Provenance and microprobe assays of phyllite‐tempered ceramics from the uplands of central Arizona

The ceramics in use across a broad upland zone of central Arizona during the early Classic period (ca. A.D. 1100–1300) were characterized by a lack of mineralogical variability; nearly all of the clay containers were tempered with one rock type, phyllite. Consequently, nearly all of the upland pottery is assigned to a single pottery type, Wingfield Plain. This compositional uniformity has frustrated ceramic provenance studies, and, as a result, little has been learned previously about the organization of ceramic production and exchange in the upland territory. There are, however, considerable and interpretable chemical differences in the phyllite‐tempered wares, as shown with microanalyses of the temper fragments and pottery clay fractions with an electron microprobe. The chemical patterning is useful for investigating issues pertaining to the upland zone, including the organization of ceramic manufacture, community arrangements, and pottery transactions during a time of prevalent hostilities in central Arizona. © 2008 Wiley Periodicals, Inc.     

Sulfide Oxidation across Diffuse Flow Zones of Hydrothermal Vents

The sulfide (H₂S/HS^?) that is emitted from hydrothermal vents begins to oxidize abiotically with oxygen upon contact with ambient bottom water, but the reaction kinetics are slow. Here, using in situ voltammetry, we report detection of the intermediate sulfur oxidation products polysulfides [ $ {\text{S}}_{\text{x}}^{2 - } $ ] and thiosulfate [ $ {\text{S}}_{ 2} {\text{O}}_{ 3}^{ 2- } $ ], along with contextual data on sulfide, oxygen, and temperature. At Lau Basin in 2006, thiosulfate was identified in less than one percent of approximately 10,500 scans and no polysulfides were detected. Only five percent of 11,000 voltammetric scans taken at four vent sites at Lau Basin in May 2009 show either thiosulfate or polysulfides. These in situ data indicate that abiotic sulfide oxidation does not readily occur as H₂S contacts oxic bottom waters. Calculated abiotic potential sulfide oxidation rates are <10^?3 ??M/min and are consistent with slow oxidation and the observed lack of sulfur oxidation intermediates. It is known that the thermodynamics for the first electron transfer step for sulfide and oxygen during sulfide oxidation in these systems are unfavorable, and that the kinetics for two electron transfers are not rapid. Here, we suggest that different metal catalyzed and/or biotic reaction pathways can readily produce sulfur oxidation intermediates. Via shipboard high-pressure incubation experiments, we show that snails with chemosynthetic endosymbionts do release polysulfides and may be responsible for our field observations of polysulfides.     

Reactivation and strain localisation in Bhavani shear zone,South India

Shear markers and shear sense indicators from the Bhavani shear zone, a member of the shear system separating the northern Archaean and southern Pan African granulite terranes of the South Indian shield, with differently exhumed crustal blocks, suggest multiphase reactivation. This is revealed by textural and geochemical characteristics of mylonites which indicate an event of prograde epidote-amphibolite facies metamorphism of the previously retrograded protolith of shear zone rocks. The amphibole varies progressively from an initial magnesio-hornblende to ferrotschermakitic hornblende with increasing Al and K while the plagioclase maintains oligoclase composition (An21-25). P-T estimates suggest metamorphic conditions of 634°C - 720°C at 3.6±0.5 to 5.8±0.5 kbar. Strain partitioning during the reactivation of the shear zone prior to the Pan African event, is responsible for the gradation in the intensity of mylonitic fabric as well as some of the opposing shear sense indicators.     

Geochemistry and sequence stratigraphy of regional Upper Cretaceous limestone units, offshore eastern Canada

Hydrocarbons occur in two regional, Upper Cretaceous limestone units—the Turonian-Coniacian Petrel Member, and the Santonian-Maastrichtian Wyandot Formation. The units form important seismic markers beneath the Scotian Shelf and the Grand Banks of Eastern Canada. They mainly consist of bioturbated chalk and minor amounts of calcareous mudstone. A search for source rock using the Δ log R technique showed intervals with source potential, but testing of core and cuttings by Rock-Eval analysis showed no source potential. Three issues are the main cause for the inconsistency: (1) unconsolidated shales that likely included organic material were lost during sample washing; (2) severe contamination by mud additives; and (3) presence of gas. The organic matter found on the shelf has been strongly oxidised, but the distal facies of these limestone units and condensed shale units above and below may yet have potential to form source rock, beyond the studied areas.     

Formation of metal in Grosvenor Mountains 95551 and comparison to ordinary chondrites

Siderophile element abundances in individual metal grains in the ungrouped chondrite Grosvenor Mountains (GRO) 95551 and in the ordinary chondrites Tieschitz H3.6, Soko-Banja LL4, and Allegan H5 were measured with laser ablation-inductively coupled plasma mass spectrometry. Matrix metal in GRO 95551 falls into two distinct compositional groups, a high-Ni group with 7.2 ± 0.4 wt% Ni and a low-Ni group with 3.7 ± 0.1 wt% Ni, indicating that kamacite/taenite equilibration at ∼1020 K was followed by rapid cooling. The nonrefractory siderophile elements P, Co, Cu, Ga, Ge, As, Pd, and Au also partition between the high-Ni and low-Ni metal in a manner consistent with kamacite/taenite fractionation, but the refractory siderophiles Ru, Re, Os, Ir, and Pt show correlated variations that are unrelated to kamacite/taenite partitioning and indicate that variations in refractory components of the metal were not completely erased during equilibration at ∼1020 K. The Ni-normalized bulk metal composition of GRO 95551 is refractory depleted and volatile rich relative to Bencubbin and related metal-rich chondrites but bears strong similarities to equilibrated ordinary chondrite metal. GRO 95551 represents a new chondrite type with chemical affinity to the ordinary chondrites. Individual metal grains in unequlibrated ordinary chondrites also have correlated variations in refractory siderophile contents that cannot be produced by redox processes alone; these variations span three orders of magnitude and diminish with increasing metamorphic grade of the ordinary chondrites.     

Surface structure effects on direct reduction of iron oxides by Shewanella oneidensis

The atomic and electronic structure of mineral surfaces affects many environmentally important processes such as adsorption phenomena. They are however rarely considered relevant to dissimilatory bacterial reduction of iron and manganese minerals. In this regard, surface area and thermodynamics are more commonly considered. Here we take a first step towards understanding the nature of the influence of mineral surface structure upon the rate of electron transfer from Shewanella oneidensis strain MR-1 outer membrane proteins to the mineral surface and the subsequent effect upon cell “activity.” Cell accumulation has been used as a proxy for cell activity at three iron oxide single crystal faces; hematite (001), magnetite (111) and magnetite (100). Clear differences in cell accumulation at, and release from the surfaces are observed, with significantly more cells accumulating at hematite (001) compared to either magnetite face whilst relatively more cells are released into the overlying aqueous phase from the two magnetite faces than hematite. Modeling of the electron transfer process to the different mineral surfaces from a decaheme (protoporphyrin rings containing a central hexacoordinate iron atom), outer membrane-bound cytochrome of S. oneidensis has been accomplished by employing both Marcus and ab initio density functional theories. The resultant model of electron transfer to the three oxide faces predicts that over the entire range of expected electron transfer distances the highest electron transfer rates occur at the hematite (001) surface, mirroring the observed cell accumulation data. Electron transfer rates to either of the two magnetite surfaces are slower, with magnetite (111) slower than hematite (001) by approximately two orders of magnitude. A lack of knowledge regarding the structural details of the heme-mineral interface, especially in regards to atomic distances and relative orientations of hemes and surface iron atoms and the conformation of the protein envelope, precludes a more thorough analysis. However, the results of the modeling concur with the empirical observation that mineral surface structure has a clear influence on mineral surface-associated cell activity. Thus surface structure effects must be accounted for in future studies of cell-mineral interactions.     

Rare Earth Element and yttrium compositions of Archean and Paleoproterozoic Fe formations revisited: New perspectives on the significance and mechanisms of deposition

The ocean and atmosphere were largely anoxic in the early Precambrian, resulting in an Fe cycle that was dramatically different than today’s. Extremely Fe-rich sedimentary deposits—i.e., Fe formations—are the most conspicuous manifestation of this distinct Fe cycle. Rare Earth Element (REE) systematics have long been used as a tool to understand the origin of Fe formations and the corresponding chemistry of the ancient ocean. However, many earlier REE studies of Fe formations have drawn ambiguous conclusions, partially due to analytical limitations and sampling from severely altered units. Here, we present new chemical analyses of Fe formation samples from 18 units, ranging in age from ca. 3.0 to 1.8 billion years old (Ga), which allow a reevaluation of the depositional mechanisms and significance of Precambrian Fe formations. There are several temporal trends in our REE and Y dataset that reflect shifts in marine redox conditions. In general, Archean Fe formations do not display significant shale-normalized negative Ce anomalies, and only Fe formations younger than 1.9 Ga display prominent positive Ce anomalies. Low Y/Ho ratios and high shale-normalized light to heavy REE (LREE/HREE) ratios are also present in ca. 1.9 Ga and younger Fe formations but are essentially absent in their Archean counterparts. These marked differences in Paleoproterozoic versus Archean REE + Y patterns can be explained in terms of varying REE cycling in the water column.Similar to modern redox-stratified basins, the REE + Y patterns in late Paleoproterozoic Fe formations record evidence of a shuttle of metal and Ce oxides across the redoxcline from oxic shallow seawater to deeper anoxic waters. Oxide dissolution—mainly of Mn oxides—in an anoxic water column lowers the dissolved Y/Ho ratio, raises the light to heavy REE ratio, and increases the concentration of Ce relative to the neighboring REE (La and Pr). Fe oxides precipitating at or near the chemocline will capture these REE anomalies and thus evidence for this oxide shuttle. In contrast, Archean Fe formations do not display REE + Y patterns indicative of an oxide shuttle, which implies an absence of a distinct Mn redoxcline prior to the rise of atmospheric oxygen in the early Paleoproterozoic. As further evidence for reducing conditions in shallow-water environments of the Archean ocean, REE data for carbonates deposited on shallow-water Archean carbonate platforms that stratigraphically underlie Fe formations also lack negative Ce anomalies. These results question classical models for deposition of Archean Fe formations that invoke oxidation by free oxygen at or above a redoxcline. In contrast, we add to growing evidence that metabolic Fe oxidation is a more likely oxidative mechanism for these Fe formations, implying that the Fe distribution in Archean oceans could have been controlled by microbial Fe uptake rather than the oxidative potential of shallow-marine environments.     

Uranium and Thorium Concentration and Isotopic Composition in Five Glass (BHVO‐2G,BCR‐2G,NKT‐1G,T1‐G,ATHO‐G) and Two Powder (BHVO‐2, BCR‐2) Reference Materials

Here we report uranium and thorium isotopic ratios and elemental concentrations measured in solid reference materials from the USGS (BHVO‐2G, BCR‐2G, NKT‐1G), as well as those from the MPI‐DING series (T1‐G, ATHO‐G). Specifically created for microanalysis, these naturally‐sourced glasses were fused from rock powders. They cover a range of compositions, elemental concentrations and expected isotopic ratios. The U‐Th isotopic ratios of two powdered source materials (BCR‐2, BHVO‐2) were also characterised. These new measurements via multi‐collector thermal ionisation mass spectrometry and multi‐collector inductively coupled plasma‐mass spectrometry can now be used to assess the relative performance of techniques and facilitate comparison of U‐Th data amongst laboratories in the geoscience community for in situ and bulk analyses.