Ramsés Capilla

Determination of trace metals in high-salinity petroleum produced formation water by inductively coupled plasma mass spectrometry following on-line analyte separation/preconcentration

A procedure is detailed for the determination of trace metals in high salinity petroleum produced formation water (PFW) by inductively coupled plasma mass spectrometry (ICP-MS) coupled with flow injection (FI) on-line matrix separation and preconcentration. High salinity PFW waters present complex composition containing various organic and inorganic substances. Mini-columns packed with Toyopearl AF-Chelate-650M iminodiacetate resin were used for the analyte separation/preconcentration of Cd, Pb, Ni, Zn, V, Co and U; Toyopearl 8-hydroxiquinoline resin for Fe, and silica immobilized 8-hydroxyquinoline resin for Mo. A Doehlert matrix and desirability function was used to generate response surfaces to optimize the column separation/preconcentration parameters. Using 7.5 mL aliquots of PFW, method limits of detection of 0.0007, 0.009, 0.017, 0.024, 0.0002, 0.047, 0.058, 0.002, 0.013 and 0.041 ng ml−1 were obtained for Cd, Pb, Ni, Zn, U, Mo, Fe, Co, V and Mn, respectively. Vanadium, Co and Mn were determined by the method of standard additions whereas Cd, Pb, Ni, Zn, Mo, Fe and U were quantitated using isotope dilution. CASS-4 (coastal seawater) certified reference material was used for method validation and high-salinity PFW (39–120‰) from Brazilian offshore platforms examined. The concentration ranges found in these waters were 0.013–1.47, 0.057–0.80, 0.229–5.1, 0.096–3360, 0.001–0.081, 0.244–69, 0.84–1419, 0.004–3.5, 0.088–0.85 and 4.2–6230 ng ml−1 for Cd, Pb, Ni, Zn, U, Mo, Fe, Co, V and Mn, respectively.

Particle Fluxes and Bulk Geochemical Characterization of the Cabo Frio Upwelling System in Southeastern Brazil: Sediment Trap Experiments between Spring 2010 and Summer 2012

Physical and biogeochemical processes in continental shelves act synergistically in both transporting and transforming suspended material, and ocean dynamics control the dispersion of particles by the coastal zone and their subsequent mixing and dilution within the shelf area constrained by oceanic boundary currents, followed by their gradual settling in a complex sedimentary scenario. One of these regions is the Cabo Frio Upwelling System located in a significantly productive area of Southeastern Brazil, under the control of the nutrient-poor western boundary Brazil Current but also with a wind-driven coastal upwelling zone, inducing cold-water intrusions of South Atlantic Central Water on the shelf. To understand these synergic interactions among physical and biogeochemical processes in the Cabo Frio shelf, a series of four experiments with a total of 98 discrete samples using sediment traps was performed from November 2010 to March 2012, located on the 145 m isobath on the edge of the continental shelf. The results showed that lateral transport might be relevant in some cases, especially in deep layers, although no clear seasonal cycle was detected. Two main physical-geochemical coupling scenarios were identified: singular downwelling events that can enhance particles fluxes and are potentially related to the Brazil Current oscillations; and events of significant fluxes related to the intrusion of the 18°C isotherm in the euphotic zone. The particulate matter settling in the Cabo Frio shelf area seems to belong to multiple marine and terrestrial sources, in which both Paraiba do Sul River and Guanabara Bay could be potential land-sources, although the particulate material might subject intense transformation (diagenesis) during its trajectory to the shelf edge.

Early diagenesis of sulfur in a tropical upwelling system, Cabo Frio, southeastern Brazil

The early diagenesis of sulfur was assessed in four short sediment cores on the continental shelf off southeastern Brazil that were deposited under the influence of an upwelling tropical system. This tropical upwelling area allows a direct focus on the coupled roles of hydrodynamic- and bioturbation-driven influences on sulfate reduction, sulfide re-oxidation and corresponding stable sulfur isotope signal formation. Under the depositional conditions of Cabo Frio, the degree of reactive iron pyritization was limited by both dissolved sulfide availability and pyrite oxidation events. Textural analyses of pyrite framboids provide evidence of re-oxidation processes, reflecting dynamic redox conditions in the sediments. The isotope composition of pore-water sulfate remained close to the modern seawater value, but very light stable sulfur isotope ratios ( 34 S/ 32 S) of chromium reducible sulfur (essentially pyrite) are found that reflect intense bioturbation-induced sulfur re-cycling. The sulfur isotope signatures developing in these tropical upwelling sites are similar to those of modern euxinic systems, although they are caused by a superimposition of sulfate reduction and an intense oxidative sulfur cycle.

Geoacoustic character, sedimentology and chronology of a cross-shelf Holocene sediment deposit off Cabo Frio, Brazil (southwest Atlantic Ocean)

The Cabo Frio region in the state of Rio de Janeiro, southeast coast of Brazil, is characterized by a local coastal upwelling system and converging littoral sediment transport systems that are deflected offshore at Cabo Frio, as a consequence of which a thick cross-shelf sediment deposit has developed over time. To investigate the evolution of this muddy deposit, geophysical, sedimentological and geochemical data from four sediment cores (3.8–4.1 m in length) recovered in water depths between 88 and 141 m were analyzed. The high-resolution seismic data show variable sediment thicknesses ranging from 1 to 20 m, comprising two sedimentary units separated by a high-impedance layer at a depth of about 10 m below the seafloor at the coring sites. According to the available age datings, the upper sedimentary unit is late Pleistocene to Holocene in age, whereas the lower unit (not dated) must, by implication, be entirely Pleistocene in age. The boomer-seismic reflection signal can be divided into three echo-types, namely transparent (inner shelf), stratified (middle shelf) and reflective (outer shelf), each type seemingly related to the local sediment composition. The upper 4 m of the upper sedimentary unit is dominated by silty sediment on the middle shelf, and by upward-fining sediments (silty sand to sandy silt) on the inner and outer shelf. The downcore trends of P-wave velocity, gamma-ray density and acoustic impedance are largely similar, but generally reversed to those of water and organic carbon contents. Total organic carbon contents increase with decreasing mean grain size, periodic fluctuations suggesting temporal changes in the regional hydrodynamics and primary productivity fuelled by the local upwelling system. The reconstruction of sedimentation rates in the course of the Holocene is based on 35 AMS age datings of organic material recovered from variable downcore depths. These range from a maximum of 13.3 cm/decade near the base of the inner shelf core (7.73–7.70 ka BP) to generally very low values (<0.11 cm/century) over the last thousand years in all cores. Over the last 6 ka there appear to have been three distinct sedimentation peaks, one between 6 and 5 ka BP, another between 4 and 3 ka PB, and one around 1 ka BP. Due to different time intervals between dates, not every peak is equally well resolved in all four cores. Based on the similar sedimentology of the inner and outer shelf cores, an essentially identical sedimentation model is proposed to have been active in both cases, albeit at different times. Thus, already during the last glacial maximum, alongshore sediment transport was deflected offshore by a change in shoreline orientation caused by the Cabo Frio structural high. The source of terrigenous material was probably a barrier-island complex that was subsequently displaced landward in the course of sea-level rise until it stabilized some 6.5 ka BP along the modern coast.

Microbial diversity in degraded and non-degraded petroleum samples and comparison across oil reservoirs at local and global scales

Microorganisms have shown their ability to colonize extreme environments including deep subsurface petroleum reservoirs. Physicochemical parameters may vary greatly among petroleum reservoirs worldwide and so do the microbial communities inhabiting these different environments. The present work aimed at the characterization of the microbiota in biodegraded and non-degraded petroleum samples from three Brazilian reservoirs and the comparison of microbial community diversity across oil reservoirs at local and global scales using 16S rRNA clone libraries. The analysis of 620 16S rRNA bacterial and archaeal sequences obtained from Brazilian oil samples revealed 42 bacterial OTUs and 21 archaeal OTUs. The bacterial community from the degraded oil was more diverse than the non-degraded samples. Non-degraded oil samples were overwhelmingly dominated by gammaproteobacterial sequences with a predominance of the genera Marinobacter and Marinobacterium. Comparisons of microbial diversity among oil reservoirs worldwide suggested an apparent correlation of prokaryotic communities with reservoir temperature and depth and no influence of geographic distance among reservoirs. The detailed analysis of the phylogenetic diversity across reservoirs allowed us to define a core microbiome encompassing three bacterial classes (Gammaproteobacteria, Clostridia, and Bacteroidia) and one archaeal class (Methanomicrobia) ubiquitous in petroleum reservoirs and presumably owning the abilities to sustain life in these environments.

Seismic peak amplitude as a predictor of TOC content in shallow marine sediments

Acoustic remote sensing is a highly effective tool for exploring the seafloor of both deep and shallow marine settings. Indeed, the acoustic response depends on several physicochemical factors such as sediment grain size, bulk density, water content, and mineralogy. The objective of the present study is to assess the suitability of seismic peak amplitude as a predictor of total organic carbon (TOC) content in shallow marine sediments, based on data collected in the Cabo Frio mud belt in an upwelling zone off southeastern Brazil. These comprise records of P-wave velocity (VP) along 680 km of high-resolution single-channel seismic surveys, combined with analyses of grain size, wet bulk density, absolute water content and TOC content for four piston-cores. TOC contents of sediments from 13 box-cores served to validate the methodology. The results show well-defined positive correlations between TOC content and mean grain size (phi scale) as well as absolute water content, and negative correlations with VP, wet bulk density, and acoustic impedance. These relationships yield a regression equation by which TOC content can be satisfactorily predicted on the basis of acoustic impedance for this region: y = − 4.84 ln(x) + 40.04. Indeed, the derived TOC contents differ by only 5% from those determined by geochemical analysis. After appropriate calibration, acoustic impedance can thus be conveniently used as a predictor of large-scale spatial distributions of organic carbon enrichment in marine sediments. This not only contributes to optimizing scientific project objectives, but also enhances the cost-effectiveness of marine surveys by greatly reducing the ship time commonly required for grid sampling.