Organic carbon deposition and phosphorus accumulation during Oceanic Anoxic Event 2 in Tarfaya, Morocco

With a multi-proxy approach, an attempt was made to constrain productivity and bottom-water redox conditions and their effects on the phosphorus accumulation rate at the Mohammed Plage section on the Tarfaya coast, Morocco, during the Cenomanian-Turonian Anoxic Event (OAE 2). A distinct δ¹³C_org isotope excursion of +2.5‰ occurs close to the top of the section. The unusually abrupt shift of the isotope excursion and disappearance of several planktonic foraminiferal species (e.g. Rotalipora cushmani and Rotalipora greenhornensis) in this level suggests a hiatus of between 40–60 kyrs at the excursion onset. Nevertheless, it was possible to determine both the long-term environmental history as well as the processes that took place immediately prior to and during OAE 2. TOC% values increase gradually from the base of the section to the top (from 2.5% to 10%). This is interpreted as the consequence of a long-term eustatic sea-level rise and subsidence causing the encroachment of less oxic waters into the Tarfaya Basin. Similarly a reduction in the mineralogically constructed ‘detrital index’ can be explained by the decrease in the continental flux of terrigenous material due to a relative sea-level rise. A speciation of phosphorus in the upper part of the section, which spans the start and mid-stages of OAE 2, shows overall higher abundances of P_reactive mass accumulation rates before the isotope excursion onset and lower values during the plateau. Due to the probable short hiatus, the onset of the decrease in phosphorus content relative to the isotope excursion is uncertain, although the excursion plateau already contains lower concentrations. The C_org/P_total and V/Al ratios suggest that this reduction was mostly likely caused by a decrease in the available bottom oxygen content (probably as a result of higher productivity) and a corresponding fall in the phosphorus retention ability of the sediment. Productivity appears to have remained high during the isotope plateau possibly due to a combination of ocean-surface fertilisation via increased aridity (increased K/Al and Ti/Al ratios) and/or higher dissolved inorganic phosphorus content in the water column as a result of the decrease in sediment P retention. The evidence for decreased P-burial has been observed in many other palaeoenvironments during OAE 2. Tarfaya's unique upwelling paleosituation provides strong evidence that the nutrient recycling was a global phenomenon and therefore a critical factor in starting and sustaining OAE 2.     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Controls on porphyroblast size along a regional metamorphic field gradient

Garnet-bearing schists from the Waterville Formation of south-central Maine provide an opportunity to examine the factors governing porphyroblast size over a range of metamorphic grade. Three-dimensional sizes and locations for all garnet porphyroblasts were determined for three samples along the metamorphic field gradient spanning lowest garnet through sillimanite grade, using high-resolution X-ray computed tomography. Comparison of crystal size distributions to previous data sets obtained by stereological methods for the same samples reveals significant differences in mode, mean, and shape of the distributions. Quantitative textural analysis shows that the garnets in each rock crystallized in a diffusion-controlled nucleation and growth regime. In contrast to the typical observation of a correlation between porphyroblast size and position along a metamorphic field gradient, porphyroblast size of the lowest-grade specimen is intermediate between the high- and middle-grade specimens’ sizes. Mean porphyroblast size does not correlate with peak temperatures from garnet-biotite Fe-Mg exchange thermometry, nor is post-crystallization annealing (Ostwald Ripening) required to produce the observed textures, as was previously proposed for these rocks. Robust pseudosection calculations fail to reproduce the observed garnet core compositions for two specimens, suggesting that these calc-pelites experienced metasomatism. For each of these two specimens, Monte Carlo calculations suggest potential pre-metasomatism bulk compositions that replicate garnet core compositions. Pseudosection analyses allow the estimation of the critical temperatures for garnet growth: ∼481, ∼477, and ∼485°C for the lowest-garnet-zone, middle-garnet-zone, and sillimanite-zone specimens, respectively. Porphyroblast size appears to be determined in this case by a combination of the heating rate during garnet crystallization, the critical temperature for the garnet-forming reaction and the kinetics of nucleation. Numerical simulations of thermally accelerated, diffusion-controlled nucleation, and growth for the three samples closely match measured crystal size distributions. These observations and simulations suggest that previous hypotheses linking the garnet size primarily to the temperature at the onset of porphyroblast nucleation can only partially explain the observed textures. Also important in determining porphyroblast size are the heating rate and the distribution of favorable nucleation sites.     

Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.     

Low-oxygen and chemical kinetic constraints on the geochemical niche of neutrophilic iron(II) oxidizing microorganisms

Neutrophilic iron oxidizing bacteria (FeOB) must actively compete with rapid abiotic processes governing Fe(II) oxidation and as a result have adapted to primarily inhabit low-O₂ environments where they can more successfully compete with abiotic Fe(II) oxidation. The spatial distribution of these microorganisms can be observed through the chemical gradients they affect, as measured using in situ voltammetric analysis for dissolved Fe(II), Fe(III), O₂, and FeS_(aq). Field and laboratory determination of the chemical environments inhabited by the FeOB were coupled with detailed kinetic competition studies for abiotic and biotic oxidation processes using a pure culture of FeOB to quantify the geochemical niche these organisms inhabit. In gradient culture tubes, the maximum oxygen levels, which were associated with growth bands of Sideroxydans lithotrophicus (ES-1, a novel FeOB), were 15-50 μM. Kinetic measurements made on S. lithotrophicus compared biotic/abiotic (killed control) Fe oxidation rates. The biotic rate can be a significant and measurable fraction of the total Fe oxidation rate below O₂ concentrations of approximately 50 μM, but biotic Fe(II) oxidation (via the biotic/abiotic rate comparison) becomes difficult to detect at higher O₂ levels. These results are further supported by observations of conditions supporting FeOB communities in field settings. Variablity in cell densities and cellular activity as well as variations in hydrous ferrous oxide mineral quantities significantly affect the laboratory kinetic rates. The microbial habitat (or geochemical niche) where FeOB are active is thus largely controlled by the competition between abiotic and biotic kinetics, which are dependent on Fe(II) concentration, P_O2, temperature and pH in addition to the surface area of hydrous ferric oxide minerals and the cell density/activity of FeOB. Additional field and lab culture observations suggest a potentially important role for the iron-sulfide aqueous molecular cluster, FeS_(aq), in the overall cycling of iron associated with the environments these microorganisms inhabit.     

Upwelling, species, and depth effects on coral skeletal cadmium-to-calcium ratios (Cd/Ca)

Skeletal cadmium-to-calcium (Cd/Ca) ratios in hermatypic stony corals have been used to reconstruct changes in upwelling over time, yet there has not been a systematic evaluation of this tracer’s natural variability within and among coral species, between depths and across environmental conditions. Here, coral skeletal Cd/Ca ratios were measured in multiple colonies of Pavona clavus, Pavona gigantea and Porites lobata reared at two depths (1 and 7 m) during both upwelling and nonupwelling intervals in the Gulf of Panama (Pacific). Overall, skeletal Cd/Ca ratios were significantly higher during upwelling than during nonupwelling, in shallow than in deep corals, and in both species of Pavona than in P. lobata. P. lobata skeletal Cd/Ca ratios were uniformly low compared to those in the other species, with no significant differences between upwelling and nonupwelling values. Among colonies of the same species, skeletal Cd/Ca ratios were always higher in all shallow P. gigantea colonies during upwelling compared to nonupwelling, though the magnitude of the increase varied among colonies. For P. lobata, P. clavus and deep P. gigantea, changes in skeletal Cd/Ca ratios were not consistent among all colonies, with some colonies having lower ratios during upwelling than during nonupwelling. No statistically significant relationships were found between skeletal Cd/Ca ratios and maximum linear skeletal extension, δ¹³C or δ¹⁸O, suggesting that at seasonal resolution the Cd/Ca signal was decoupled from growth rate, coral metabolism, and ocean temperature and salinity, respectively. These results led to the following conclusions, (1) coral skeletal Cd/Ca ratios are independent of skeletal extension, coral metabolism and ambient temperature/salinity, (2) shallow P. gigantea is the most reliable species for paleoupwelling reconstruction and (3) the average Cd/Ca record of several colonies, rather than of a single coral, is needed to reliably reconstruct paleoupwelling events.     

The Fe-C system at 5 GPa and implications for Earth’s core

Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe₃C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe₃C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe₃C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe₃C. Fe₃C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe₃C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe₃C.     

Uranophane dissolution and growth in CaCl2-SiO2(aq) test solutions

The dissolution and growth of uranophane [Ca(UO₂)₂(SiO₃OH)₂·5H₂O] have been examined in Ca- and Si-rich test solutions at low temperatures (20.5 ± 2.0 °C) and near-neutral pH (∼6.0). Uranium-bearing experimental solutions undersaturated and supersaturated with uranophane were prepared in matrices of ∼10⁻² M CaCl₂ and ∼10⁻³ M SiO₂(aq). The experimental solutions were reacted with synthetic uranophane and analyzed periodically over 10 weeks. Interpretation of the aqueous solution data permitted extraction of a solubility constant for the uranophane dissolution reaction and standard state Gibbs free energy of formation for uranophane ( kJ mol⁻¹).     

Coupled and complex: Human-environment interaction in the Greater Yellowstone Ecosystem, USA

Complexity theory has received considerable attention over the past decade from a wide variety of disciplines. Some who write on this topic suggest that complexity theory will lead to a unifying understanding of complex phenomena; others dismiss it as a passing and disruptive fad. We suggest that for the analysis of coupled natural/human systems, the truth emerges from the middle ground. As an approach focused as much on the connections among system elements as the elements themselves, we argue that complexity theory provides a useful conceptual framework for the study of coupled natural/human systems. It is, if nothing else, a framework that leads us to ask interesting questions about, for example, sustainability, resilience, threshold events, and predictability.In this paper we attempt to demystify the ongoing discussions on complexity theory by linking its evocative and overloaded terminology to real-world processes. We illustrate how a shift in focus from system elements to connections among elements can lead to meaningful insight into human-environment interactions that might otherwise be overlooked. We ground our discussion in ongoing interdisciplinary research surrounding Yellowstone National Park’s northern elk winter range; a tightly coupled natural/human system that has been the center of debate, conflict, and compromise for more than 135 years.     

Phase Relations and Melting of Anhydrous K-bearing Eclogite from 1200 to 1600{degrees}C and 3 to 5 GPa

To investigate eclogite melting under mantle conditions, wehave performed a series of piston-cylinder experiments usinga homogeneous synthetic starting material (GA2) that is representativeof altered mid-ocean ridge basalt. Experiments were conductedat pressures of 3·0, 4·0 and 5·0 GPa andover a temperature range of 1200–1600°C. The subsolidusmineralogy of GA2 consists of garnet and clinopyroxene withminor quartz–coesite, rutile and feldspar. Solidus temperaturesare located at 1230°C at 3·0 GPa and 1300°C at5·0 GPa, giving a steep solidus slope of 30–40°C/GPa.Melting intervals are in excess of 200°C and increase withpressure up to 5·0 GPa. At 3·0 GPa feldspar, rutileand quartz are residual phases up to 40°C above the solidus,whereas at higher pressures feldspar and rutile are rapidlymelted out above the solidus. Garnet and clinopyroxene are theonly residual phases once melt fractions exceed 20% and garnetis the sole liquidus phase over the investigated pressure range.With increasing melt fraction garnet and clinopyroxene becomeprogressively more Mg-rich, whereas coexisting melts vary fromK-rich dacites at low degrees of melting to basaltic andesitesat high melt fractions. Increasing pressure tends to increasethe jadeite and Ca-eskolaite components in clinopyroxene andenhance the modal proportion of garnet at low melt fractions,which effects a marked reduction in the Al₂O₃ and Na₂O contentof the melt with pressure. In contrast, the TiO₂ and K₂O contentsof the low-degree melts increase with increasing pressure; thusNa₂O and K₂O behave in a contrasted manner as a function ofpressure. Altered oceanic basalt is an important component ofcrust returned to the mantle via plate subduction, so GA2 maybe representative of one of many different mafic lithologiespresent in the upper mantle. During upwelling of heterogeneousmantle domains, these mafic rock-types may undergo extensivemelting at great depths, because of their low solidus temperaturescompared with mantle peridotite. Melt batches may be highlyvariable in composition depending on the composition and degreeof melting of the source, the depth of melting, and the degreeof magma mixing. Some of the eclogite-derived melts may alsoreact with and refertilize surrounding peridotite, which itselfmay partially melt with further upwelling. Such complex magma-genesisconditions may partly explain the wide spectrum of primitivemagma compositions found within oceanic basalt suites. KEY WORDS: eclogite; experimental petrology; mafic magmatism; mantle melting; oceanic basalts