Hydrocarbons in benthic algae from the eastern Gulf of Mexico

Thirty-six samples of benthic algae were collected from the continental shelf along the eastern Gulf of Mexico. The algae contain 82.8±143 ppm aliphatic hydrocarbons by dry weight and 11.8±22.7 ppm aromatic and polyolefinic hydrocarbons. The aliphatic constituents of red algae are composed almost entirely of n-C₁₇ (70 to 95% of aliphatic weight); green algae have varying amounts of n-alkanes in the range of n-C₁₅ to n-C₁₉, with homologous series of odd carbon number n-alkenes. Phytadienes occur as high as 740 ppm dry weight in the green algae and do not appear to be related to time or place of collection or to presence of any petroleum pollutants. The single brown algal species contains predominantly n-C₁₅. About 30% of the samples have hydrocarbons resembling degraded petroleum residues, but no petroleum pollution of recent origin was detected in any specimen.     

Transformations of <Emphasis Type="Italic">n</Emphasis>-alkanes from petroleum pollutants in alluvial groundwaters

Investigations presented in this paper were aimed at defining the alterations of n-alkane composition in cases of oil-polluted alluvial sediments. Therefore, oil-polluted groundwater samples, taken in five different time intervals during a period of 28 months, were investigated. Samples of alluvial sediments were taken from two boreholes within an oil refinery at Pancevo, Yugoslavia. In both boreholes significant alterations with characteristic degradation of "oil" n-alkanes with no odd- or even-member predominance were observed, as well as subsequent synthesis of new ones with pronounced even-member predominance, and with maxima at C₁₆ and C₁₈. Since no additional contamination of boreholes was observed by analyses of steranes and triterpanes, the observed changes can only be attributed to microbial activity. It is assumed that for the degradation of oil n-alkanes, as well as for the synthesis of "new" n-alkanes, algae such as dinoflagellates are responsible. This assumption was confirmed by identification of n-alcohols with even-member predominance (C₁₄–C₂₀), by identification of cholesterol, as well as of n-fatty acids with even-member predominance (C₁₄–C₁₈) in the extract with n-alkane even-member predominance. Electronic Publication     

Ecological significance of salp fecal pellets collected by sediment traps in the eastern North Pacific

Five sediment traps were moored at depths of 740, 940, 1 440, 3 440 and 4 240 m for 7 d in December 1982 at Station 5 in the eastern North Pacific about 400 km from San Francisco. Dark green sinking particles enclosed in tough membrane consisted of mostly coccolithophores with some diatoms, dinoflagellates and chrysophytes. The average size of the particles was 10x5x2 mm. These characteristics indicate that the particles were fecal pellets of salp inhabiting the surface waters. Vertical fluxes of the organic carbon and nitrogen through sinking of the salp fecal pellets ranged from 6.7 to 23 mgC m^-2 d^-1 and from 0.88 to 3.2 mgN m^-2 d^-1, respectively. These values were several times higher than those determined in other oceanic areas by sediment trap experiments. Hydrocarbons consisting of short-chain n-alkanes (n-C₁₅-C₂₀) with n-C₁₇, the most predominant component, heneicosa-hexaene (n-C_21:6), br-C₂₅ alkenes and long-chain n-alkanes (n-C₂₁-C₃₀), without any odd or even carbon number predominance, were found from five depths. The presence of short-chain n-alkanes and n-C_21:6 indicated that phytoplankton in the surface waters was a primary source of organic matter in the sinking particles. Two isomers of br-C_25:3 and br-C_25:4 alkenes found in these particles also indicated that br-C₂₅ alkenes were the important biological marker of fecal pellet of zooplankton. The distribution pattern of the long-chain n-alkanes suggested that the sinking particles may be affected by bacteria to some extent. Fatty acids of the sinking particles were separated into free, triglyceride and wax ester fractions consisting of mono- and poly-unsaturated, and saturated fatty acids, with a range from C₁₄ to C₃₀. Concentrations of mono- and poly-unsaturated fatty acids decreased more rapidly toward the deep than those of saturated fatty acids, which cause low ratios of mono- and poly-unsaturated fatty acids/saturated fatty acids. This indicates that unsaturated fatty acids were more rapidly decayed by marine microbes than saturated fatty acids in the deep water, despite the fact that a significant amount of unsaturated fatty acids still remained in the sinking particles collected from the deep waters. Our results revealed that the salp fecal pellet plays an important role in supplying foods to organisms in intermediate and deep seas.     

Very long-chain aliphatic hydrocarbons in lipids of mussels (Mytilus edulis) suspended in the water column near petroleum operations off Sable Island,Nova Scotia,Canada

Mussels (Mytilus edulis) suspended in the water column in 1994 and 1995 for the monitoring of oil drilling operations off Sable Island, Nova Scotia were examined for hydrocarbon profiles, particularly aliphatic hydrocarbons. A spring bloom of phytoplankton occurred during the 90-d suspension period in 1995. Hydrocarbons isolated from the 1995 suspended mussels showed very high concentrations of both biogenic hydrocarbons and very long-chain n-alkanes from C₂₀ to C₃₂, initially thought to be petrogenic. Both types of hydrocarbons were either not detected or were only present in trace amounts in the mussels suspended in 1994 at similar sites. The biogenic hydrocarbons in the 1995 mussels were apparently of planktonic origin, from the spring bloom, and were dominated by heneicosahexaene (21:6), followed by pristance, heptadecane, and varions monounsaturated and polyunsaturated phytenes, heptadecenes, nonadecenes and heneicosenes. They could be readily hydrogenated to yield the basic alkanes. The 1995 mussels suspended within 1 km from the oil well platform were probably slightly tainted by petrogenic hydrocarbons, as evidenced by the detection of phytane and high concentrations of total aliphatic hydrocarbons, whereas the mussels suspended 10 km from the platform showed only high concentrations of biogenic hydrocarbons and the novel long-chain n-alkanes. The occurrence of an unusual phytoplankton bloom during the suspension period severely interfered with the petroleum monitoring role of mussels by altering the mussel hydrocrbon profiles through the accumulation into and probably selective depuration of xenobiotic hydrocarbons from the mussel, tissues.J. Parsons (deceased)     

Selective pseudosolubilization capability of Pseudomonas sp. DG17 on n-alkanes and uptake mechanisms analysis

Pseudosolubilized ability of Pseudomonas sp. DG17 on n-alkanes, role of biosurfactants in n-octadecane uptake and trans-membrane transport mechanism of n-octadecane were studied by analyzing amount of pseudosolubilized oil components in water phase, and the fraction of radiolabeled ¹⁴C n-octadecane in the broth and cell pellet. GC-MS results showed that pseudosolubilized oil components were mainly C₁₂ to C₂₈ of n-alkanes. In n-octadecane broth, pseudosolubilized n-octadecane could be accumulated as long as pseudosolubilized rate was faster than mineralization rate of substrate, and the maximum concentration of pseudosolubilized n-octadecane achieved to 45.37 mg·L^?1. All of these results showed that Pseudomonas sp. DG17 mainly utilized alkanes by directly contacting with pseudosolubilized small oil droplets in the water phase. Analysis of ¹⁴C amount in cell pellet revealed that an energy-dependent system mainly controlled the trans-membrane transport of n-octadecane.     

(<Emphasis Type="Italic">Z</Emphasis>)-9-Pentacosene − contact sex pheromone of the locust borer, <Emphasis Type="Italic">Megacyllene robiniae</Emphasis>

Summary. Male locust borers, Megacyllene robiniae (Förster), responded to females only after contacting them with their antennae, indicating that mate recognition was mediated by a contact sex pheromone. GC-MS analyses of whole-body extracts of males and females determined that the profiles of compounds in the extracts were qualitatively similar, but differed considerably in the ratios of compounds between sexes. Biological activities of reconstructed blends of the most abundant straight-chain (nC₂₃, nC₂₄, nC₂₅, nC₂₆), methyl-branched (3me-C₂₃, 3me-C₂₅), and unsaturated (Z9:C₂₃, Z9:C₂₅, Z9:C₂₇ compounds in extracts from females were assessed in arena bioassays, assessing four distinct steps in the mating behavior sequence of males (orientation, arrestment, body alignment, mounting and attempting to couple the genitalia). Males were unresponsive to freeze-killed, solventwashed females treated with blends of straight-chain and methyl-branched alkanes, but responded strongly to females treated with the blend of alkenes. Further trials determined that the complete sequence of mating behaviors, up to and including coupling the genitalia, was elicited by Z9:C₂₅ alone. Z9:C₂₅ comprised 16.4 ± 1.3% of the total hydrocarbons in whole-body hexane extracts of females and was co-dominant with two other hydrocarbons that were not active. In contrast, in solid phase microextraction (SPME) wipe samples from several areas of the cuticle, Z9:C₂₅ appeared as the single dominant peak, comprising 34.6 – 37.8% of the sampled hydrocarbons. Our data indicate that Z9:C₂₅ is a contact sex pheromone of M. robiniae, being the most abundant hydrocarbon on the surface of the cuticular wax layer of females where it is readily accessible to the antennae of males.     

Geochemical and ecological significance of soil lipids under Rhododendron ponticum stands

The bio-geographical significance of Rhododendron ponticum spp. baeticum (Ericaceae) as a relict species is well recognized. However, out of its native habitat it is an invasive exotic considered a major threat to natural ecosystems in areas of Atlantic Western Europe. The studies on the impact of Rhododendron influence on soil organic matter composition and associated ecological implications, i.e. presence of bioactive compounds with ecological significance, are limited. This work describes the soil lipid assemblage in three sites under Rhododendron stands and adjacent sites with deciduous oak (Quercus canariensis), both in their native habitats in Southern Spain (Sierra de Luna, Cádiz). The results are discussed in terms of organic matter dynamics and the presence of molecules that may be associated with Rhododendron invasive success. The soils are acid Xerochrepts formed on siliceous sands. Composite soil samples were taken at two depths (0?C10?cm and 10?C20?cm) and soxhlet extracted with a dichloromethane-methanol mixture (3:1). Soil lipid assemblage was studied by GC/MS after fractionation and appropriate derivatization of extracts. The qualitative chemical composition of soil extractable lipids under Rhododendron is reported here for the first time. Our results show that soil n-alkane and fatty acid distributions are compatible with an input from plant epicuticular waxes, as well as with the occurrence of selective preservation of long-chain fatty acids with depth. The pattern of short-chain n-alkanes found in surface samples indicates an anthropogenic contamination threat from nearby industrialized areas of ??Campo de Gibraltar??. The presence of branched iso and anteiso C₁₅ and C₁₇, ??-hydroxy fatty acids and the sterol brassicasterol points to high microbial soil activity. Finally, the pentacyclic triterpenes taraxerone and taraxerol were detected in soils with Rhododendron but not with Quercus. These are known bio-active plant compounds and could be related with the effectiveness of Rhododendron as an invasive exotic species.     

Isotopic evidences for microbiologically mediated and direct C input to soil compounds from three different leaf litters during their decomposition

We show the potentiality of coupling together different compound-specific isotopic analyses in a laboratory experiment, where ¹³C-depleted leaf litter was incubated on a ¹³C-enriched soil. The aim of our study was to identify the soil compounds where the C derived from three different litter species is retained. Three ¹³C-depleted leaf litter (Liquidambar styraciflua L., Cercis canadensis L. and Pinus taeda L., δ¹³C_vsPDB ≈ ?43‰), differing in their degradability, were incubated on a C4 soil (δ¹³C_vsPDB ≈ ?18‰) under laboratory-controlled conditions for 8 months. At harvest, compound-specific isotope analyses were performed on different classes of soil compounds [i.e. phospholipids fatty acids (PLFAs), n-alkanes and soil pyrolysis products]. Linoleic acid (PLFA 18:2ω6,9) was found to be very depleted in ¹³C (δ¹³C_vsPDB ≈ from ?38 to ?42‰) compared to all other PLFAs (δ¹³C_vsPDB ≈ from ?14 to ?35‰). Because of this, fungi were identified as the first among microbes to use the litter as source of C. Among n-alkanes, long-chain (C27–C31) n-alkanes were the only to have a depleted δ¹³C. This is an indication that not all of the C derived from litter in the soil was transformed by microbes. The depletion in ¹³C was also found in different classes of pyrolysis products, suggesting that the litter-derived C is incorporated in less or more chemically stable compounds, even only after 8 months decomposition.     

Structure and function of Dufour gland pheromones from the crazy ant <Emphasis Type="Italic">Paratrechina longicornis</Emphasis>

Summary. Dufour glands of Paratrechina longicornis were analyzed chemically using GC-MS techniques. The glands contained twelve alkanes between C₉ and C₂₀ chain length with undecane and tridecane as the main components, six alkenes (1- and 4-undecene, 1-, 4-, and 6- tridecene, and heptadecadiene), two alkyl formates (C₁₁ and C₁₃), and saturated and polyunsaturated acids. Many of the alkanes and alkenes were behaviorally active causing a short lasting attraction of ants with different intensity. Detection of the major gland compound undecane in recruitment trails by in vivo SPME sampling provided evidence for its use as a recruitment pheromone. Both poison gland (formic acid) and Dufour gland (undecane) contents were detected on SPME fibers which had been attacked by the ants.     

Alkanes and hopanes for pollution source apportionment in coking plant soils

Polluted soils of former coking plants are characterized by multiple organic contributions, e.g. coal tar, coal, coke, soot, and natural organic matter, that can either be sources of polycyclic aromatic hydrocarbons (PAHs) or act as sorption surfaces for pollutants. The contamination level is usually based on the quantification of 16 PAHs but it does not provide any information on PAH sources. We studied the aliphatic fractions of 25 soil samples from a former coking plant site by microscopy and gas chromatography-mass spectrometry (GC-MS). The microscopic investigation allowed to identify four main organic contributions: coal tar, coal, coke, and natural organic matter. These isolated sources were analyzed and considered as reference materials. Although the PAH distributions were very similar in the 25 contaminated soils, alkanes and hopanes distributions were representative from various contributions characterizing the relative enrichment in coal, coal tars, or natural organic matter. Two principal component analyses based on n-alkanes and hopanes showed that three molecular indices, the carbon preference index, the low molecular weight/high molecular weight n-alkanes ratio, and the 18α(H)-22,29,30-trisnorhopane/(18α(H)-22,29,30-trisnorhopane+17α(H)-22,29,30-trisnorhopane) ratio allow to classify polluted soils according to various organic contributions.     

Application of an odd/even predominance of n-alkanes in oil–source rock correlation: taking the lower Paleozoic strata of the Tarim Basin as an example

The composition and distribution of n-alkanes carbon numbers reflect the source of kerogenic organic matter, sedimentary environment, and maturity of the rocks. The comparison results of the n-alkanes GC (gas chromatography) chromatograms in the Tazhong Low Uplift show that the n-alkanes of the source rocks in Upper Ordovician display an odd carbon number predominance. At the same time, Cambrian–Lower Ordovician exhibit an even carbon number predominance. The correlation between oil and source rock illustrates that crude oils in the fields of well TZ10-12 and well TZ24 stem from the Upper Ordovician source rocks. The origins of the crude oils in the fields of well TZ161-162 and well TZ45 are Cambrian–Lower Ordovician. The strata corresponding to the crude oils with odd/even carbon number predominance match the oil–source rock correlation. Thus, the characteristics of odd/even carbon number predominance in n-alkane compounds are effective for oil–source rock correlation in the Tazhong Low Uplift, Tarim Basin.     

Evidence for n-alkane consumption and oxidation by filamentous cyanobacteria from oil-contaminated coasts of the Arabian Gulf

Microcoleus chthonoplastes and Phormidium corium were isolated from microbial mats covering all sediments along the Arabian Gulf coasts. These isolates could consume and oxidise n-alkanes. The establishment of axenic cultures faced the problem that with progressive axenity the cyanobacterial growth seemed to cease. The associated organotrophic bacteria, Rhodococcus rhodochrous, Arthrobacter nicotianae, Pseudomonas sp. and Bacillus sp., could utilize n-alkanes. The total number of these organotrophs was about 2×10⁶ cells g⁻¹ fresh culture, and R. rhodochrous was the most dominant. In order to test the potential of cyanobacteria for n-alkane consumption, experiments were constructed to rule out the role of the associated organotrophic bacteria. Aliquots, 0.5 g fresh cyanobacterial samples, each containing about 1×10⁶ organotrophic bacterial cells (≡0.001 mg fresh bacteria) were incubated in inorganic medium aliquots supplied with an n-alkane. The same was repeated using 1.0×10⁶ cells each of the four organotrophic bacteria instead of the cyanobacterial samples. The nonaxenic cyanobacterial samples consumed up to 60% of the available alkane, whereas no detectable consumption was measured in any of the pure organotrophic bacterial cultures. For all organotrophic bacteria, the numbers had to be increased ten-thousand times in order that detectable alkane consumption might become measurable. The fatty acids resulting from the n-alkane oxidation were found incorporated in cell lipid classes characteristic of cyanobacteria, namely in galactolipids and sulfolipids. These results may imply that the two test cyanobacteria contribute directly to n- alkane uptake and oxidation. Received: 6 May 1997 / Accepted: 2 October 1997     

Investigation of the sources of aliphatic hydrocarbons in the mussel Mytilus edulis from north sea oil production platforms by Capillary glc and CGCMS†

Aliphatic hydrocarbons isolated from mussels collected over a 20 month period from three North Sea Forties field oil production platforms have been examined by capillary gas chromatography and gas chromatography‐mass spectrometry.

The biological hydrocarbons consist predominantly (300–700 μh g^‐1 lipid) of C₃₁ and C₃₃ n‐alkenes with 2, 3 and 4 double bonds probably derived from a dietary intake of Emiliania huxleyi, a microscopic coccolithophorid alga. In some of the mussels C₁₈, C₂₀ and C₂₂ n‐alkanes are present in unusually high abundance compared to their odd carbon number homologues. Possible reasons for this distribution are discussed.

The concentrations of fossil fuel hydrocarbons (mainly unresolved complex mixtures) in the mussels ranged from 330 to 5,298 μg g^‐1 of lipid. No significant increase in values was detected two months after the start of discharge of treated Forties production water from the Forties D platform.

To determine the pollutant hydrocarbon sources, the sterane and terpane distributions of hydrocarbon fractions isolated from the mussels and from a number of fossil fuels, including Forties crude oil, were examined by mass fragmentography. The steranes in the mussels from the Forties C and D platforms contained higher proportions of regular 14α(H), 17α(H) components than Forties oil in which the steranes were mainly 13ß(H), 17α(H) diasteranes. In addition, the terpane distributions of the mussel fractions differed markedly from that of Forties crude oil, particularly in the relative abundance of diterpanes to triterpanes, which was higher in the mussel fractions than in the oil, and in the absence of 17α(H), 18α(H), 21ß(H)‐18, 30‐bisnorhopane, a known component of Forties crude. Furthermore, the ratio of C₂₉ to C₃₀ triterpanes was greater than unity in the mussels but much less than unity in the Forties oil. These data preclude Forties or other similar North Sea crudes as the major source of pollutant aliphatic hydrocarbons in the mussels. The relative concentrations and distributions of steranes and triterpanes suggest that the most likely source of pollutants is a Middle Eastern based oil derived either from rig activities, or from background pollution in the North Sea. The low concentration of ≥ C₂₇ steranes in the more polluted mussels (e.g. Forties B; UCM > 200 ppm dry wt.) suggests that gas oils used on the platforms may be the major source of petrogenic hydrocarbons in these samples.     

Terminal double bonds in the alkenes and acetates of defensive secretion from the thrips Suocerathrips linguis Mound & Marullo, 1994 (Thysanoptera: Phlaeothripidae)

Defensive secretions of adult males and females of the subsocial thrips Suocerathrips linguis were examined using gas chromatography–mass spectrometry (GC–MS). The samples contained six long-chain acetates and five aliphatic alkanes and alkenes. Whole-body extracts yielded six methyl esters of fatty acids as well as hexadecyl acetate. Structures of the two main components, (11Z)-icosa-11,19-dienyl acetate and octadecyl acetate, were confirmed. The third most abundant substance was identified as octadec-17-enyl acetate, which is a new natural product. In addition, (9Z)-octadec-9-enyl acetate was identified along with other acetates. Pure icosadienyl acetate was found to remain liquid down to −15°C, and is the solvent for the solid components of the secretion cocktail. A tentative biosynthetic pathway for all of the 12 acetates, alkanes and alkenes is discussed, considering especially the components with terminal double bonds that are uncommon in Thysanoptera and other insects.     

Bioavailability of hydrophobic organic contaminants and quality of organic carbon

U.S. laws require that contaminant bioaccumulation potential be evaluated before dredged material can be recycled. Simple fugacity models, e.g. organic contaminant aqueous partition coefficient (K _oc)-derived theoretical bioaccumulation potential, are commonly used to estimate the partitioning of hydrophobic organic contaminants between sediment organic matter and organism lipid. K _oc-derived models, with or without the addition of a soot carbon term, did not accurately or consistently predict total polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls partitioning of eight sediments from ongoing dredging operations onto C₁₈-coated filter paper. These models also failed to predict the partitioning of individual PAHs from these eight sediments. These data underscore the trade-offs between the ease of using simple models and the uncertainty of predicted partitioning values.     

Lipid storage and composition in tropical surgeonfishes (Teleostei: Acanthuridae)

The lipid composition of tropical marine reef fishes is poorly known, despite their use as food by local human populations and recent interest in health-related benefits of fish lipids. We examined the composition of lipids from epaxial muscle, liver, and two storage sites [mesenteries surrounding the gut (intraperitoneal fat, IPFs) and retroperitoneal fat bodies (FBs) posterior to the peritoneal cavity] in three species of surgeonfishes from Ishigaki Island, Japan: Naso lituratus (Bloch and Schneider, 1801), Acanthurus lineatus (Linnaeus, 1758), and A. bariene (Lesson, 1830). Triacylglycerols dominated all samples of neutral lipid and constituted ≥ 99% of FBs and IPFs. Polar lipids generally contained large fractions of phosphatidylethanolamine and phosphatidylcholine. Quantified fatty acids ranged in length from C₁₄ to C₂₄. C₁₆ fatty acids prevailed (>35% of neutral fatty acids, >23% of polar fatty acids), although C₁₈ (>16 and >14%, respectively) and C₂₀ acids (>8 and >19%, respectively) were also common. Saturated fatty acids, dominated by palmitic acid (16:0), comprised 38.7 to 50.7% of acids from neutral lipids and 30.8 to 41.1% from polar lipids. The most common monounsaturated acids were 18:1n9 and 20:1n9. Polyunsaturated acids were prevalent in polar lipids (especially 20:4n6, 20:5n3, 22:2n3, 22:5n3, 22:5n6 and 22:6n3). Common polyunsaturated acids of neutral lipids were 18:2n6, 18:4n3, several n-3 and n-6 C₂₀ acids, 22:2n3 and 22:5n3. IPF and FB were almost identical across species, and lipids of fat bodies (IPFs, FBs) were more similar to those of muscle than those of liver for all three species. The FBs appear to constitute an accessory storage site, which overcomes constraints on lipid storage imposed by a small, inflexible abdominal cavity that contains both viscera and consistently voluminous gut contents. Fatty acid signatures indicate that largely overlooked epiphytic or epilithic diatoms contribute significantly to lipid acquisition. The combination of large quantities of both saturated and n-3 and other polyunsaturated fatty acids in surgeonfishes, in contrast to low saturates and high polyunsaturated acids in lipids of commercially important cool-water fishes, suggests that a study of dietary effects of fish lipids on human inhabitants of the tropics may be instructive insofar as human health and nutrition are concerned. Received: 16 March 1998 / Accepted: 6 August 1998     

Photosynthesis and carbon storage between tides in a brown alga, Fucus vesiculosus

Intertidal macroalgae may spend a significant part of their lives in air. During photosynthesis in air, they encounter much lower concentrations of inorganic carbon than in seawater. Because they accumulate inorganic carbon from seawater, we investigated whether they similarly accumulate it from air. We measured photosynthesis in the intertidal species Fucus vesiculosus L. during 1990 and 1991 with a gas-phase O₂ electrode or CO₂-exchange apparatus in air and with a liquid-phase O₂ electrode in seawater. Maximum rates were rapid and similar in air and seawater regardless of the method. Tissue from seawater could carry on photosynthesis in CO₂-free air, indicating that carbon was stored in the tissue. After 2 h, this store was depleted and photosynthesis ceased. Supplying CO₂ in air replenished the store. Under identical conditions, terrestrial C₃ and C₄ species showed no evidence of this store, but a CAM (crassulacean acid metabolism) species did. However, in contrast to the CAM behavior, F. vesiculosus did not store CO₂ significantly in the dark. We found a small acid-releasable pool of carbon in the tissue that disappeared as photosynthesis depleted the carbon store. However, the pool was too small to account for the total carbon stored. While CO₂ was being acquired or released from the store in the light, photosynthesis was not inhibited by 21% O₂. These results indicate that there are two parallel paths for the supply of CO₂ to photosynthesis. The first depends on inorganic carbon in seawater or in air and supports rapid photosynthesis. The second involves CO₂ slowly released from an organic intermediate. The release protects CO₂ fixation from the inhibitory effects of 21% O₂. Photosynthesis in F. vesiculosus thus appears to be C₃-like in its rapid fixation of CO₂ from a small inorganic pool into phosphoglycerate. However, it is C₄-like in its pre-fixation of carbon in an organic pool in the light, and is CAM-like in its ability to slowly use this pool as a sole source of CO₂. The organic pool may serve to protect photosynthetic CO₂ fixation against the inhibitory effects of O₂ in air and in the boundary layer in seawater. Received: 6 March 1998 / Accepted: 16 October 1998     

Alkanes and alkenes in marine benthic algae

Saturated and olefinic hydrocarbons were determined in additional species of benthic marine algae from the Cape Cod (Massachusetts, USA) area (see: Youngblood et al., 1971). The distribution of homologous and isomeric olefins was studied in plants of different age and in morphologically different parts of the same specimen. With two minor exceptions, only normal alkanes and alkenes are present. The methylene-interrupted C₁₉- and C₂₁-polyolefins are particularly abundant; ¹-heneicosahexaene and the corresponding pentaene are common to all brown algae, while the corresponding ³-isomers occur in green algae. The hydrocarbon concentration, the alkene-to-alkane ratio and the polyolefin content are highest in young plants or in rapidly growing tissues of older plants. This suggests a deeper involvement in cell biochemistry of straight-chain hydrocarbons than previously considered. The biosynthesis of the plant polyolefins remains to be explored; no immediately obvious precursors of the ¹-polyolefins were found among the algal fatty acids. The hydrocarbon composition of these benthic algae differs greatly from that of fossil fuels in its simplicity and predominately unsaturated nature. The separation of the isomers by gas chromatography and their structural elucidation by mass spectrometry, alone and in combination with hydrogenation and ozonolysis, are discussed.Contribution No. 3155 of the Woods Hole Oceanographic Institution.     

Impacts of n-alkane concentration on soil bacterial community structure and alkane monooxygenase genes abundance during bioremediation processes

Petroleum hydrocarbons, mainly consisting of n-alkanes and polycyclic aromatic hydrocarbons (PAHs), are considered as priority pollutants and biohazards in the environment, eventually affecting the ecosystem and human health. Though many previous studies have investigated the change of bacterial community and alkane degraders during the degradation of petroleum hydrocarbons, there is still lack of understanding on the impacts of soil alkane contamination level. In the present study, microcosms with different n-alkane contamination (1%, 3% and 5%) were set up and our results indicated a complete alkane degradation after 30 and 50 days in 1%- and 3%-alkane treatments, respectively. In all the treatments, alkanes with medium-chain length (C₁₁-C₁₄) were preferentially degraded by soil microbes, followed by C₂₇-alkane in 3% and 5% treatments. Alkane contamination level slightly altered soil bacterial community, and the main change was the presence and abundance of dominant alkane degraders. Thermogemmatisporaceae, Gemmataceae and Thermodesulfovibrionaceae were highly related to the degradation of C₁₄- and C₂₇-alkanes in 5% treatment, but linked to alkanes with medium-chain (C₁₁-C₁₈) in 1% treatment and C₂₁-alkane in 3% treatment, respectively. Additionally, we compared the abundance of three alkane-monooxygenase genes, e.g., alk_A, alk_P and alk_R. The abundance of alk_R gene was highest in soils, and alk_P gene was more correlated with alkane degradation efficiency, especially in 5% treatment. Our results suggested that alkane contamination level showed non-negligible effects on soil bacterial communities to some extents, and particularly shaped alkane degraders and degrading genes significantly. This study provides a better understanding on the response of alkane degraders and bacterial communities to soil alkane concentrations, which affects their biodegradation process.

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Antioxidant responses in the polychaete Perinereis gualpensis (Nereididae) exposed to the carbon nanomaterial fullerene (C60)

The objective of this study was to analyse biochemical responses induced by the carbon nanomaterial fullerene (C₆₀) in the polychaete Perinereis gualpensis (Nereididae). The activity of glutathione-S-transferase (GST), glutathione reductase (GR) and glutamate cysteine ligase (GCL), as well as total antioxidant capacity, concentration of glutathione (GSH) and malondialdehyde (TBARS), were analysed. Estuarine worms were maintained in sediments collected at an unpolluted site and spiked with fullerene (3 mg C₆₀·g^?1 sediment). A control group was run in parallel. Scanning electron microscope (SEM) images of sediment and fullerene indicated that the size of the carbon nanomaterial should enable it to be ingested by the polychaete. No evidence of oxidative damage (TBARS) was observed in any of the treatments, and the same was true for GSH and GCL measurements (p>0.05). Total antioxidant capacity was higher in the C₆₀ group after 2 and 7 d when compared with the control group (p<0.05), suggesting that fullerene is acting as an antioxidant. The fact that P. gualpensis is an infaunal organism diminishes the chance of fullerene photoexcitation with consequent reactive oxygen species production. Thus, the data indicated an absence of toxic responses mediated by oxidative stress in estuarine worms exposed to C₆₀ mixed in sediments.