Long-chain aliphatic wax esters isolated from the sponge Chalinula saudensis (Demospongia) along the Jeddah coast of the Red Sea

A esponja Chalinula saudensis ocorre ao longo da costa de Jeddah, Arabia Saudita, mas apenas recentemente foi isolada e identificada. No presente estudo a matéria orgânica total da esponja foi extraída por solventes e o extrato foi separado por partição sucessiva através do emprego de hexano e água, clorofórmio e água e finalmente t-butanol e água. A camada contendo clorofórmio foi então separada por cromatografia em sílica. Os resultados mostraram a presença de ésteres de quatro ácidos graxos de cadeira longa (C28H56O2, C30H60O2, C32H62O2 e C36H70O2), sendo que o segundo deles foi também identificado nos corais Millepora dichotoma e Millepora platyphylla. Não se tem evidência da presença dos demais compostos em outros organismos marinhos, embora haja relatos para ésteres semelhantes de cadeia longa, mas contendo diferentes cadeias alifáticas e diferentes pesos moleculares. Os compostos isolados em C. saudensis são geralmente ceras e sua presença na esponja tem importância não só nas rotas de biosíntese, mas servem como isolantes nas variações sazonais adversas.The sponge Chalinula saudensis, which occurs along the Jeddah coast, has only recently been isolated and identified. In this study, the total crude organic matter of the sponge was extracted by solvents. The total crude extract was further separated by partitioning it with hexane and water, then with water and chloroform, and finally with water and t-butanol. The chloroform layer was subjected to separation by preparative layer chromatography on silica. One fraction contained four long-chain fatty acid esters, C28H56O2, C30H60O2, C32H62O2 and C36H70 O2. The second ester, C30H60O2, has been identified in the fire corals Millepora dichotoma and Millepora platyphylla. The others have not previously been reported from marine organisms; however similar long-chain esters with different long aliphatic chains and with different molecular weights have been identified from other marine organisms. These compounds are normally waxy and their presence in Chalinula saudensis plays a vital role in the biosynthetic pathways. They also act as insulators against seasonal variations

Formation of Zn- and Fe-sulfides near hydrothermal vents at the Eastern Lau Spreading Center: implications for sulfide bioavailability to chemoautotrophs

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Speciation and fate of trace metals in estuarine sediments under reduced and oxidized conditions, Seaplane Lagoon, Alameda Naval Air Station (USA)

We have identified important chemical reactions that control the fate of metal-contaminated estuarine sediments if they are left undisturbed (in situ) or if they are dredged. We combined information on the molecular bonding of metals in solids from X-ray absorption spectroscopy (XAS) with thermodynamic and kinetic driving forces obtained from dissolved metal concentrations to deduce the dominant reactions under reduced and oxidized conditions. We evaluated the in situ geochemistry of metals (cadmium, chromium, iron, lead, manganese and zinc) as a function of sediment depth (to 100 cm) from a 60 year record of contamination at the Alameda Naval Air Station, California. Results from XAS and thermodynamic modeling of porewaters show that cadmium and most of the zinc form stable sulfide phases, and that lead and chromium are associated with stable carbonate, phosphate, phyllosilicate, or oxide minerals. Therefore, there is minimal risk associated with the release of these trace metals from the deeper sediments contaminated prior to the Clean Water Act (1975) as long as reducing conditions are maintained. Increased concentrations of dissolved metals with depth were indicative of the formation of metal HS(- )complexes. The sediments also contain zinc, chromium, and manganese associated with detrital iron-rich phyllosilicates and/or oxides. These phases are recalcitrant at near-neutral pH and do not undergo reductive dissolution within the 60 year depositional history of sediments at this site. The fate of these metals during dredging was evaluated by comparing in situ geochemistry with that of sediments oxidized by seawater in laboratory experiments. Cadmium and zinc pose the greatest hazard from dredging because their sulfides were highly reactive in seawater. However, their dissolved concentrations under oxic conditions were limited eventually by sorption to or co-precipitation with an iron (oxy)hydroxide. About 50% of the reacted CdS and 80% of the reacted ZnS were bonded to an oxide-substrate at the end of the 90-day oxidation experiment. Lead and chromium pose a minimal hazard from dredging because they are bonded to relatively insoluble carbonate, phosphate, phyllosilicate, or oxide minerals that are stable in seawater. These results point out the specific chemical behavior of individual metals in estuarine sediments, and the need for direct confirmation of metal speciation in order to constrain predictive models that realistically assess the fate of metals in urban harbors and coastal sediments

Geochemical classification of brine-filled Red Sea deeps

The major geochemical characteristics of Red Sea brine are summarized for 11 brine-filled deeps located along the central graben axis between 19°N and 27°N. The major element composition of the different brine pools is mainly controlled by variable mixing situations of halite-saturated solution (evaporite dissolution) with Red Sea deep water. The brine chemistry is also influenced by hydrothermal water/rock interaction, whereas magmatic and sedimentary rock reactions can be distinguished by boron, lithium, and magnesium/calcium chemistry. Moreover, hydrocarbon chemistry (concentrations and δ13C data) of brine indicates variable injection of light hydrocarbons from organic source rocks and strong secondary (bacterial or thermogenic) degradation processes. A simple statistical cluster analysis approach was selected to look for similarities in brine chemistry and to classify the various brine pools, as the measured chemical brine compositions show remarkably strong concentration variations for some elements. The cluster analysis indicates two main classes of brine. Type I brine chemistry (Oceanographer and Kebrit Deeps) is controlled by evaporite dissolution and contributions from sediment alteration. The Type II brine (Suakin, Port Sudan, Erba, Albatross, Discovery, Atlantis II, Nereus, Shaban, and Conrad Deeps) is influenced by variable contributions from volcanic/magmatic rock alteration. The chemical brine classification can be correlated with the sedimentary and tectonic setting of the related depressions. Type I brine-filled deeps are located slightly off-axis from the central Red Sea graben. A typical “collapse structure formation” which has been defined for the Kebrit Deep by evaluating seismic and geomorphological data probably corresponds to our Type I brine. Type II brine located in depressions in the northern Red Sea (i.e., Conrad and Shaban Deeps) could be correlated to “volcanic intrusion-/extrusion-related” deep formation. The chemical indications for hydrothermal influence on Conrad and Shaban Deep brine can be related to brines from the multi-deeps region in the central Red Sea, where volcanic/magmatic fluid/rock interaction is most obvious. The strongest hydrothermal influence is observed in Atlantis II brine (central multi-deeps region), which is also the hottest Red Sea brine body in 2011 (~68.2 °C)

Fecal sterols and pahs in sewage polluted marine environment along the eastern Red Sea coast, South of Jeddah, Saudi Arabia

404-410Water and sediment samples were takes near the sewage discharge point on the eastern Red Sea Coast of Jeddah and analyzed for PAH and fecal sterols like coprostanol, cholesterol and cholestanol. PAH were estimated spectrofluorometrically and then further analyzed by GC-MS. Sterols were derivatized by BSTFA into their corresponding trimethyl silyl derivatives and then analyzed by gas chromatography and quantified with standard sterols. PAH ranged from 1.5 to 6.5 g 1-1 in eight stations. Concentration of coprostanol in water samples showed a maximum of 8.2 g 1-1 at station XVIII and minimum 0.1 g 1-1 at station 10C. The analysis of the sediment samples indicated much higher values for fecal sterols. It was found to be 785 g 1-1 in sediment and 6.5 g 1-1 in the water samples at station XVIII. PAH did not show any distinct increase in the sediment samples. According to Grimaldt equation the value of r* (5 / 5 + 5) was determined. Out of a total of sixteen samples, fourteen samples had a value of 0.7 or higher than 0.7. This indicate a definite and a positive sewage contamination infecting almost the whole area studied. The GC-MS of the PAH indicate the presence of phenanthrene, benzophenone and 2,4-diisoprophyl naphthalene, methylnaphthalene, and 9-H-methylene flourene. Present study infers that the sewage; either untreated or partially treated is dumped into the sea

Expelled subsalt fluids form a pockmark field in the eastern Red Sea

This study aimed to constrain the source area of fluids responsible for the formation of a pockmark field in the eastern Red Sea. The newly discovered field extends over an area of at least 1,000 km2 at a water depth of ~400 m. The pockmarks have modal diameters of 140–150 m and are either randomly distributed on the seafloor or aligned within valleys approximately 25 m deep and several kilometres in length. Seismic data show that chimneys and/or regions of acoustic turbidity prevail beneath the pockmark field down to the top of Miocene evaporites, which are widespread in the Red Sea. Four gravity cores were taken from the pockmark field. For most of the cores, geochemical analyses show that porewater has a higher Cl concentration than the local seawater and increased Cl/Br ratios, which indicate an origin from evaporites. The adsorbed hydrocarbons are of thermal origin, with C1/(C2+C3) ratios between 4 and 23 and stable carbon isotope data for methane varying from δ13C of –34 to –36.4‰ with respect to Vienna Pee Dee Belemnite. On the basis of the calculated maturity of the source rock of 1.2–1.4 Ro, local thermal gradients and sedimentation rates, its deeper depth boundary is approximated at 2,000 to 2,200 m. The results indicate that the adsorbed hydrocarbons sampled at the seafloor had to pass through an evaporite sequence of potentially several hundred metres to a few km in thickness. The most likely explanation for the increased permeability of the evaporite sequence is brittle deformation triggered by extensive local tectonic movements and supported by high fluid overpressure within the evaporite sequence