Grain-size analyses and bulk chemistry determined in surface sediment samples along the Chilean continental margin in the Southeast Pacific Ocean

Physical, chemical, and mineralogical properties of a set of surface sediment samples collected along the Chilean continental slope (21-44°S) are used to characterise present-day sedimentation patterns and sediment provenance on the Chilean margin. Despite the presence of several exceptional latitudinal gradients in relief, oceanography, tectonic evolution, volcanic activity and onshore geology, the present-day input of terrigenous sediments to the Chilean continental margin appears to be mainly controlled by precipitation gradients, and source-rock composition in the hinterland. General trends in grain size denote a southward decrease in median grain-size of the terrigenous (Corganic, CaCO3 and Opal-free) fraction, which is interpreted as a shift from aeolian to fluvial sedimentation. This interpretation is supported by previous observations of southward increasing bulk sedimentation rates. North-south trends in sediment bulk chemistry are best recognised in the iron (Fe) and titanium (Ti) vs. potassium (K) and aluminium (Al) ratios of the sediments that most likely reflect the contribution of source rocks from the Andean volcanic arc. These ratios are high in the northernmost part, abruptly decrease at 25°S, and then more or less constantly increase southwards to a maximum at ~40°S.

Sesquióxidos de hierro en bosques templado húmedos del estado de Hidalgo, México

Se estudian las formas de hierro extraídas con oxalato ácido de amonio, pirofosfato de sodio, ditionito-citrato-bicarbonato, así como el hierro total en disolución en suelos Alisoles en el municipio de Acaxochitlán, Hidalgo, México. Los suelos estudiados soportan distintos tipos de vegetación forestal: Pinus patula Schlecht and Cham (Pp), Pinus teocote, (Pt) y Quercus spp, (Q). El objetivo del trabajo fue determinar si la vegetación influye significativamente sobre las diferentes fracciones de hierro (Fe) en el suelo. Los contenidos de Fe total son significativamente mayores en suelos bajo vegetación de Pp (14,5% de Fe2O3), el mayor porcentaje de ferrihidrita (38,0% del Fe total en suelo) y de complejos organominerales de Fe y óxidos amorfos de Fe (20,9% y 16,3% respectivamente del Fe total en suelo, se dio en el bosque de Pt. En los suelos bajo bosques de Pp predominaron formas de Fe lábil (56,7% del Fe total en suelo) y formas cristalinas de Fe (goetita/hematita). La vegetación de Q mostró mayor alteración de los suelos y en el caso de Pt y Pp se presentó una mayor evolución en el proceso de organización estructural de los oxihidróxidos de Fe. El tipo de vegetación forestal influye en el grado de evolución del suelo, y en la distribución, contenido y formas de óxidos de Fe. En un orden de mayor a menor el contenido de Fe total en el suelo fue Pinus patula > Quercus spp > Pinus teocote.

Surface water properties, phytoplankton composition and photosynthesis rates of Amundsen Sea sites

The phytoplankton community composition and productivity in waters of the Amundsen Sea and surrounding sea ice zone were characterized with respect to iron (Fe) input from melting glaciers. High Fe input from glaciers such as the Pine Island Glacier, and the Dotson and Crosson ice shelves resulted in dense phytoplankton blooms in surface waters of Pine Island Bay, Pine Island Polynya, and Amundsen Polynya. Phytoplankton biomass distribution was the opposite of the distribution of dissolved Fe (DFe), confirming the uptake of glacial DFe in surface waters by phytoplankton. Phytoplankton biomass in the polynyas ranged from 0.6 to 14 µg Chl a / L, with lower biomass at glacier sites where strong upwelling of Modified Circumpolar Deep Water from beneath glacier tongues was observed. Phytoplankton blooms in the polynyas were dominated by the haptophyte Phaeocystis antarctica, whereas the phytoplankton community in the sea ice zone was a mix of P. antarctica and diatoms, resembling the species distribution in the Ross Sea. Water column productivity based on photosynthesis versus irradiance characteristics averaged 3.00 g C /m**2/d in polynya sites, which was approximately twice as high as in the sea ice zone. The highest water column productivity was observed in the Pine Island Polynya, where both thermally and salinity stratified waters resulted in a shallow surface mixed layer with high phytoplankton biomass. In contrast, new production based on NO3 uptake was similar between different polynya sites, where a deeper UML in the weakly, thermally stratified Pine Island Bay resulted in deeper NO3 removal, thereby offsetting the lower productivity at the surface. These are the first in situ observations that confirm satellite observations of high phytoplankton biomass and productivity in the Amundsen Sea. Moreover, the high phytoplankton productivity as a result of glacial input of DFe is the first evidence that melting glaciers have the potential to increase phytoplankton productivity and thereby CO2 uptake, resulting in a small negative feedback to anthropogenic CO2 emissions.

(Table 1) Vertical turbulent eddy diffusivity of selected stations from the Nathaniel B. Palmer cruise NBP09-01

Dissolved iron (DFe) and total dissolvable Fe (TDFe) were measured in January-February 2009 in Pine Island Bay, as well as in the Pine Island and Amundsen polynyas (Amundsen Sea, Southern Ocean). Iron (Fe) has been shown to be a limiting nutrient for phytoplankton growth, even in the productive continental shelves surrounding the Antarctic continent. However, the polynyas of the Amundsen Sea harbor the highest concentrations of phytoplankton anywhere in Antarctica. Here we present data showing the likely sources of Fe that enable such a productive and long lasting phytoplankton bloom. Circumpolar Deep Water (CDW) flows over the bottom of the shelf into the Pine Island Bay where DFe and TDFe were observed to increase from 0.2 to 0.4 nM DFe and from 0.3-4.0 to 7-14 nM TDFe, respectively. At the southern end of Pine Island Bay, the CDW upwelled under the Pine Island Glacier, bringing nutrients (including Fe) to the surface and melting the base of the glacier. Concentrations of DFe in waters near the Pine Island Glacier and the more westward lying Crosson, Dotson, and Getz Ice Shelves varied between 0.40 and 1.31 nM, depending on the relative magnitude of upwelling, turbulent mixing, and melting. These values represent maximum concentrations since associated ligands (which increase the solubility of Fe in seawater) were saturated with Fe (Thuroczy et al., 2012, doi:10.1016/j.dsr2.2012.03.009). The TDFe concentrations were very high compared to what previously has been measured in the Southern Ocean, varying between 3 and 106 nM. In the Pine Island Polynya, macronutrients and DFe were consumed by the phytoplankton bloom and concentrations were very low. We calculate that atmospheric dust contributed < 1% of the Fe necessary to sustain the phytoplankton bloom, while vertical turbulent eddy diffusion from the sediment, sea ice melt, and upwelling contributed 1.0-3.8%, 0.7-2.9%, and 0.4-1.7%, respectively. The largest source was Fe input from the PIG, which could satisfy the total Fe demand by the phytoplankton bloom by lateral advection of Fe over a range of 150 km from the glacier. The role of TDFe as a phytoplankton nutrient remains unclear, perhaps representing an important indirect Fe source via dissolution and complexation by dissolved organic ligands (Gerringa et al., 2000, doi:10.1016/S0304-4203(99)00092-4; Borer et al., 2005, doi:10.1016/j.marchem.2004.08.006).

Geochemistry of middle Eocene-lower Oligocene pelagic sediments of ODP Hole 105-647A

Geochemical analyses of the middle Eocene through lower Oligocene lithologic Unit IIIC (260-518 meters below seafloor [mbsf]) indicate a relatively constant geochemical composition of the detrital fraction throughout this depositional interval at Ocean Drilling Program (ODP) Site 647 in the southern Labrador Sea. The main variability occurs in redox-sensitive elements (e.g., iron, manganese, and phosphorus), which may be related to early diagenetic mobility in anaerobic pore waters during bacterial decomposition of organic matter. Initial preservation of organic matter was mediated by high sedimentation rates (36 m/m.y.). High iron (Fe) and manganese (Mn) contents are associated with carbonate concretions of siderite, manganosiderite, and rhodochrosite. These concretions probably formed in response to elevated pore-water alkalinity and total dissolved carbon dioxide (CO2) concentrations resulting from bacterial sulfate reduction, as indicated by nodule stable-isotope compositions and pore-water geochemistry. These nodules differ from those found in upper Cenozoic hemipelagic sequences in that they are not associated with methanogenesis. Phosphate minerals (carbonate-fluorapatite) precipitated in some intervals, probably as the result of desorption of phosphorus from iron and manganese during reduction. The bulk chemical composition of the sediments differs little from that of North Atlantic Quaternary abyssal red clays, but may contain a minor hydrothermal component. The silicon/ aluminum (Si/Al) ratio, however, is high and variable and probably reflects original variations in biogenic opal, much of which is now altered to smectite and/or opal CT. An increase in the sodium/potassium (Na/K) ratio in the upper Eocene corresponds to the beginning of coarsergrained feldspar flux to the site, possibly marking the onset of more vigorous deep currents. Although the Site 647 cores provide a nearly complete high-resolution, high-latitude Eocene-Oligocene record, the high sedimentation rate and somewhat unusual diagenetic conditions have led to variable alteration of benthic foraminifers and fine-fraction carbonate and have overprinted the original stable-isotope records. Planktonic foraminifers are less altered, but on the whole, there is little chance of sorting out the nature and timing of environmental change on the basis of our stable-isotope analyses.

Sea surface temperature reconstruction on three sediment profiles off Portugal

Sea Surface Temperature (SST), river discharge and biological productivity have been reconstructed from a multi-proxy study of a high-temporal-resolution sedimentary sequence recovered from the Tagus deposition center off Lisbon (Portugal) for the last 2000 years. SST shows 2 °C variability on a century scale that allows the identification of the Medieval Warm Period (MWP) and the Little Ice Age (LIA). High Iron (Fe) and fine-sediment deposition accompanied by high n-alkane concentrations and presence of freshwater diatoms during the LIA (1300-1900 AD) (Science 292 (2001) 662) suggest augmented river discharge, whereas higher total-alkenone concentrations point to increased river-induced productivity. During the MWP (550-1300 AD) (Science 292 (2001) 662) larger mean-grain size and low values of magnetic susceptibility, and concentrations of Fe, n-alkanes, and n-alcohols are interpreted to reflect decreased runoff. At the same time, increased benthic and planktonic foraminifera abundances and presence of upwelling related diatoms point to increased oceanic productivity. On the basis of the excellent match found between the negative phases of the North Atlantic Oscillation (NAO) index and the intensified Tagus River discharge observed for the last century, it is hypothesized that the increased influx of terrigenous material during the LIA reflects a negative NAO-like state or the occurrence of frequent extreme NAO minima. During the milder few centuries of the MWP, stronger coastal upwelling conditions are attributed to a persistent, positive NAO-like state or the frequent occurrence of extreme NAO maxima. The peak in magnetic susceptibility, centered at 90 cm composite core depth (ccd), is interpreted as the result of the well-known 1755 AD Lisbon earthquake. The Lisbon earthquake and accompanying tsunami are estimated to have caused the loss of 39 cm of sediment (355 years of record-most of the LIA) and the instantaneous deposition of a 19-cm sediment bed.

CO2 and vitamin B12 interactions determine bioactive trace metal requirements of a subarctic Pacific diatom

Phytoplankton growth can be limited by numerous inorganic nutrients and organic growth factors. Using the subarctic diatom Attheya sp. in culture studies, we examined how the availability of vitamin B(12) and carbon dioxide partial pressure (pCO(2)) influences growth rate, primary productivity, cellular iron (Fe), cobalt (Co), zinc (Zn) and cadmium (Cd) quotas, and the net use efficiencies (NUEs) of these bioactive trace metals (mol C fixed per mol cellular trace metal per day). Under B(12)-replete conditions, cells grown at high pCO(2) had lower Fe, Zn and Cd quotas, and used those trace metals more efficiently in comparison with cells grown at low pCO(2). At high pCO(2), B(12)-limited cells had ~50% lower specific growth and carbon fixation rates, and used Fe ~15-fold less efficiently, and Zn and Cd ~3-fold less efficiently, in comparison with B(12)-replete cells. The observed higher Fe, Zn and Cd NUE under high pCO(2)/B(12)-replete conditions are consistent with predicted downregulation of carbon-concentrating mechanisms. Co quotas of B(12)-replete cells were 5- to 14-fold higher in comparison with B(12)-limited cells, suggesting that >80% of cellular Co of B(12)-limited cells was likely from B(12). Our results demonstrate that CO(2) and vitamin B(12) interactively influence growth, carbon fixation, trace metal requirements and trace metal NUE of this diatom. This suggests the need to consider complex feedback interactions between multiple environmental factors for this biogeochemically critical group of phytoplankton in the last glacial maximum as well as the current and future changing ocean.

Development of magnetic carbon xerogels for catalytic wet peroxide oxidation

Hybrid magnetic carbon composites have been recently proposed as the next step in the evolution of catalysts for catalytic wet peroxide oxidation (CWPO), with several synergistic effects arising from the combination of the high catalytic activity of metal species with the proven catalytic properties of carbon-based materials in CWPO [1]. Bearing this in mind, this work sought the development of novel magnetic carbon xerogels, composed by interconnected carbon microspheres with iron (Fe) and/or cobalt (Co) microparticles embedded in their structure. As inferred from the extensive characterization performed, materials with distinctive properties were obtained upon inclusion of different metal precursors during the sol-gel polymerization of resorcinol and formaldehyde, followed by thermal annealing.

Heme Cytotoxicity and the Pathogenesis of Immune-Mediated Inflammatory Diseases

Heme, iron (Fe) protoporphyrin IX, functions as a prosthetic group in a range of hemoproteins essential to support life under aerobic conditions. The Fe contained within the prosthetic heme groups of these hemoproteins can catalyze the production of reactive oxygen species. Presumably for this reason, heme must be sequestered within those hemoproteins, thereby shielding the reactivity of its Fe-heme. However, under pathologic conditions associated with oxidative stress, some hemoproteins can release their prosthetic heme groups. While this heme is not necessarily damaging per se, it becomes highly cytotoxic in the presence of a range of inflammatory mediators such as tumor necrosis factor. This can lead to tissue damage and, as such, exacerbate the pathologic outcome of several immune-mediated inflammatory conditions. Presumably, targeting "free heme" may be used as a therapeutic intervention against these diseases.

Nutrient deficiencies in greater yam and their effects on leaf nutrient concentrations

This paper describes the first systematic study of nutritional deficiencies of greater yam (Dioscorea alata). Yam plants (cv. 'Mahoa'a') were propagated from tuber discs and grown in nutrient solution, with nutrients supplied following a modified programmed nutrient-addition method. After an establishment period of four weeks, deficiencies of nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), iron (Fe), boron (B), manganese (Mn), copper (Cu), zinc (Zn), and molybdenum (Mo) were induced by omitting the relevant nutrient from the solution. Foliar symptoms were recorded photographically. Notably, deficiencies of the mobile macronutrients failed to induce senescence of oldest leaves, while vine growth and younger leaves were affected. Leaf blades of the main stem were sampled in sequence and analyzed chemically, providing the distribution of each nutrient from youngest to oldest leaves in both adequately supplied and deficient plants. The nutrient-concentration profiles, together with the visible symptoms, indicated that little remobilization of mobile macronutrients had occurred. For both macro- and micronutrients, young leaves gave the best separation of nutrient concentrations between well-nourished and deficient plants.

Petrology of weathered lower lias clays

In weak argillaceous rocks the unweathered strength may be barely sufficient to meet civil engineering reguirements and any reductjon due to weathering will be critical. This study investigates the weathering of the Lower Lias clays with particular reference to their petrography and engineering properties. Investigations revealed the Midland Basin of deposition to contain reasonable thicknesses of clay, relatively uniform in nature with a well developed weathered zone, From the available exposures, the weathering zone of the Blockley Clay pit was selected and sampled for laboratory investigations of; Structure, Mineralogy and Chemistry and Engineering Properties. The nature and orientation of the fissures in the unweathered clay were analysed. A close relationship was found to exist between the major joint set and the ground surface, with stress release due to excavation being almost negligible. Thin sections of the clay, examined for structural data, suggested that there exist layers or areas that have been disturbed as a result of density differences. Shear planes were found in both the unweathered and weathered clay, in the latter case often associated with remoulding of the material. A direct measure of remoulding was obtained from the birefringence ratio. The fabric was examined in closer detail using the scanning electron microscope. Mineralogy, as revealed by X-ray and optical techniques indicated illite as the dominant clay mineral, with kaolinite subsidiary; quartz, calcite, pyrite, chlorite/vermiculite are present as accessory minerals. Weathering changes this relationship, calcite and pyrite being removed early in the process, with illite being degraded. The cementing action of calcite and iron oxides was investigated however, this was shown to be negligible. Quantitative measurements of both fixed (with minerals) and free (oxide coatings) iron were obtained by atomic absorption, with the Fe 3+/ Fe2+ ratio obtained by Mossbauer spectroscopy, Evidence indicates that free iron oxide coatings only become important as a result of weathering with the maximum concentration in the very highly weathered material. Engineering index properties and shear strength values were taken throughout the profile, Relationships between moisture content and strength, liquid limit and iron (Fe) were obtained and a correlation between the weathering zomes and the shear strength/depth curve has been established.

Síntese e caracterização estrutural, magnética e térmica da hidroxiapatita dopada com ferro

In this work, composites were prepared using high energy mechanical milling from the precursors hydroxyapatite - HAp (Ca10(PO4)6(OH)2) and metallic iron ( -Fe ). The main goal here is to study composites in order to employ them in magnetic hyperthermia for cancer therapy. The produced samples were characterized by X-ray di raction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), magnetization curves as a function of applied eld (MxH), and nally measurements of magnetic hyperthermia. The XRD patterns of the milled samples HAp/Fe revealed only the presence of precursor materials. The SEM showed clusters with irregular shapes. The magnetization curves indicated typical cases of weak ferromagnetic behavior. For samples submitted to grinding and annealing, the identi ed phases were: HAp (Ca10(PO4)6(OH)2), hematite (Fe2O3) and Calcium Iron Phosphate (Ca9Fe(PO4)7). Analyzing the results of MxH, there was a reduction of the saturation magnetization, given that the Fe was incorporated into HAp. Hysteresis curves obtained at 300 K are characteristics of samples possessing over a phase. At 77 K, the behavior of the hysteresis curve is in uenced by the presence of hematite, which is antiferromagnetic. Already at T = 4.2 K, it is observed a weak ferromagnetic behavior. Furthermore, there is the e ect of exchange bias. Regarding the magnetic hyperthermia, the results of temperature measurements as a function of the alternating eld are promising for applications in magnetic hyperthermia and other biomedical applications.

Sediment geochemistry PASOM research cruise (2009) - Murray Ridge region, northern Arabian Sea

In this study, we investigate phosphorus (P) and iron (Fe) cycling in sediments along a depth transect from within to well below the oxygen minimum zone (OMZ) in the northern Arabian Sea (Murray Ridge). Pore-water and solid-phase analyses show that authigenic formation of calcium phosphate minerals (Ca-P) is largely restricted to where the OMZ intersects the seafloor topography, likely due to higher depositional fluxes of reactive P. Nonetheless, increased ratios of organic carbon to organic P (Corg/Porg) and to total reactive P (Corg/Preactive) in surface sediments indicate that the overall burial efficiency of P relative to Corg decreases under the low bottom water oxygen concentrations (BWO) in the OMZ. The relatively constant Fe/Al ratio in surface sediments along the depth transect suggest that corresponding changes in Fe burial are limited. Sedimentary pyrite contents are low throughout the ~25 cm sediment cores at most stations, as commonly observed in the Arabian Sea OMZ. However, pyrite is an important sink for reactive Fe at one station in the OMZ. A reactive transport model (RTM) was applied to quantitatively investigate P and Fe diagenesis at an intermediate station at the lower boundary of the OMZ (bottom water O2: ~14 µmol/L). The RTM results contrast with earlier findings in showing that Fe redox cycling can control authigenic apatite formation and P burial in Arabian Sea sediment. In addition, results suggest that a large fraction of the sedimentary Ca-P is not authigenic, but is instead deposited from the water column and buried. Dust is likely a major source of this Ca-P. Inclusion of the unreactive Ca-P pool in the Corg/P ratio leads to an overestimation of the burial efficiency of reactive P relative to Corg along the depth transect. Moreover, the unreactive Ca-P accounts for ~85% of total Ca-P burial. In general, our results reveal large differences in P and Fe chemistry between stations in the OMZ, indicating dynamic sedimentary conditions under these oxygen-depleted waters.

Pore water and solid-phase measurements on sediment cores from the Black Sea

The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe) oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ. Here we combine detailed geochemical analyses of the sediment and pore water with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P) and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. Our results show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g. vivianite) are converted to sulfide phases, leading to an enrichment in solid phase S and the release of phosphate to the pore water. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front. Our model results further demonstrate that downward migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM (~ 1-100 pmol/cm**3/d) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the pore water at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.

Age, 232Th, 230Th, 238U, CaCO3, organic carbon, lithogenic fraction and opal concentrations of 4 sediment cores from the southwest Pacific, with calculated 230Th-normalized mass flux

No clear scenario has yet been able to explain the full carbon drawdown that occurred during the Last Glacial Maximum (LGM); however, increased export production (EP) in the Subantarctic Zone (SAZ) of the Southern Ocean due to iron (Fe) fertilisation has been proposed to have provided a key mechanism affecting the air-sea partitioning of carbon. We chronicle changes in marine EP based on four sediment cores in Subtropical Waters (STW) and SAZ around New Zealand since the LGM. For the first time in this region, we present 230-Thorium normalised fluxes of biogenic opal, carbonate (CaCO3), excess Barium (xsBa), and organic Carbon (Corg). In STW and SAZ, these flux variations show that EP did not change markedly since the LGM. The only exception was a site in the SAZ close to the STF, where we suggest the STF shifted over the core site, driving increased EP. To understand why EP was mostly low and constant we investigated dust deposition changes by measuring lithogenic fluxes at the four sites. These data are coherent with an increased dust deposition in the southwest Pacific during the LGM. Additionally, we infer an increased lithogenic material discharge from erosion and glacier melts during the deglaciation, limited to the Campbell Plateau. Therefore, we propose that even though increased glacial dust deposition may have relieved Fe limitation within the SAZ, the availability of silicic acid (Si(OH)4) limited any resultant increase in carbon export during the LGM. Consequently, we infer low Si(OH)4 concentrations in the SAZ that have not significantly changed since the LGM. This result suggests that both Si(OH)4 and Fe co-limit EP in the SAZ around New Zealand, which would be consistent with modern process studies.