Factors Controlling Sulfide Geochemistry in Sub-tropical Estuarine and Bay Sediments

The primary factors that control the concentration of total reduced (inorganic) sulfide in coastal sediments are believed to be the availability of reactive iron, dissolved sulfate and metabolizable organic carbon. We selected nine sites in shallow (<3 m), close to sub-tropical, estuaries and bays along the central Texas coast that represented a range in sediment grain size (a proxy for reactive iron), salinity (a proxy for dissolved sulfate), and total organic carbon (a proxy for metabolizable organic carbon). Based on these parameters a prediction was made of which factor was likely to control total reduced sulfide at each site and what the relative total reduced sulfide concentration was likely to be. To test the prediction, the sediments were analyzed for total reduced sulfide, acid volatile sulfide, and citrate dithionate-extractable, HCl-extractable and total Fe in the solid phase. Using solid-state gold–mercury amalgam microelectrodes and voltammetry, we determined pore water depth profiles of Fe(II) and ΣH₂S and presence or absence of FeS_(aq). At five of the nine sites the calculated degree of sufildization of citrate dithionite-reactive-iron was close to or greater than 1 indicating that rapidly reactive iron was probably the limiting factor for iron sulfide mineral formation. At one site (salinity = 0.9) dissolved Fe(II) was high, ΣH₂S was undetectable and the total reduced sulfide concentration was low indicating sulfate limitation. At the last three sites a low degree of sulfidization and modest total reduced (inorganic) sulfide concentrations appeared to be the result of a limited supply of metabolizable organic carbon. Fe(II)–S(-II) clusters (FeS_(aq)) were undetectable in 10 out of 12 bay sediment profiles where ΣH₂S was close to or below detection limits, but was observed in all other porewater profiles. Acid volatile sulfide, but not total reduced sulfide, was well correlated with total organic carbon and ranged from being undetectable in some cores to representing a major portion of total reduced sulfide in other cores. Although predicted controls on total reduced sulfide were good for very low salinity water or sandy sediments, they were only right about half the time for the other sediments. The likely reasons for the wrong predictions are the poor correlation of total organic carbon with grain size and differing fractions of metabolizable organic carbon in different sedimentary environments. Differences in sediment accumulation rates may also play a role, but these are difficult to determine in this region where hurricanes often resuspend and move sediments. This study demonstrates the need to examine more complex and often difficult to determine parameters in anoxic “normal marine” sediments if we are to understand what controls the concentration and distribution of sulfides.     

An experimental and theoretical determination of oxygen isotope fractionation in the system magnetite-H2O from 300 to 800°C

Oxygen isotope fractionations have been determined between magnetite and water from 300 to 800°C and pressures between 10 and 215MPa. We selected three reaction pathways to investigate fractionation: (a) reaction of fine-grained magnetite with dilute aqueous NaCl solutions; (b) reduction of fine-grained hematite through reaction with dilute acetic acid; and (c) oxidation of fine iron power in either pure water or dilute NaCl solutions. Effective use of acetic acid was limited to temperatures up to about 400°C, whereas oxide-solution isotope exchange experiments were conducted at all temperatures. Equilibrium ¹⁸O/¹⁶O fractionation factors were calculated from the oxide-water experiments by means of the partial isotope exchange method, where generally four isotopically different waters were used at any given temperature. Each run product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and on a limited basis, high-resolution transmission electron microscopy (HRTEM) and Mössbauer spectroscopy. Results from the microscopic examinations indicate the formation of well-crystallized octahedra and dodecahedra of magnetite where the extent of crystallization, grain size, and grain habit depend on the initial starting material, P, T, solution composition, and duration of the run.The greatest amount of oxygen isotope exchange (∼90% or greater) was observed in experiments where magnetite either recrystallized in the presence of 0.5 m NaCl from 500 to 800°C or formed from hematite reacted with 0.5 m acetic acid at 300, 350 and 400°C. Fractionation factors (10³ ln α_mt-H2O) determined from these partial exchange experiments exhibit a steep decrease (to more negative values) with decreasing temperature down to about 500°C, followed by shallower slope. A least-squares regression model of these partial exchange data, which accounts for analytical errors and errors generated by mass balance calculations, gives the following expression for fractionation that exhibits no minimum: 1000lnα_lmt-lw=−8.984(±0.3803)x+3.302(±0.377)x²—0.426(±0.092)x³ with an R² = 0.99 for 300 ≤ T≤ 800°C (x = 10⁶/T²). The Fe oxidation results also exhibit this type of temperature dependence but shifted to slightly more negative 10³ ln α values; there is the suggestion that a kinetic isotope effect may contribute to these fractionations. A theoretical assessment of oxygen isotope fractionation using β-factors derived from heat capacity and Mössbauer temperature (second-order Doppler) shift measurements combined with known β-factors for pure water yield fractionations that are somewhat more negative compared to those determined experimentally. This deviation may be due to the combined solute effects of dissolved magnetite plus NaCl (aq), as well as an underestimation of β_mt at low temperatures. The new magnetite-water experimental fractionations agree reasonably well with results reported from other experimental studies for temperatures ≥ 500°C, but differ significantly with estimates based on quasi-theoretical and empirical approaches. Calcite-magnetite and quartz-magnetite fractionation factors estimated from the combination of magnetite β’s calculated in this study with those for calcite and quartz reported by Clayton and Kieffer (1991) agree very closely with experimentally determined mineral-pair fractionations.     

Strontium-calcium ratios in Cenozoic planktonic foraminifera

The $\text{Sr}\text{Ca}$ ratio and other parameters have been measured in fossil planktonic foraminifera from the Atlantic and Pacific Ocean basins in order to evaluate the $\text{Sr}\text{Ca}$ ratio of seawater during the last 75 million years. Results on well-preserved samples indicate that the ratio has increased to its present value by 10–15% during the Cenozoic, and that minima occurred between 55-45 Ma and 10-5 Ma, when the ratio was 15–25% less than at present. The long-term increase may reflect either decreasing deposition of aragonite with a high $\text{Sr}\text{Ca}$ ratio in shallow seas, or decreasing seafloor spreading rates and consequently decreasing hydrothermal supply of Ca during the Cenozoic. Other geologic evidence suggests that the Eocene minimum (near 50 Ma) may have resulted from increased aragonite sedimentation, while the Late Miocene minimum (between 10-5 Ma) may have been caused by an increased rate of seawater-basalt exchange when seafloor spreading rates increased on the East Pacific Rise near 10 Ma.     

Pronounced occurrence of long-chain alkenones and dinosterol in a 25,000-year lipid molecular fossil record from Lake Titicaca, South America

Our analysis of lipid molecular fossils from a Lake Titicaca (16° S, 69° W) sediment core reveals distinct changes in the ecology of the lake over an ∼25,000-yr period spanning latest Pleistocene to late Holocene time. Previous investigations have shown that over this time period Lake Titicaca was subject to large changes in lake level in response to regional climatic variability. Our results indicate that lake algal populations were greatly affected by the changing physical and chemical conditions in Lake Titicaca. Hydrocarbons are characterized by a combination of odd-numbered, mid- to long-chain (C₂₁-C₃₁) normal alkanes and alkenes. During periods when lake level was higher (latest Pleistocene, early Holocene, and late Holocene), the C₂₁n-alkane, and the C₂₅ and C₂₇ alkenes dominate hydrocarbon distributions and indicate contribution from an algal source, potentially the freshwater alga Botryococcus braunii. The C₃₀ 4 α-methyl sterol (dinosterol) increases sharply during the mid-Holocene, suggesting a greatly increased dinoflagellate presence at that time. Long-chain alkenones (LCAs) become significant during the early Holocene and are highly abundant in mid-Holocene samples. There are relatively few published records of LCA detection in lake sediments but their occurrence is geographically widespread (Antarctica, Asia, Europe, North America). Lake Titicaca represents the first South American lake and the first low-latitude lake in which LCAs have been reported. LCA abundance and distribution may be related to the temperature-dependent response of an unidentified algal precursor. Although the LCA unsaturation indices cannot be used to determine absolute Lake Titicaca temperatures, we suspect that the published LCA U₃₇^K unsaturation calibrations can be applied to infer relative temperatures for early to mid-Holocene time when LCA concentrations are high. Using these criteria, the U₃₇^K unsaturation indices suggest relatively warmer temperatures in the mid-Holocene. In contrast to previous speculation, lipid analysis provides little evidence of a greatly increased presence of aquatic plants during the mid-Holocene. Instead, it appears that a few algal species were dominant in the lake. Based on the dramatic rise in abundances of LCAs and dinosterol during the early to mid-Holocene, we suspect that the algal producers of these compounds rose in response to a combination of physical and chemical changes in the lake. These include temperature, salinity, and alkalinity changes that occurred as lake level dropped sharply during a multi-millennial drought affecting the Central Andean Altiplano.     

Did Paleogene North Atlantic rift-related eruptions drive early Eocene climate cooling?

The delivery of volcanogenic sulphur into the upper atmosphere by explosive eruptions is known to cause significant temporary climate cooling. Therefore, phreatomagmatic and phreatoplinian eruptions occurring during the final rifting stages of active flood basalt provinces provide a potent mechanism for triggering climate change.

During the early Eocene, the northeast Atlantic margin was subjected to repeated ashfall for 0.5 m.y. This was the result of extensive phreatomagmatic activity along 3000 km of the opening northeast Atlantic rift. These widespread, predominantly basaltic ashes are now preserved in marine sediments of the Balder Formation and its equivalents, and occur over an area extending from the Faroe Islands to Denmark and southern England. These ash-bearing sediments also contain pollen and spore floras derived from low diversity forests that grew in cooler, drier climates than were experienced either before or after these highly explosive eruptions. In addition, coeval plant macrofossil evidence from the Bighorn Basin, Wyoming, USA, also shows a comparable pattern of vegetation change. The coincidence of the ashes and cooler climate pollen and spore floras in northwest Europe identifies volcanism as the primary cause of climate cooling. Estimates show that whilst relatively few phreatomagmatic eruptive centres along the 3000 km opening rift system could readily generate 0.5–1 °C cooling, on an annual basis, only persistent or repeated volcanic phases would have been able to achieve the long-term cooling effect observed in the floral record. We propose that the cumulative effect of repeated Balder Formation eruptions initiated a biodiversity crisis in the northeast Atlantic margin forests. Only the decline of this persistent volcanic activity, and the subsequent climatic warming at the start of the Eocene Thermal Maximum allowed the growth of subtropical forests to develop across the region.     

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

Source and movement of helium in the eastern Morongo groundwater Basin: The influence of regional tectonics on crustal and mantle helium fluxes

We assess the role of fracturing and seismicity on fluid-driven mass transport of helium using groundwaters from the eastern Morongo Basin (EMB), California, USA. The EMB, located ∼200 km east of Los Angeles, lies within a tectonically active region known as the Eastern California Shear Zone that exhibits both strike-slip and extensional deformation. Helium concentrations from 27 groundwaters range from 0.97 to 253.7 × 10⁻⁷ cm³ STP g⁻¹H₂O, with corresponding ³He/⁴He ratios falling between 1.0 and 0.26 R_A (where R_A is the ³He/⁴He ratio of air). All groundwaters had helium isotope ratios significantly higher than the crustal production value of ∼0.02 R_A. Dissolved helium concentrations were resolved into components associated with solubility equilibration, air entrainment, in situ production within the aquifer, and extraneous fluxes (both crustal and mantle derived). All samples contained a mantle helium-3 (³He_m) flux in the range of 4.5 to 1351 × 10⁻¹⁴ cm³ STP ³He cm⁻² yr⁻¹ and a crustal flux (J₀) between 0.03 and 300 × 10⁻⁷ cm³ STP ⁴He cm⁻² yr⁻¹. Groundwaters from the eastern part of the basin contained significantly higher ³He_m and deep crustal helium-4 (⁴He_dc) concentrations than other areas, suggesting a localized source for these components. ⁴He_dc and ³He_m are strongly correlated, and are associated with faults in the basin. A shallow thermal anomaly in a >3,000 m deep graben in the eastern basin suggests upflow of fluids through active faults associated with extensional tectonics. Regional tectonics appears to drive large scale crustal fluid transport, whereas episodic hydrofracturing provides an effective mechanism for mantle-crust volatile transport identified by variability in the magnitude of degassing fluxes (³He_m and J₀) across the basin.     

Evolution of a Holocene banner bank controlled by morphodynamics and structural setting of a macrotidal coast: Saint-Brieuc Bay(NW-Europe)

The morphology and internal structure of the Horaine Bank(Bay of Saint-Brieuc, NW France) are described based on multibeam echosounder and high-resolution seismic datasets coupled with vibro-core data. The Horaine Bank shows large-scale bedforms in the lee of a submerged rocky shoal, which allowed defining it as a Banner Bank.The internal structure of the sandbank reveals four seismic units(U1–U4) on a Cambrian basement(U0). The basal unit U1 is interpreted as reworked lowstand fluvial sediments those infilled micro incised valleys during a rise in sea level. This unit is overlain by paleo-coastal barrier sand-spit(U2) whose development was controlled by swell in the context of a rapid rise in sea level. The successive prograding unit(U3) is interpreted as flooding deposits in continuity with unit U2. The unit U4 is characterized by oblique reflectors oriented in two opposite directions. This last unit, dated post 3500 yr BP, corresponds to migrating dunes superimposed on the bank and observable in the high-resolution bathymetric data. The strong correlation between tidal currents and the apparent clockwise migration of dune crests suggests the presence of a tidal gyre controlling the present-day dynamics of most of the Horaine bank dunes. This study proposes a new model for the construction of banner banks characterized by the gradual transition of a sand spit to a banner bank during marine transgression and ensuing hydrodynamic variability.     

Variogram Model Selection via Nonparametric Derivative Estimation

Before optimal linear prediction can be performed on spatial data sets, the variogram is usually estimated at various lags and a parametric model is fitted to those estimates. Apart from possible a priori knowledge about the process and the user's subjectivity, there is no standard methodology for choosing among valid variogram models like the spherical or the exponential ones. This paper discusses the nonparametric estimation of the variogram and its derivative, based on the spectral representation of positive definite functions. The use of the estimated derivative to help choose among valid parametric variogram models is presented. Once a model is selected, its parameters can be estimated—for example, by generalized least squares. A small simulation study is performed that demonstrates the usefulness of estimating the derivative to help model selection and illustrates the issue of aliasing. MATLAB software for nonparametric variogram derivative estimation is available at http://www-math.mit.edu/~gorsich/derivative.html. An application to the Walker Lake data set is also presented.