the groupIIoils are different from both the Wenchang and Enping source rocks and the carbon isotopic profiles of their n-alkanes exhibit a “V” feature with increasing carbon number. The results of artificial thermal maturation experiments indicate that, from the early stage to the peak stage of oil generation (with EasyRo between 0.64% and 1.02%), the δ¹³C values of n-alkanes in the pyrolysis oils become heavier by about 3‰ with increasing thermal maturity, but the shape of the carbon isotopic profiles are not significantly changed. Calculated δ¹³C values of n-alkanes in “mixed” artificial pyrolysis oils indicate that the mixture of oils generated from the same source rocks with different maturities could not change the carbon isotopic profile of the n-alkanes, however, a mixing of the Wenchang and Enping oils could give the “V” feature in the profiles, similar to the groupIIoils in this area. The groupIIoils appear to be mixed Wenchang and Enping oils, the latter being the dominant component in the mixture. We conclude that the source organic matter and the degree of mixing are the main factors controlling the carbon isotopic characteristics of n-alkanes in crude oils in the western Pearl River Mouth Basin.     

The invasion of the intertidal canopy-forming alga Fucus serratus L. to southwestern Iceland: Possible community effects

The intertidal serrated wrack, Fucus serratus L. (Fucales: Phaeophyceae), has become an abundant canopy-forming alga along a ca. 100 km stretch of shore in southwestern Iceland in the last century. Its distribution has not changed noticeably since a survey in 1975/1976. Many experimental studies have shown that canopy-forming algae can have profound effects on the community structure. Although such experiments involving F. serratus are few it was decided to test predictions from these experiments on a geographical scale by comparing community compositions within the area where F. serratus is a dominant algae (since at least 1975/1976) with an adjacent area of similar size where F. serratus is absent (with a single exception without consequences). The work is based on measurements on some 372 stations in the F. serratus area, termed region A, and 227 stations from the F. serratus-free area, termed region B. Percentage cover of algae and sessile invertebrates was estimated on 2 m² on each station and animals collected from 800 cm² from each station. The vertical distribution of F. serratus was most similar to that of Fucus distichus and the two species often grew intermingled on the lower part of the shore. F. serratus appeared to have reduced the cover of F. distichus in the lowermost part of the shore, while having little or no effect on other canopy-forming species. The low abundance of Semibalanus balanoides in the F. serratus area (region A) is in line with experiments showing detrimental effect on this barnacle by whiplash of F. serratus. In general algal grazers were more abundant in region A, consistent with the greater attractiveness of F. serratus than other canopy-forming species to grazers, although this may be partly explained by the abundance of understorey algae in region A.     

Sensitivity of two psychrophilic diatoms to crude oil and fuel oil

Two pure cultures of diatoms, a Nitzschia sp. and a Chaetoceros sp., were grown at 0°C or 10°C in the presence of two crude oils and two fuel oils. The petroleum samples were absorbed onto filter paper discs and added directly to the algal cultures. In all cases the organisms were much more sensitive to the crude oils or fuel oils when growing at 0°C than at 10°C. The rate of photosynthesis measured by an oxygen electrode for Nitzschia sp. grown and tested at 0°C was not affected during 3 hours' incubation with some four times the amount of a crude oil or fuel oil that blocked growth. The experiments lead to the cautious suggestion that psychrophilic algae will prove some fivefold more sensitive than mesophilic algae to petroleum pollution.     

Biomarkers derived from heterolytic and homolytic cleavage of allylic hydroperoxides resulting from alkenone autoxidation

Laboratory incubation of alkenone mixtures with tert-butyl hydroperoxide and di-tert-butyl nitroxide (radical initiator) in hexane, as a means to simulate alkenone autoxidation processes, rapidly led to the formation of allylic hydroperoxides, whose presence was recently demonstrated in Emiliania huxleyi cells. After incubation in seawater and subsequent reduction with NaBH₄ (to reduce residual hydroperoxides before analysis), these reaction products quickly disappeared and were replaced by complex mixtures of n-alcohols, fatty acids, alkyldiols and hydroxyacids. Methyl alkenones produced saturated n-alkan-1-ols and fatty acids ranging from C₁₃ to C₁₆ and two series of C₁₃−C₁₆ (ω-1)-hydroxyacids and (1,ω-1)-diols. Ethyl alkenones also afforded C₁₃−C₁₆ saturated n-alkan-1-ols and fatty acids, accompanied by the production of C₁₄−C₁₇ (ω-2)-hydroxyacids and (1,ω-2)-diols. Deuterium labelling allowed us to show that most of the n-alkan-1-ols, hydroxyacids and alkyldiols resulted from the reduction during the NaBH₄ treatment of the corresponding aldehydes, ketoxyacids and ketoxyaldehydes formed from heterolytic or homolytic cleavages of allylic hydroperoxyl groups resulting from the oxidation of the double bonds of di- and triunsaturated alkenones. Amongst these products, the (ω-1)- and (ω-2)-hydroxyacids formed after NaBH₄ reduction of the (ω-1)- and (ω-2)-ketoxyacids were selected as potential biomarkers for alkenone autoxidation. Re-examination of lipid extracts of post-bloom seawater particulate matter samples from the DYFAMED station in the Ligurian Sea (where strong autoxidative alteration of the lipid distributions had previously been detected) showed the presence of significant amounts of 12-hydroxytetradecanoic, 13-hydroxytetradecanoic, 14-hydroxyhexadecanoic and 15-hydroxyhexadecanoic acids thus providing good evidence that these autoxidative processes occur in natural samples.     

Geochemical and biological marker assessment of depositional environments using Brazilian offshore oils

A combined geochemical and molecular characterization of a wide selection of oils from the major Brazilian offshore basins has been undertaken. The elemental (sulphur, nickel and vanadium) and bulk (^oAPI and δ¹³C) properties of each sample been considered, together with its molecular composition determined using liquid and gas chromatography, and quantitative biological marker investigations using gas chromatography-mass spectrometry for alkanes.The results reveal significant differences in the chemical features of the various oils which enable them to be divided into five groups. The distinction of the groups appears to reflect differences in the depositional environment of the source rocks of the oils. Each group is correlated tentatively with source rocks laid down in a specific depositional regime, namely lacustrine freshwater, lacustrine saline water, marine evaporitic, marine carbonate or marine deltaic. The diagnostic features that allow this classification are: the relative abundance and carbon number distributions of n-alkanes; pristane/phytane ratios; sulphur, nickel and vanadium contents; carbon isotope data; the absolute concentrations of hopanes and steranes, and their abundance relative to 4-methylsteranes and, also the occurrence and abundance of several specific biological markers, including 18α(H)-oleanane, gammacerane, β-carotane, tricyclic terpanes, higher acyclic isoprenoids, 28, 30-bisnorhopane and 25, 28, 30-trisnorhopane. This investigation shows the value of a combined geochemical and molecular approach in the assessment of the palaeoenvironment of deposition of the source rocks which gave rise to the oils.     

The long-term effects of crude oil on microbial processes in subarctic marine sediments

Subarctic marine sediments were exposed to fresh and ‘weathered’ crude oil from Cook Inlet, Alaska. The crude oil was thoroughly mixed with the sediment at various concentrations and some of the oil-sediment mixtures were placed on top of unamended sediments. Both sediments with added oil and those overlain by oiled sediments were investigated. These sediments were placed either in trays or aquaria. The trays were incubated in situ near the site from which the sediments were originally collected. The aquaria were maintained at simulated in situ conditions by maintaining a continuous flow of fresh seawater through them. The sediments were exposed to crude oil for periods up to 1.5 years. Sediments exposed to 50‰ fresh crude oil showed significant decreases in nitrogen fixation and denitrification rates and redox potentials. Also observed were increases in CO₂ production rates and methane concentrations. These same changes were observed in sediments exposed to 1‰. When ‘weathered’ crude oil was added to the sediments, the same changes were observed except there was no reduction in nitrogen fixation activity. In most cases, the observed effects were less marked when the sediments were amended with ‘weathered’ crude oil than with the same concentration of fresh crude oil. Untreated sediments that were overlain with treated sediments showed the same changes as those sediments that were thoroughly mixed with crude oil. The presence of fresh crude oil at 50‰ essentially eliminated burrowing activity of the benthic infauna. Under these conditions, there was an accumulation of detritus particles on the oiled sediments that was not present in the untreated controls.     

Impact of crude oil on sulphate reduction and methane production in sediments impacted by the Amoco Cadiz oil spill

The activities of methane-producing and sulphate-reducing bacteria in intertidal sediments along the Brittany coast of France were examined in order to determine the effect of the Amoco Cadiz oil spill on sediment microbial processes. Porewater chemistry, methane production, sulphate rate and [2?¹⁴C]-acetate metabolism did not vary significantly between beach, estuary, and marsh sites, oiled or unoiled, after the Amoco Cadiz spill. Oiled sediments contained highly weathered oil of Amoco Cadiz origin, but unoiled comparison sites also contained hydrocarbons from anthropogenic sources. The additions of weathered Amoco Cadiz mousse, fresh and slightly weathered light Arabian crude oil, benzene or toluene to sediments from the oiled and unoiled marsh site did not significantly affect rates of sulphate reduction or methane production. The oxidation of [2?^14C]-acetate to ¹⁴CO₂, however, was significantly decreased when mousse, crude oil, benzene or toluene was added to sediments from the unoiled site. Inhibition seemed to be proportional to the extent of weathering. Sediments recently exposed to Amoco Cadiz crude oil were less affected by a second oiling, suggesting that the indigenous populations may have been replaced by organisms more resistant to oil toxicity. These results suggested that the Amoco Cadiz oil spill did not have major long-term effects on sulphate reduction or methane production.     

Benzo[a]pyrene-dione-stimulated oxyradical production by microsomes of digestive gland of the common mussel, Mytilus edulis L

The potential of benzo[ a]pyrene (BaP) quinones (diones) to stimulate NAD(P)H-dependent hydroxyl radical (·OH) production (2-keto-4-methiolbutyric acid (KMBA) oxidation) by digestive gland microsomes of M. edulis was studied using iron/EDTA as a promotor of the Haber-Weiss reaction (O₂⁻ + H₂O₂ = ·OH + OH⁻ + O₂). Stimulation of basal rates of KMBA oxidation was observed for all three diones. Stimulation was similar for the 1,6- and 3,6-diones, but much less for the 6,12-dione, and greater for the NADH than the NADPH-dependent reaction, viz. % increases of 78 to 333 (NADH) compared to 0 to 78 (NADPH). Maximal KMBA oxidation was obtained at dione concentrations of 12.5 to 50 μm. Inhibition of KMBA oxidation by Superoxide dismutase and catalase indicated the involvement of respectively Superoxide anion radical (O₂⁻) and hydrogen peroxide (H₂O₂) in 1,6-dione stimulated NADPH-dependent · OH formation. The apparent K_m values of xenobiotic-stimulated KMBA oxidation were lower for BaP-diones than for the model redox cycling quinone menadione (2-methyl-1,4-naphthoquinone), viz. in μm, 0.6 to 14.6 (NADH) and 4.4 to 28.5 (NADPH) compared to 315 to 457 (NADH) and 72 to 103 (NADPH). The results are consistent with metabolism of BaP to diones and resultant enhanced generation of oxyradicals being a potential mechanism of pollutant-mediated toxicity in molluscs.     

Hemocytes of Mytilus edulis affected by Prudhoe Bay crude oil emulsion

Hemocytes and tissues of Mytilus edulis were examined after 4–5 or 8–9 week's exposure to 390 μg/liter or 740 μg/liter Prudhoe Bay crude oil emulsion, during the animals' most metabolically active season. A reduction in hemocytes occurred in animals exposed to 740 μg/liter after 4–5 weeks. After 8–9 weeks, hemocyte counts of both test groups increased, due to higher densities of granulocytes, yet the phagocytic response was reduced. Agranulocyte densities were reduced in animals exposed to 390 μg/liter, due to lower counts of 2–3 μm agranulocytes. Further, adipogranular cell percentages in test animals were reduced. The results from oil-exposed mussels suggest a stress condition and have implications for monitoring.     

Origin of crude oils from oilfields in the Zagros Fold Belt,southern Iraq: Relation to organic matter input and paleoenvironmental conditions

Crude oil samples from Cretaceous and Tertiary reservoir sections in the Zagros Fold Belt oil fields, southern Iraq were investigated using non-biomarker and biomarker parameters. The results of this study have been used to assess source of organic matter, and the genetic link between oils and their potential source rocks in the basin. The oils are characterized by high sulphur and trace metal (Ni, V) contents and relatively low API gravity values (17.4–22.7° API). This indicates that these oils are heavy and generated from a marine source rock containing Type II-S kerogen. This is supported by their biomarker distributions of normal alkanes, regular isoprenoids, terpanes and steranes and the bulk carbon isotope compositions of their saturated and aromatic hydrocarbons. The oils are characterized by low Pr/Ph ratios (<1), high values of the C₃₅ homohopane index and C₃₁-22R/C₃₀ hopane ratios, relatively high C₂₇ sterane concentrations, and the predominance of C₂₉-norhopane. These biomarkers suggest that the oils were generated predominantly from a marine carbonate source rock, deposited under reducing conditions and containing plankton/algal and microorganisms source input. The presence of gammacerane also suggests water column stratification during source rock deposition.The biomarker characteristics of the oils are consistent with those of the Middle Jurassic Sargelu carbonate as the effective source rock in the basin. Biomarker maturity data indicate that the oils were generated from early maturity source rocks.