Phosphorus accumulation rates in metalliferous sediments on the East Pacific Rise

Based on phosphorus, iron and manganese analyses in 16 cores (5 dated) from the crest and flanks of the East Pacific Rise and the Bauer Deep we estimate that phosphorus is being deposited about 20 times faster in metalliferous sediments near the rise crest than in adjacent flank deposits, and about 40 times faster on the crest than in the Bauer Deep. Almost all of the phosphorus on the rise crest is contained in poorly crystallized hydrothermal iron oxyhydroxides, supporting Berner's (1973) proposal of phosphate sorption by these phases. The phosphate is probably derived from seawater, but some hydrothermal contribution cannot be excluded at this time. Flux estimates indicate that metalliferous sedimentation could remove 15–40% of the pre-agricultural river input of dissolved phosphate.     

Speleothem calcite farmed in situ: Modern calibration of δO and δC paleoclimate proxies in a continuously-monitored natural cave system

Understanding the relationships between speleothem stable isotopes (δ¹³C δ¹⁸O) and in situ cave forcing mechanisms is important to interpreting ancient stalagmite paleoclimate records. Cave studies have demonstrated that the δ¹⁸O of inorganically precipitated (low temperature) speleothem calcite is systematically heavier than the δ¹⁸O of laboratory-grown calcite for a given temperature. To understand this apparent offset, rainwater, cave drip water, groundwater, and modern naturally precipitated calcite (farmed in situ) were grown at multiple locations inside Hollow Ridge Cave in Marianna, Florida. High resolution micrometeorological, air chemistry time series and ventilation regimes were also monitored continuously at two locations inside the cave, supplemented with periodic bi-monthly air gas grab sample transects throughout the cave.Cave air chemistry and isotope monitoring reveal density-driven airflow pathways through Hollow Ridge Cave at velocities of up to 1.2 m s⁻¹ in winter and 0.4 m s⁻¹ in summer. Hollow Ridge Cave displays a strong ventilation gradient in the front of the cave near the entrances, resulting in cave air that is a mixture of soil gas and atmospheric CO₂. A clear relationship is found between calcite δ¹³C and cave air ventilation rates estimated by proxies pCO₂ and ²²²Rn. Calcite δ¹³C decreased linearly with distance from the front entrance to the interior of the cave during all seasons, with a maximum entrance-to-interior gradient of Δδ¹³C_CaCO3 = −7‰. A whole-cave “Hendy test” at multiple contemporaneous farming sites reveals that ventilation induces a +1.9 ± 0.96‰ δ¹³C offset between calcite precipitated in a ventilation flow path and calcite precipitated on the edge or out of flow paths. This interpretation of the “Hendy test” has implications for interpreting δ¹³C records in ancient speleothems. Calcite δ¹³C_CaCO3 may be a proxy not only for atmospheric CO₂ or overlying vegetation shifts but also for changes in cave ventilation due to dissolution fissures and ceiling collapse creating and plugging ventilation windows.Farmed calcite δ¹⁸O was found to exhibit a +0.82 ± 0.24‰ offset from values predicted by both theoretical calculations and laboratory-grown inorganic calcite. Unlike δ¹³C_CaCO3, oxygen isotopes showed no ventilation effects, i.e. Δδ¹⁸O_CaCO3 appears to be a function of growth temperature only although we cannot rule out a small effect of (unmeasured) gradients in relative humidity (evaporation) accompanying ventilation. Our results support the findings of other cave investigators that water-calcite fractionation factors observed in speleothem calcite are higher that those measured in laboratory experiments. Cave and laboratory calcite precipitates may differ mainly in the complex effects of kinetic isotope fractionation. Combining our data with other recent speleothem studies, we find a new empirical relationship for cave-specific water-calcite oxygen isotope fractionation across a range of temperatures and cave environments:

1000lnα=16.1(10³T^-1)-24.6     

Fractionation of palladium and platinum in a Mesozoic diabase sheet, Gettysburg basin, Pennsyvania: implications for mineral exploration

The York Haven diabase sheet displays clear-cut evidence of fractionation of Pd and Pt during differentiation of a high-Ti (about 1.1%) quartz-normative tholeiitic magma (York Haven type). At York Haven the sheet is about 750 m thick. It is characterized by abundant cumulus MgO-rich orthopyroxene (bronzite), and is markedly depleted in incompatible elements relative to the chilled margins. In contrast, at Reesers Summit, 16 km to the northwest, the sheet is about 500 m thick and consists of evolved rocks that have contents of incompatible elements two to three times greater than in the enclosing chilled margins. These evolved rocks represent complementary fractions to the cumulate rocks at York Haven. Mineralogic, petrologic and geochemical variations suggest considerable lateral migration and fractionation of the initial magma.Chilled margins of both sections have essentially the same Pd and Pt contents (10 ppb each) and similar Pd to Pt ratios (1.2). During differentiation, the cumulate rocks at York Haven were enriched in Pt and depleted in Pd, whereas at Reesers Summit, the low-MgO diabase and ferrogabbro zone were enriched in Pd relative to Pt. Anomalously high contents of Pd (to 165 ppb), Au (to 54 ppb), and Te (to 26 ppb) were found in an iron- (to 18%) and chlorine- (to 0.44%) rich ferrogabbro at Reesers Summit, suggesting possible late or post-magmatic enrichment of precious metals. Field relations, geochemical and petrographic data provide guides for further exploration for Pd and Pt in differentiated high-Ti quartz-normative diabase sheets. Based on present information, the most favorable sites for economic deposits are late-stage differentiates enriched in Fe and Cl.     

Early diagenesis in sediments from the eastern equatorial Pacific,I. Pore water nutrient and carbonate results

Interstitial waters were extracted from cores at three locations in the eastern equatorial Pacific and analyzed for nutrients, dissolved carbonate species, Mn and Fe. From the depth variation in pore water chemistry, we infer that organic matter oxidation reactions occur with depth in the following sequence: O₂ reduction, NO₃^? and MnO₂ reduction, and then ferric iron reduction. From NO₃^? results we infer that O₂ is largely or totally consumed within the top few centimeters of sediment. NO₃^? is completely reduced at a sediment depth of 20 cm at a site near the crest of the East Pacific Rise, but is preserved at levels of 20–30 μmol/kg at 40 cm depth at a Guatemala Basin site.We have calculated the alkalinity for pore water samples assuming ions diffuse according to relative ionic diffusion coefficients, that the stoichiometry of organic matter oxidation reactions is that of “Redfield” organic matter, and that the pore waters are saturated throughout with respect to CaCO₃. The measured alkalinity increase is only about half of the predicted value. The difference is probably a result of either enhanced mixing of the pore water in the top few centimeters of sediments by biological or physical processes, or the occurrence of an inorganic reaction which consumes alkalinity.At depths of oxygen and nitrate reduction in the sediments, the ion concentration product of CaCO₃ is the same, within the analytical error, as the solubility product of Ingle et al. [34] at 1 atm and 4°C. This result indicates CaCO₃ resaturation on pressure change during coring. Where pore water Mn concentrations become measurable, the ion concentration product increases, indicating either supersaturation with respect to calcite or that another phase is controlling the carbonate solubility.     

Oxygen isotope partitioning between phosphate and carbonate in mammalian apatite

The oxygen isotope compositions of phosphate and structural carbonate in mammalian enamel and bone apatite are linked to that of body water at constant body temperature near 37°C, but the isotope systematics of oxygen in structural carbonate are not well understood. Using coupled measurements of the oxygen isotope composition of structural carbonate and phosphate from horse tooth enamel, the apparent oxygen isotope fractionation factor between structural carbonate and body water is estimated to be 1.0263 ± 0.0014. These estimates provide a quantitative basis for using the oxygen isotope composition of structural carbonate in mammalian biogenic apatite for ecological, climatological, and physiological reconstruction.     

Does sedimentary organic delta 13C record variations in quaternary ocean [CO2(aq)]?

Ocean surface water [CO2(aq)] variations based on glacial/interglacial changes in sediment delta 13Corg are shown to compare favorably with reconstructions based on ice core [CO2]. In particular, an approximate 80 microatmospheres increase in atmospheric pCO2 during the last glacial-interglacial transition is calculated to correspond to a 3-4 micromolar increase in ocean surface water [CO2(aq)] at atmospheric equilibrium. A widespread marine delta 13Corg decrease of 1-2% accompanied this event and was not preceded by an equivalent isotopic change in surface water total dissolved inorganic carbon. These observations support the hypothesis that [CO2(aq)] influences photosynthetic isotope fractionation between marine inorganic and organic carbon pools, and therefore that plankton/sediment delta 13Corg may serve as a proxy for surface water [CO2(aq)].     

Early diagenesis of organic matter in Peru continental margin sediments: Phosphorite precipitation

Pore water chemistry (total dissolved CO₂, NH₄, NO₃, NO₂, PO₄, Si(OH)₄, Ca, Mg, Fe, Mn, SO₄, H₂S and F, and titration alkalinity), solid phase chemistry (C_org, P_org, C_TOT, N_TOT, F, Si_OPAL and S_II), and sediment characteristics (porosity, dry bulk density and formation factors) were determined on a centimeter-scale spacing in the upper 20–40 cm of sediments under intense upwelling areas on the Peru continental shelf. These data demonstrate that carbonate fluorapatite (CFA) is precipitating from pore waters in the upper few centimeters of a gelatinous mud with high organic carbon content (up to 20% C_org), very high porosity ( > 0.96 ml cm⁻³) and very low dry bulk density (< 0.1 g cm⁻³). Dissolved phosphate concentrations at the sediment-water interface range from 20 to 100 μM, orders of magnitude higher than bottom-water concentrations, and much higher than predicted from regeneration of organic matter. The mechanism of this interfacial phosphate release is unclear, but is apparently uncoupled from carbon and nitrogen metabolism and thus may be linked either to dissolution of fish debris or to the presence of a microbial mat in surficial sediments. Fluoride is incorporated into CFA by diffusion from the overlying seawater, and carbonate ions are provided from pore-water alkalinity. Magnesium concentrations in this reaction zone are not significantly different from those of seawater, suggesting that magnesium depletion is not a necessary prerequisite for CFA precipitation.

The environment of precipitation is interface-linked rather than driven by organic diagenesis of phosphorus deeper in the sediment. Most of the cores display a wide range of diagenetic characteristics below the immediate interfacial region, but almost all show the precipitation signature near the interface. This interface-linked early diagenetic porewater environment for the precipitation of CFA explains many of the geochemical characteristics of phosphorites and provides a “testable” model to compare the modern phosphogenic analog with ancient phosphorite deposits. Two of the cores display very high solid phase phosphorus and fluoride contents reflecting the presence of apparently modern pelletal apatites.     

Sources and sinks of methylgermanium in natural waters

New data have extended our understanding of the distribution and behavior of methylgermanium in the environment. Laboratory attempts to induce aerobic methylation with known biological and abiotic methylating agents were unsuccessful; this confirmed previous field observations of methylgermanium's unreactive behavior. However, biomethylation of inorganic germanium was observed in the anaerobic digestor of a sewage treatment plant, which suggested a terrestrial methanogenic source. Attempts to locate such a source in methanogenic swamps and their drainages reveal very low methylgermanium concentrations typical of other remote, pristine rivers. Polluted rivers have monomethylgermanium (MMGe) and dimethylgermanium (DMGe) concentrations 3–100 times higher than those of pristine rivers, which suggests an anthropogenic source of methylgermanium as a result of the synergistic effects of sewage treatment and coal-ash derived inorganic germanium contamination. A new high-precision profile of MMGe and DMGe in the Sargasso Sea shows conservative behavior with no vertical gradients. However, marine anoxic basins have both inorganic germanium enrichment and methylgermanium depletion, which suggests that of marine anaerobic processes are responsible for demethylating marine organogermanium. These results all suggest that methylgermanium is produced on the continents, is unreactive in the open ocean, and is destroyed in marine anoxic environments. The residence time of organogermanium in the sea, based on a continental source (pristine rivers), is at least 1 Ma, consistent with its unreactive nature, its observed distribution in the ocean, and rates of destruction in anoxic basins.     

Evolution of tholeiitic diabase sheet systems in the eastern United States: examples from the Culpeper Basin, Virginia-Maryland, and the Gettysburg Basin, Pennsylvania

High-TiO₂, quartz-normative (HTQ) tholeiite sheets of Early Jurassic age have intruded mainly Late Triassic sedimentary rocks in several early Mesozoic basins in the eastern United States. Field observations, petrographic study, geochemical analyses and stable isotope data from three HTQ sheet systems in the Culpeper basin of Virginia and Maryland and the Gettysburg basin of Pennsylvania were used to develop a general model of magmatic differentiation and magmatic-hydrothermal interaction for HTQ sheets. The three sheet systems have remarkably similar major-oxide and trace-element compositions. Cumulus and evolved diabase in comagmatic sheets separated by tens of kilometers are related by igneous differentiation. Differentiated diabase in all three sheets have petrographic and geochemical signatures and fluid inclusions indicating hydrothermal alteration beginning near magmatic temperatures and continuing to relatively low temperatures. Sulfur and oxygen isotope data are consistent with a magmatic origin for the hydrothermal fluid.The three sheet systems examined apparently all had a similar style of crystal-liquid fractionation that requires significant lateral migration of residual magmatic liquid. The proposed magmatic model for HTQ sheets suggests that bronzite-laden magma was intruded in an upper crustal magma chamber, with bronzite phenocrysts collecting in the lower part of the magma chamber near the feeder dike. Early crystallization of augite and Ca-poor pyroxene before significant plagioclase crystallization resulted in density-driven migration of lighter residual magmatic liquids along lateral and vertical pressure gradients towards the upper part of the sheet. The influence of water on the physical properties of the residual liquid, including density, viscosity and liquidus temperature, may have facilitated the lateral movement more than 15 km up dip in the sheets. Exsolution of a Cl- and S-rich metal-bearing aqueous fluid from residual magma resulted in concentration and redistribution of incompatible and aqueoussoluble elements in late-stage differentiated rocks. This proposed hydrothermal mechanism has important economic implications as it exerts a strong control on the final distribution of noble metals in these types of diabase sheets.     

Geochemical behavior of inorganic germanium in an unperturbed estuary

Eleven monthly estuarine profiles of dissolved inorganic germanium (Ge_i) and silica (Si) in a natural, pristine river/bay system demonstrate that Ge-removal and -input parallel the seasonal silica cycle, reflecting Ge-uptake by and -dissolution from diatoms. The Ge/Si atom ratio of the river is 0.6 ± 0.15 × 10^?6, which is near the average value for continental granites and for uncontaminated, remote, natural rivers (0.7 ± 0.3 × 10^?6). The $\text{Ge}\text{Si}$ ratio escaping this estuary to the ocean is 0.8 × 10^?6, reflecting some estuarine enhancement of the fluvial Ge-flux, probably due to release of Ge_i from fluvial particulates. Nevertheless, the post-estuarine $\text{Ge}\text{Si}$ ratio is not significantly different from the continental crustal ratio but is very different from the ratio in sea-floor hot springs and mid-ocean ridge hydrothermal plumes (4 ± 2 × 10^?6) and in oceanic basalts (2.6 × 10^?6). Thus natural estuarine processes do not obscure the contrasting $\text{Ge}\text{Si}$ signatures entering the ocean from dissolution of continental and sea-floor silicates.