Foraminiferal changes and geochemical profiles across the Cenomanian/Turonian boundary in central and south-east Poland

Two sections of the Upper Cenomanian and Lower Turonian in central and south-east Poland were investigated for foraminifers, CaCO₃content, carbon content insoluble in HCl (C_org) and in the carbonates (C_carb), carbon and oxygen isotopic composition of bulk-rock carbonates and elemental abundances. The Cenomanian/Turonian boundary interval is characterized by the appearance of more marly facies, a δ¹³C and δ¹⁸O stable isotope anomaly, a considerable increase in C_org content and decrease in C_carb content and substantial changes in the foraminiferal assemblages. A major carbon stable isotope excursion with a shift of +2 (PDB) occurs in the lowermost Whiteinella archaeocretacea Zone. The late Cenomanian δ¹³C anomaly is associated with heavy δ¹⁸O values. The peak value of δ¹³C corresponds to the minima in P/B ratio and in diversity of foraminiferal assemblages. A late Cenomanian anoxic event is thought to be responsible for changes in foraminiferal assemblages. However, elemental abundance analyses do not show changes in the concentrations of trace elements. This may be explained by the long distance between studied area and a source of enrichment which was probably located in the western hemisphere.     

Shoreline change at an infinite jetty for wave time series

Future shoreline changes on a sandy beach with a structure such as a jetty or groin can be estimated when wave time series is known (i.e. sequence of wave height, period, and direction). This paper presents an extension of an existing solution (Pelnard-Considere, 1956) for the linearized partial differential equation for shoreline change at an infinite jetty where waves are time varying and when the angle of the shoreline is small with respect to the waves breaking at the shoreline. The novel solution provided in this paper allows the previous constant wave condition solution to be extended to the case where wave properties (i.e. wave direction, wave height, and wave period) are time varying. Example usage of the method presented shows that shorelines may be of different final plan form shape for time varying wave conditions even though the sediment transport along adjacent beaches is not spatially varying (i.e. spatially constant) from time step to time step. Although this difference in shape may have been known previously using numerical models, it could not be proved analytically. Reversals of wave height, period, and direction time series are shown to provide different final shoreline shapes even though the time series consists of the same waves although in different ordered time. The solution provided will allow one line numerical shoreline models to be tested using an analytic solution.     

Vent fluid chemistry of the Rainbow hydrothermal system (36°N, MAR): Phase equilibria and in situ pH controls on subseafloor alteration processes

The Rainbow hydrothermal field is located at 36°13.8′N-33°54.15′W at 2300 m depth on the western flank of a non-volcanic ridge between the South AMAR and AMAR segments of the Mid-Atlantic Ridge. The hydrothermal field consists of 10-15 active chimneys that emit high-temperature (∼365 °C) fluid. In July 2008, vent fluids were sampled during cruise KNOX18RR, providing a rich dataset that extends in time information on subseafloor chemical and physical processes controlling vent fluid chemistry at Rainbow. Data suggest that the Mg concentration of the hydrothermal end-member is not zero, but rather 1.5-2 mmol/kg. This surprising result may be caused by a combination of factors including moderately low dissolved silica, low pH, and elevated chloride of the hydrothermal fluid. Combining end-member Mg data with analogous data for dissolved Fe, Si, Al, Ca, and H₂, permits calculation of mineral saturation states for minerals thought appropriate for ultramafic-hosted hydrothermal systems at temperatures and pressures in keeping with constraints imposed by field observations. These data indicate that chlorite solid solution, talc, and magnetite achieve saturation in Rainbow vent fluid at a similar pH_(T,P) (400 °C, 500 bar) of approximately 4.95, while higher pH values are indicated for serpentine, suggesting that serpentine may not coexist with the former assemblage at depth at Rainbow. The high Fe/Mg ratio of the Rainbow vent fluid notwithstanding, the mole fraction of clinochlore and chamosite components of chlorite solid solution at depth are predicted to be 0.78 and 0.22, respectively. In situ pH measurements made at Rainbow vents are in good agreement with pH_(T,P) values estimated from mineral solubility calculations, when the in situ pH data are adjusted for temperature and pressure. Calculations further indicate that pH_(T,P) and dissolved H₂ are extremely sensitive to changes in dissolved silica owing to constraints imposed by chlorite solid solution-fluid equilibria. Indeed, the predicted correlation between dissolved silica and H₂ defines a trend that is in good agreement with vent fluid data from Rainbow and other high-temperature ultramafic-hosted hydrothermal systems. We speculate that the moderate concentrations of dissolved silica in vent fluids from these systems result from hydrothermal alteration of plagioclase and olivine in the form of subsurface gabbroic intrusions, which, in turn are variably replaced by chlorite + magnetite + talc ± tremolite, with important implications for pH lowering, dissolved sulfide concentrations, and metal mobility.     

Quantification of the ferric/ferrous iron ratio in silicates by scanning transmission X-ray microscopy at the Fe L2,3 edges

Estimation of Fe³⁺/ΣFe ratios in materials at the submicrometre scale has been a long-standing challenge in the Earth and environmental sciences because of the usefulness of this ratio in estimating redox conditions as well as for geothermometry. To date, few quantitative methods with submicrometric resolution have been developed for this purpose, and most of them have used electron energy-loss spectroscopy carried out in the ultra-high vacuum environment of a transmission electron microscope (TEM). Scanning transmission X-ray microscopy (STXM) is a relatively new technique complementary to TEM and is increasingly being used in the Earth sciences. Here, we detail an analytical procedure to quantify the Fe³⁺/ΣFe ratio in silicates using Fe L_2,3-edge X-ray absorption near edge structure (XANES) spectra obtained by STXM, and we discuss its advantages and limitations. Two different methods for retrieving Fe³⁺/ΣFe ratios from XANES spectra are calibrated using reference samples with known Fe³⁺ content by independent approaches. The first method uses the intensity ratio of the two major peaks at the L₃-edge. This method allows mapping of Fe³⁺/ΣFe ratios at a spatial scale better than 50 nm by the acquisition of 5 images only. The second method employs a 2-eV-wide integration window centred on the L₂ maximum for Fe³⁺, which is compared to the total integral intensity of the Fe L₂-edge. These two approaches are applied to metapelites from the Glarus massif (Switzerland), containing micrometre-sized chlorite and illite grains and prepared as ultrathin foils by focused ion beam milling. Nanometre-scale mapping of iron redox in these samples is presented and shows evidence of compositional zonation. The existence of such zonation has crucial implications for geothermometry and illustrates the importance of being able to measure Fe³⁺/ΣFe ratios at the submicrometre scale in geological samples.     

Microplankton provide 9 Ma age for sediment in the Macquarie Island ophiolite complex

Macquarie Island in the southwest Pacific Ocean (55°S) is unique as an exposed location for studying oceanic crust generated by slow seafloor spreading—regions where rocks are difficult to date using radiometric methods. Bolboforms, an extinct group of poorly known microplankton, in sediment intercalated with pillow lavas yield tight constraints (9.01–8.78 Ma) on the age of formation of the dominantly seafloor volcanic sequence constituting the south of the island. The occurrence of Bolboforma metzmacheri extends the known geographic range of this Late Miocene zonal marker species in the southwest Pacific. A monospecific calcareous nannoplankton flora (Reticulofenestra perplexa) accompanied by the foraminifer Neogloboquadrina pachyderma in sediment from the north part of the island indicates a slightly older age (9.5–9.3 Ma), consistent with a radiometric date (9.2 ± 0.4 Ma) from nearby volcanics. The new age data indicate that the ocean floor volcanic sequence formed early in the Late Miocene, possibly along short segments of a slow-spreading mid-ocean ridge. Bolboforms have potential to provide fine-scale dating in other similarly complex ridge systems that are difficult to date by other means.     

Hydrogen Cyanide Accumulation and Transformations in Non-polluted Salt Marsh Sediments

While cyanide is known to be produced by many organisms, including plants, bacteria, algae, fungi and some animals, it is generally thought that high levels of cyanide in aquatic systems require anthropogenic sources. Here, we report accumulation of relatively high levels of cyanide in non-polluted salt marsh sediments (up to 230 μmol kg^?1). Concentrations of free cyanide up to 1.92 μmol L^?1, which are toxic to aquatic life, were detected in the pore-waters. Concentration of total (free and complexed) cyanide in the pore-waters was up to 6.94 μmol L^?1. Free cyanide, which is released to the marsh sediments, is attributed to processes associated with decomposition of cord grass, Spartina alterniflora, roots and possibly from other sources. This cyanide is rapidly complexed with iron and adsorbed on sedimentary organic matter. The ultimate cyanide sink is, however, associated with formation of thiocyanate by reaction with products of sulfide oxidation by Fe(III) minerals, especially polysulfides. The formation of thiocyanate by this pathway detoxifies two poisonous compounds, polysulfides and hydrogen cyanide, preventing release of free hydrogen cyanide from salt marsh sediments into overlying water or air.     

Influence of the natural oxidation of the leachate organic fraction from a landfill on groundwater quality, Belo Horizonte: Minas Gerais, south-eastern Brazil

The objective of this work was to evaluate the influence of the natural degradation of the leachate organic fraction from the Belo Horizonte landfill on groundwater chemical evolution. The work focused on the modifications introduced by redox reactions in the presence of terminal electron acceptors. Twenty-one sampling points distributed along 13 monitoring wells were selected for the analysis of the chemical indicators of interest (TDS, SO ₄ ^?2 , Fe⁺², Ba, pH and Eh). The behaviour of the variables involved in the alteration of the water quality was assessed by the spatial distribution of target parameters, elaboration of redox diagrams and chemical modelling that focused on the determination of mineral saturation indexes. The study showed a trend toward pyrite precipitation, which leads to the removal of chemical species such as divalent iron and sulphur as sulphide from the system. This removal disturbs the chemical equilibrium, typically by moving the reactions to replenish the sulphate concentration present in the groundwater. This process occurs primarily through the dissolution of compounds that have sulphate in their chemical composition, such as barite, suggesting that part of the barium concentration in the subsurface can be of geogenic origin. This study demonstrated the importance of knowing the nature of the geochemical processes in groundwater contaminated by urban solid waste.     

Nature and degree of aqueous alteration in CM and CI carbonaceous chondrites

We investigated the petrologic, geochemical, and spectral parameters that relate to the type and degree of aqueous alteration in nine CM chondrites and one CI (Ivuna) carbonaceous chondrite. Our underlying hypothesis is that the position and shape of the 3 μm band is diagnostic of phyllosilicate mineralogy. We measured reflectance spectra of the chondrites under dry conditions (elevated temperatures) and vacuum (10^?8 to 10^?7 torr) to minimize adsorbed water and mimic the space environment, for subsequent comparison with reflectance spectra of asteroids. We have identified three spectral CM groups in addition to Ivuna. “Group 1,” the least altered group as determined from various alteration indices, is characterized by 3 μm band centers at longer wavelengths, and is consistent with cronstedtite (Fe‐serpentine). “Group 3,” the most altered group, is characterized by 3 μm band centers at shorter wavelengths and is consistent with antigorite (serpentine). “Group 2” is an intermediate group between group 1 and 3. Ivuna exhibits a unique spectrum that is distinct from the CM meteorites and is consistent with lizardite and chrysotile (serpentine). The petrologic and geochemical parameters, which were determined using electron microprobe analyses and microscopic observations, are found to be consistent with the three spectral groups. These results indicate that the distinct parent body aqueous alteration environments experienced by these carbonaceous chondrites can be distinguished using reflectance spectroscopy. High‐quality ground‐based telescopic observations of Main Belt asteroids can be expected to reveal not just whether an asteroid is hydrated, but also details of the alteration state.