Ana Luiza Spadano Albuquerque

A review of nitrogen isotopic alteration in marine sediments

Key Points: Use of sedimentary nitrogen isotopes is examined; On average, sediment 15N/14N increases approx. 2 per mil during early burial; Isotopic alteration scales with water depth Abstract: Nitrogen isotopes are an important tool for evaluating past biogeochemical cycling from the paleoceanographic record. However, bulk sedimentary nitrogen isotope ratios, which can be determined routinely and at minimal cost, may be altered during burial and early sedimentary diagenesis, particularly outside of continental margin settings. The causes and detailed mechanisms of isotopic alteration are still under investigation. Case studies of the Mediterranean and South China Seas underscore the complexities of investigating isotopic alteration. In an effort to evaluate the evidence for alteration of the sedimentary N isotopic signal and try to quantify the net effect, we have compiled and compared data demonstrating alteration from the published literature. A >100 point comparison of sediment trap and surface sedimentary nitrogen isotope values demonstrates that, at sites located off of the continental margins, an increase in sediment 15N/14N occurs during early burial, likely at the seafloor. The extent of isotopic alteration appears to be a function of water depth. Depth-related differences in oxygen exposure time at the seafloor are likely the dominant control on the extent of N isotopic alteration. Moreover, the compiled data suggest that the degree of alteration is likely to be uniform through time at most sites so that bulk sedimentary isotope records likely provide a good means for evaluating relative changes in the global N cycle.

A 21 000 cal years paleoclimatic record from Caçó Lake, northern Brazil: evidence from sedimentary and pollen analyses

Abstract Sedimentological studies including seismic profiles, mineralogy and organic geochemistry on two cores from the center and margin of Caco Lake, Maranhao State, northern Brazil, revealed variable climatic and environmental conditions during the last 21 cal kyr BP. Between 21 and 17 cal kyr BP, during the Late Glacial Maximum, regional climate was predominantly dry, interrupted by short humid phases, as reflected by a succession of very thin layers of sand and organic matter. The Late Pleistocene climate was relatively wet as is suggested by rapid lake-level rise and forest expansion. The Late Pleistocene humid climate differed significantly from present conditions. We suggest that Late Glacial humid conditions were the consequence of intensification of the Inter-Tropical Convergence Zone or shifts of its position, resulting in Antarctic cold-front occurrences. The abrupt climatic changes during this period were marked by siderite deposition into Caco Lake, which appears to be related to regional hydrologic changes linked to global/Northern Hemisphere events. The Holocene was characterized by lower moisture availability and a distinct dry period until 7 cal kyr BP, in response to South American insolation conditions.

The eutrophication history of a tropical water supply reservoir in Brazil

Guarapiranga Reservoir is the second most important public water supply in São Paulo, Brazil and has been eutrophic for several decades. We inferred the major ecological shifts for the period 1919–2010 related to multiple stressors (forest flooding, hydrological change, use of algicide and eutrophication), using geochemistry (TOC, TN, TP, C/N, δ15N, δ13C) and diatom assemblages in a short (75-cm) sediment core. Thirty-two diatom species were abundant in the core and stratigraphically constrained incremental sum of squares analysis enabled identification of three diatom zones and four subzones, i.e. depths at which marked changes in species composition occurred. Early diatom assemblages were dominated by benthic, oligotrophic taxa, mainly Eunotia, influenced by flooded vegetation after dam construction. A shift to dominance by a planktonic species (Eunotia tukanorum) occurred ca. 1932, during the period of initial physical disturbance and early use of the water body as a public water supply. Diatoms and geochemical variables show that the reservoir was oligotrophic from ~1919 to 1947. Eutrophication began ~1975 and by the early 1980s the reservoir had become eutrophic, in response to an explosive increase in human population in the watershed. Severe cultural eutrophication has persisted since ~1990. Higher concentrations of copper in the sediments, beginning in 1991, reflect the increased use of copper sulfate to control cyanobacteria blooms and provide a chronological marker. Higher δ15N values in recent sediments indicate greater sewage inputs and low C/N values reflect the predominant contribution of algae to sediment organic matter. Eutrophic taxa Cyclotella meneghiniana and Nitzschia sp. dominate recent diatom assemblages, along with Aulacoseira granulata, a species that is tolerant of copper sulfate. Diatom assemblages reflect multiple stressors, however, geochemical information provides a better understanding of the early phase of the reservoir. Paleolimnologically documented trophic state changes in this important drinking water supply are largely attributable to increased urbanization of the drainage basin and inputs of sewage. Management efforts should focus on mitigating this nutrient source.

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.

Mercury deposition during the previous century in an upwelling region; Cabo Frio, Brazil

To investigate the upwelling influence on Hg biogeochemical cycles and the sedimentological changes during the previous ≈ 150 years, four sediment box-cores were sampled along an inshore offshore transect on the Southeastern Brazilian continental shelf. Mercury values were found to be relatively low, with means ranging between 8.08 and 30.4 ng g(-1). Mercury fluxes along the sediment cores are directly related to the well documented historical regional activity and global atmospheric deposition. The narrow relationship between mercury and organic carbon suggest that upwelling phenomenon and primary production may play an important role on Hg input and distribution along continental shelf depositional settings.

Holocene oscillations of Southwest Atlantic shelf circulation based on planktonic foraminifera from an upwelling system (off Cabo Frio, Southeastern Brazil)

The Brazil Current (BC) is a relevant feature in the Atlantic Meridional Overturning Circulation (AMOC). Its behavior during slowdown or intense AMOC remains poorly known because of the lack of paleoceanographic records, especially for the Holocene. Here, we investigate changes in a western boundary upwelling system (Cabo Frio, off Southeastern Brazil) which are driven by variations in the BC and NE winds during the last 9 kyr. To assess the variability of the BC, we used δ18O, Mg/Ca, and assemblages of planktonic foraminifera. Our results indicate five oceanographic phases during the last 9 kyr. During Phase I (from 9.0 to 7.0 cal kyr BP), the BC diverged offshore from the modern upwelling area because of the low sea level, increasing the influence of shelf waters and coastal upwelling plumes on foraminifera assemblages. Phase II (7.0–5.0 kyr BP) was marked by the approach of the internal front of the BC with low intensity and episodes of strong productivity that were linked primarily to the upwelling of the South Atlantic Central Water (SACW) and/or Subpolar Shelf Waters (SPSWs) (cold). Phase III (5.0–3.5 kyr BP) was a transition, marking a large oceanographic and climatic change from the weakening of the AMOC. The internal front of the BC became warm and subsurface SACW upwelling was stronger. In Phase IV (3.5–2.5 kyr BP), the BC acquired its modern dynamics, but weak NE winds weakened the SACW’s contribution to upwelling events. Finally, in Phase V (last 2.5 kyr BP), the NE winds reintensified, promoting frequent episodes of upwelling and intrusion by SPSWs during the Medieval Climate Anomaly.

Nutrient regeneration susceptibility under contrasting sedimentary conditions from the Rio de Janeiro coast, Brazil

Dissolved silicate (DSi), NH4(+), NO3(-) and PO4(3-) susceptibility to be exchanged between sediment pore waters and overlying waters was evaluated in Jurujuba Sound (JS station) and Coroa Grande Sound (CGS station), southeastern Brazil. Sedimentary elemental (C, N and P) and isotopic (δ(13)C and δ(15)N) compositions evidenced stronger anthropogenic fertilization in JS station. Net NO3(-) influxes from overlying waters occurred, which was two orders of magnitude higher under the more fertilized condition. This condition resulted in 6-13-times higher net effluxes of NH4(+), DSi and PO4(3-) to overlying waters. Vertical alternation between production and consumption processes in pore waters contributed for a more limited regeneration in CGS station. This was associated with diagenetic responses to sedimentary grain size variability in deeper layers and biological disturbance in upper layers. Nearly continuous production of NH4(+), DSi and PO4(3-) in pore waters implied in intensified susceptibility to remobilization under the eutrophic condition of JS station.

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.