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Degradation of 1,1,2,2-tetrachloroethane and accumulation of vinyl chloride in wetland sediment microcosms and in situ porewater: Biogeochemical controls and associations with microbial communities

The biodegradation pathways of 1,1,2,2-tetrachloroethane (TeCA) and 1,1,2-trichloroethane (112TCA) and the associated microbial communities in anaerobic wetland sediments were evaluated using concurrent geochemical and genetic analyses over time in laboratory microcosm experiments. Experimental results were compared to in situ porewater data in the wetland to better understand the factors controlling daughter product distributions in a chlorinated solvent plume discharging to a freshwater tidal wetland at Aberdeen Proving Ground, Maryland. Microcosms constructed with wetland sediment from two sites showed little difference in the initial degradation steps of TeCA, which included simultaneous hydrogenolysis to 112TCA and dichloroelimination to 1,2-dichloroethene (12DCE). The microcosms from the two sites showed a substantial difference, however, in the relative dominance of subsequent dichloroelimination of 112TCA. A greater dominance of 112TCA dichloroelimination in microcosms constructed with sediment that was initially iron-reducing and subsequently simultaneously iron-reducing and methanogenic caused approximately twice as much vinyl chloride (VC) production as microcosms constructed with sediment that was methanogenic only throughout the incubation. The microcosms with higher VC production also showed substantially more rapid VC degradation. Field measurements of redox-sensitive constituents, TeCA, and its anaerobic degradation products along flowpaths in the wetland porewater also showed greater production and degradation of VC with concurrent methanogenesis and iron reduction. Molecular fingerprinting indicated that bacterial species [represented by a peak at a fragment size of 198 base pairs (bp) by MnlI digest] are associated with VC production from 112TCA dichloroelimination, whereas methanogens (190 and 307 bp) from the Methanococcales or Methanobacteriales family are associated with VC production from 12DCE hydrogenolysis. Acetate-utilizing methanogens (acetotrophs) appear to be involved in the biodegradation of VC. The relative abundance of Methanosarcinaceae, the only methanogen group with acetotrophic members, doubled in microcosms in which degradation of VC was observed. In addition, molecular analyses using primers specific for known dehalorespiring bacteria in the Dehalococcoides and Desulfuromonas groups showed the presence of these bacteria in microcosm slurry from the site that showed the highest VC production and degradation. Determination of biogeochemical controls and microbial consortia involved in TeCA degradation is leading to a better understanding of the heterogeneity in biodegradation rates and daughter product distribution in the wetland, improving capabilities for developing remediation and monitoring plans.

Journal of Contaminant Hydrology

Integration of channel and floodplain suites. I. Developmental sequence and lateral relations of alluvial paleosols.

The lower Eocene Willwood Formation of the Bighorn Basin, northwest Wyoming, consists of about 770 m of alluvial rocks that exhibit extensive mechanical and geochemical modifications resulting from Eocene pedogenesis. Willwood paleosols vary considerably in their relative degrees of maturity; maturity is defined as stage of development as a function of the amount of time required to form. Five arbitrary stages are proposed to distinguish these soils of different maturities in the Willwood Formation. Stage 1 soils, the least mature, are entisols; stage 2 and stage 3 soils are intermediate in maturity and are probably alfisols; and stage 4 and stage 5 soils, the most mature, are spodosols. These stages are not only time-progressive elements of an in situ maturation sequence for Willwood soil formation, but, in the lateral dimension, they are also usually distributed sequentially. Study of Willwood paleosols indicates that an inverse relationship exists between soil maturity and short-term sediment accumulation rate. The least mature Willwood paleosols formed in areas of relatively high net rates of sediment accumulation on 1) channel, levee, and crevasse-splay sediments of the proximal alluvial ridge, and 2) deposits filling large and small paleovalleys formed by major episodes of gullying (lowered baselevels). In contrast, the fine-grained sediments of the distal floodplain, where net sediment accumulation rates were relatively low, experienced development of much more mature soils. Soils of intermediate maturities occur in the order of their stage on intervening proximal floodplain and distal alluvial ridge sediments. Adjacent bodies of sedimentary rock that differ in their ancient soil properties because of distance from areas of relatively high sediment accumulation are denoted by the new term pedofacies . The remarkable sequence of paleosols in the Willwood Formation clearly illustrates several important principles of soil-sediment interrelationships in aggrading alluvial systems that have broad application to other deposits. This is especially true in view of the widespread distribution of paleosols in nearly all ancient fluvial rocks. Further study of Willwood paleosols will not only enable precise lateral correlation of coeval alluvial sediments, and thereby fluvial sedimentary events, from the distal to the proximal realms of the floodplain but will also contribute to increasingly informative evaluations of the nature, tempo, and mode of alluvial succession.

Journal of Sedimentary Petrology

Gas and ash emissions associated with the 2010–present activity of Sinabung Volcano, Indonesia

Sinabung Volcano (Sumatra, Indonesia) awoke from over 1200 years of dormancy with multiple phreatic explosions in 2010. After a period of quiescence, Sinabung activity resumed in 2013, producing frequent explosions, lava dome extrusion, and pyroclastic flows from dome collapses, becoming one of the world's most active volcanoes and displacing over 20,000 citizens. This study presents a compilation of the geochemical datasets collected by the Indonesian Center for Volcanology and Geological Hazard Mitigation (CVGHM) from 2010 - current (2016), which provides insights into the evolution of the eruption. Based on observations of SO2 emissions, ash componentry, leachate chemistry, and bulk ash geochemistry, the eruption can be split into five distinct phases. The initial stage of phreatic summit explosions occurred from August - October 2010, during which background SO2 emissions averaged ~550 ± 180 t/d (1 s.d.). An eruptive pause (phase two) starting in October 2010 abruptly ended in September 2013 with a resumption of conduit-clearing eruptions. This third phase had a relatively modest background SO2 emission rate (avg. ~410 ± 275 t/d) and produced ash consisting entirely of accidental ejecta with high S/Cl leachate ratios (up to 30), suggestive of deep-sourced magma and the incorporation of hydrothermal sulfur-bearing phases. The most intense phase of the eruption (phase four) occurred from December 2013 to February 2014, when juvenile magma first reached the surface. This period included dozens of large eruptions per day, high SO2 emission rates (average: 1,120 ± 1,030 t/d, peak: ~3,800 t/d), the onset of lava dome extrusion, and a dramatic drop in S/Cl ash leachates to ratios < 5, all reflecting increased degassing from shallow magma and the clearing out of sulfurous phases from the old hydrothermal system. From late February 2014 through the time of writing (September 2016), Sinabung settled into a relatively steady state of lower activity (phase five). Ash emissions now consist of dominantly juvenile material, and background SO2 emission rates have been progressively decreasing to an average of ~250 - 300 t/d. Starting August 2016, SO2 emissions started being measured in a continuous manner using a network of permanent scanning DOAS instruments. We find that long-term SO2 emission rates have been gradually declining at Sinabung since early 2014, consistent with an apparent decrease in magma supply. Our degassing model suggests that large explosions and pyroclastic flows could continue in the near-term owing to conduit plugging and dome collapses, remaining a major threat until the magma supply rate decreases further and the eruption ends.

Sumatra

Channel-fill coal beds along the western margin of the Eastern Kentucky Coal Field

Four channel-filling coal beds from the lower part of the Breathitt Formation (lower Middle Pennsylvanian, late Westphalian A) were examined palynologically, petrographically and geochemically to determine the paleoenvironmental conditions under which these peats accumulated. These results were then compared with detailed sedimentological analyses of the strata overlying the coal in the channels to see if any genetic relationship between coal composition and the origin of the overburden could be drawn. All four of the coal beds used in this study are located in the western-most part of the Eastern Kentucky Coal Field and occur at, or near, the Early Pennsylvanian unconformity (0–30 m). Lycospora and Densosporites (and related crassicingulate taxa, e.g. Cristatisporites , Cingulizonates and Radiizonates ) dominate the studied assemblages, with Granulatisporites (and related trilete, sphaerotriangular genera, e.g. Leiotriletes and Lophotriletes ), Laevigatosporites and Schulzospora being common accessory genera. Petrographically, all four coals contain high percentages of vitrinite macerals (avg. 78.6% mineral matter free), moderate amounts of liptinite (or exinite) macerals (avg. 14.9%, mmf) and low percentages of inertinite macerals (avg. 6.5%, mmf). Strata above the coals consist of dark, carbonaceous shales, and heterolithic strata that exhibit varying degrees of bioturbation. Commonly occurring trace fossils include Arenicolites , Monocraterion , Planolites and Skolithos . Although marine-influenced strata, as determined from detailed sedimentology and ichnology (the study of trace fossils), covers all four coal beds, they are not uniformly high in total total sulfur content as might be expected. Rather they are extremely variable, ranging from 1–9% (dry basis) total sulfur. Ash yields are also variable ranging from 6.2–54.3% (dry basis). It is probable that the origin of the very first sediments covering the peat, as well as the amount of brackish water influence during peat accumulation, were important factors in determining the total sulfur content of the resultant coal. Initial sedimentation of fresh water clays and silts may have acted as a barrier to downward percolation/diffusion of sulfate bearing waters, or may have served as a site for sulfide formation, thereby keeping the total sulfur content of the underlying coal low. If initial sedimentation was of brackish or marine origin, as indicated by bioturbated laminae directly above the coal, or if the peat was subject to frequent brackish or marine water influence during accumulation, then sulfide generation might proceed unchecked, resulting in high sulfur coal.

International Journal of Coal Geology

Limnological and climatic environments at Upper Klamath Lake, Oregon during the past 45 000 years

Upper Klamath Lake, in south-central Oregon, contains long sediment records with well-preserved diatoms and lithological variations that reflect climate-induced limnological changes. These sediment archives complement and extend high resolution terrestrial records along a north-south transect that includes areas influenced by the Aleutian Low and Subtropical High, which control both marine and continental climates in the western United States. The longest and oldest core collected in this study came from the southwest margin of the lake at Caledonia Marsh, and was dated by radiocarbon and tephrochronology to an age of about 45 ka. Paleolimnological interpretations of this core, based upon geochemical and diatom analyses, have been augmented by data from a short core collected from open water environments at nearby Howards Bay and from a 9-m core extending to 15 ka raised from the center of the northwestern part of Upper Klamath Lake. Pre- and full-glacial intervals of the Caledonia Marsh core are characterized and dominated by lithic detrital material. Planktic diatom taxa characteristic of cold-water habitats (Aulacoseira subarctica and A. islandica) alternate with warm-water planktic diatoms (A. ambigua) between 45 and 23 ka, documenting climate changes at millennial scales during oxygen isotope stage (OIS) 3. The full-glacial interval contains mostly cold-water planktic, benthic, and reworked Pliocene lacustrine diatoms (from the surrounding Yonna Formation) that document shallow water conditions in a cold, windy environment. After 15 ka, diatom productivity increased. Organic carbon and biogenic silica became significant sediment components and diatoms that live in the lake today, indicative of warm, eutrophic water, became prominent. Lake levels fell during the mid-Holocene and marsh environments extended over the core site. This interval is characterized by high levels of organic carbon from emergent aquatic vegetation (Scirpus) and by the Mazama ash (7.55 ka), generated by the eruption that created nearby Crater Lake. For a brief time the ash increased the salinity of Upper Klamath Lake. High concentrations of molybdenum, arsenic, and vanadium indicate that Caledonia Marsh was anoxic from about 7 to 5 ka. After the mid-Holocene, shallow, but open-water environments returned to the core site. The sediments became dominated (>80%) by biogenic silica. The open-water cores show analogous but less extreme limnological and climatic changes more typical of mid-lake environments. Millennial-scale lake and climate changes during OIS 3 at Upper Klamath Lake contrast with a similar record of variation at Owens Lake, about 750 km south. When Upper Klamath Lake experienced cold-climate episodes during OIS 3, Owens Lake had warm but wet episodes; the reverse occurred during warmer intervals at Upper Klamath Lake. Such climatic alternations apparently reflect the variable position and strength of the Aleutian Low during the mid-Wisconsin.

Oregon

Caldera life-cycles of the Yellowstone hotspot track: Death and rebirth of the Heise Caldera

As one of the most geochemically unique drill cores recovered within the Yellowstone–Snake River Plain (YSRP) province, the Sugar City geothermal test well was drilled into intra-caldera rhyolite lavas and tuffs erupted during the middle to late Pliocene and the resurgent basaltic volcanism erupted during the Pleistocene. This sequence parallels the two main stages proposed for YSRP hotspot calderas: i.e. the eruption of several large-volume, ash-flow tuff sheets followed by caldera collapse, then cessation of major rhyolitic activity and gradual subsidence accompanied by filling and eventual burial of the caldera by basalt lava flows. We employ stratigraphic relationships, paleomagnetism, and major, trace element, and Sr–Nd isotope geochemistry to develop models for the origin of the basaltic and rhyolitic magmas within a geographical and temporal context. The basalts are characterized by distinct groupings based on depth and geochemistry and reflect the dominant compositions observed on the surface, e.g. Snake River olivine tholeiite (SROT) and evolved type (e.g. Craters of the Moon). We also observe contaminated basalts that interacted with rhyolite/granite. The basaltic magma formed by shallow partial melting in the plume channel carved into the lithosphere. The older rhyolites preserve the classical characteristics of A-type granites and display major element and trace element concentrations typical for Eastern SRP caldera centres and minimal stratigraphic variation. Multiple lines of evidence document extensive magmatic differentiation and coupled basalt–rhyolite interactions. We find that the most plausible origin for the rhyolites is via partial melting of a hybrid source, comprising Archean crustal components and younger juvenile mafic intrusions. Assimilation of hydrothermally altered material is also required for some eruptive units. The rhyolites did not evolve from residual magma left over from the climactic Kilgore eruption (4·0 Ma), but instead represent discrete magma generation events in the course of a few hundred thousand years between 4·0 to 3·8 Ma. Beginning at approximately 3.3 Ma, basalts were able to erupt through the solidified composite pluton that formed below the caldera. The transition from rhyolite to basalt is tied to the declining flux of basaltic magma as North America moved away from the Yellowstone hotspot core.

Journal of Petrology

The geochemical and textural transition between the Reef Package and its hanging wall, Stillwater Complex, Montana, USA

The highest grade Pd-Pt deposit on Earth, the J-M Reef, is hosted in coarse-grained to pegmatoidal cumulates called the Reef Package. Decades of mine development of the J-M Reef have revealed that a distinct discontinuity in rock fabric marks the top of the rock unit that hosts economic-grade sulfide mineralization. Mine geologists refer to this discontinuity as the hanging wall contact. This contact is the top of the Reef Package and is always locatable—either by the change in rock fabric or by distinctive hanging wall textures of silicate minerals—even when the reef sulfide mineralization is absent. This rather subtle textural feature is used reliably by mine geologists to follow the Reef during exploration and mine development. Although some high tenor sulfides (>1000 ppm Pd in 100% sulfide) are found sporadically in the hanging wall cumulates, these accumulations are too small to be economically viable. We present quantitative rock fabric data for four Reef Package and hanging wall intersections collected by electron back-scattered diffraction (EBSD). Plagioclase fabrics in the hanging wall are characterized by low variance in grain sizes and a strong point maximum concentration of (010) and a perpendicular girdle distribution of [100] consistent with an axial B-type fabric. These fabrics are indicative of either compaction of the crystal mush or crystal settling of nucleated crystals, the bulk magma in a chamber. Conversely, the fabrics of the Reef Package show higher variance grain in size distributions and weak to undeveloped preferred orientation of plagioclase crystals that did not undergo significant alignment or textural equilibration of plagioclase grains. The absence of foliation in the Reef Package stands in contrast both to hanging wall fabrics and to other reported EBSD datasets of plagioclase crystals orientations from the Bushveld Complex, the Skaergaard Intrusion, and the Rum Intrusion. Furthermore, plagioclase crystal size distributions for the Reef Package show flatter slopes and convex profiles with fewer crystals at small size fractions indicating the dissolution of small crystals during partial melting and textural coarsening (i.e . Ostwald ripening) and crystal growth. Crystal growth was favored over the nucleation of new crystals during prolonged interaction with a hot infiltrating melt into the resident mush resulting in the coarse-grained textures of the Reef Package cumulates. The hanging wall contact represents a boundary between partially remelted crystal mush of the Reef Package, where sulfide mineralization formed and accumulated, and an overlying essentially barren cumulate pile. The hanging wall cumulates formed following the cessation of footwall erosion and the resumption of crystal accumulation by normal magma chamber processes.

Montana

Global petrologic variations on the moon: A ternary-diagram approach.

A ternary-diagram approach for determination of global petrologic variations on the lunar surface is presented that incorporates valuable improvements in our previous method of using geochemical variation diagrams. This new approach uses a ternary diagram that is subdivided into equally spaced segments along each of its three sides and has a triangular area in its center. The segments are assigned distinct colors that cover the range of the visible spectrum. The apexes are assigned the three primary colors, and the center triangle, which represents equal proportions of the three apexes, is assigned the color gray. The apexes are assigned the average Fe and (Th/Ti) c (ratio normalized to chondrites) compositions of KREEP/Mg-suite rocks, mare basalts, and ferroan anorthosites. The composition of each picture element (pixel) within these Apollo orbital gamma ray databases is used to determine its position within the ternary diagram. The color corresponding to this ternary position is then placed on a classification map at that pixel's position within the orbital databases. Error databases produced for the Fe and (Th/Ti) c data were used to exclude pixels having high errors. The resultant classification map shows spatial transitions among petrologic units, allows direct determination of the relative proportions of each end-member composition in a pixel, and increases the geologic interpretability of these data over that of the individual elemental databases. The classification units correspond remarkably well to observed geologic units, when we consider the spatial resolution (100 km) of the gamma ray spectrometer. Our results are as follows: (1) The highlands contain large areas of relatively pure ferroan anorthosite. (2) The average composition of the upper lunar crust is represented by an “anorthositic gabbro” composition, which supports the “magma-ocean” hypothesis for lunar crustal genesis. (3) KREEP/Mg-suite rocks are a minor fraction of the upper lunar crust. (4) Within the farside highlands, areas of KREEP/Mg-suite rocks coincide mostly with areas of crustal thinning, which are probably areas of KREEP basalt extrusions or localized excavations of Mg-suite rocks or KREEP-rich rocks. (5) Portions of the east limb and farside highlands have considerable amounts of a mafic, chondritic Th/Ti component (like mare basalt) whose occurrences coincide with mapped concentrations of light plains that display dark-halo craters; the presence of this component supports the hypothesis that mare volcanism had occurred within this highland region before the end of final heavy bombardment.

Journal of Geophysical Research Solid Earth

Programed oil generation of the Zubair Formation, Southern Iraq oil fields: Results from Petromod software modeling and geochemical analysis

1D petroleum system modeling was performed on wells in each of four oil fields in South Iraq, Zubair (well Zb-47), Nahr Umr (well NR-9), West Qurna (well WQ-15 and 23), and Majnoon (well Mj-8). In each of these fields, deposition of the Zubair Formation was followed by continuous burial, reaching maximum temperatures of 100°C (equivalent to 0.70%Ro) at depths of 3,344–3,750 m of well Zb-47 and 3,081.5–3,420 m of well WQ-15, 120°C (equivalent to 0.78%Ro) at depths of 3,353–3,645 m of well NR-9, and 3,391–3,691.5 m of well Mj-8. Generation of petroleum in the Zubair Formation began in the late Tertiary, 10 million years ago. At present day, modeled transformation ratios (TR) indicate that 65% TR of its generation potential has been reached in well Zb-47, 75% TR in well NR-9 and 55-85% TR in West Qurna oil field (wells WQ-15 and WQ-23) and up to 95% TR in well Mj-8, In contrast, younger source rocks are immature to early mature (<20% TR), whereas older source rocks are mature to overmature (100% TR). Comparison of these basin modeling results, in Basrah region, are performed with Kifle oil field in Hilla region of western Euphrates River whereas the Zubair Formation is immature within temperature range of 65–70°C (0.50%Ro equivalent) with up to 12% (TR = 12%) hydrocarbon generation efficiency and hence poor generation could be assessed in this last location. The Zubair Formation was deposited in a deltaic environment and consists of interbedded shales and porous and permeable sandstones. In Basrah region, the shales have total organic carbon of 0.5–7.0 wt%, Tmax 430–470°C and hydrogen indices of up to 466 with S2 = 0.4–9.4 of kerogen type II & III and petroleum potential of 0.4–9.98 of good hydrocarbon generation, which is consistent with 55–95% hydrocarbon efficiency. These generated hydrocarbons had charged (in part) the Cretaceous and Tertiary reservoirs, especially the Zubair Formation itself, in the traps formed by Alpine collision that closed the Tethys Ocean between Arabian and Euracian Plates and developed folds in Mesopotamian Basin 15–10 million years ago. These traps are mainly stratigraphic facies of sandstones with the shale that formed during the deposition of the Zubair Formation in transgression and regression phases within the main structural folds of the Zubair, Nahr Umr, West Qurna and Majnoon Oil fields. Oil biomarkers of the Zubair Formation Reservoirs are showing source affinity with mixed oil from the Upper Jurassic and Lower Cretaceous strata, including Zubair Formation organic matters, based on presentation of GC and GC-MS results on diagrams of global petroleum systems.

Arabian Journal of Geosciences

Mudstone sedimentation at high latitudes: Ice as a transport medium for mud and supplier of nutrients

Controls on mudstone deposition at high latitudes are poorly known relative to low latitudes. In recent sediments deposited in these environments, ice significantly influences sediment transport and primary productivity. The products of ice transport are relatively well known in glacimarine settings, but are less well known from below melting sea ice. This latter setting is significant as today it is associated with high primary organic productivity. The aim of this study is to assess how sea ice might have controlled lithofacies variability and organic-matter distribution and preservation in an ancient marine, siliciclastic mudstone-dominated succession deposited at high latitudes. Combined sedimentary logging, optical and electron optical (back-scatte red electron imagery), geochemical, and isotopic methods were used to determine sample variability in forty-five samples collected from the Lower Cretaceous succession in the Mikkelsen Bay State #1 borehole (North Slope, Alaska). The succession overall fines upward and contains muddy sandstones and sand- and silt-bearing, clay-rich mudstones towards its base in contrast to clay-rich and clay-dominated mudstones towards its top. Some of the mudstone units exhibit thin (< 5 mm), relic-beds that fine upward weakly. In some units small (0.5 mm), bed-parallel silt-filled microburrows disrupt depositional laminae whereas in others pervasive burrowing completely obliterates original depositional textures. Many of the units are pelleted. These mudstones are unusual in that they contain minor but very striking outsize grains, composed of subrounded to rounded sand and granule-size material. In addition, they are good petroleum source rocks, with between 2.8 and 5.9 wt % total organic carbon, of predominantly Type II kerogen. The organic matter has an isotopic signature ranging from -25.4??? ??13C to -28.1??? ??13C. Thin tuffs (< 20 mm) and carbonate-cemented units are also present. Given the absence of significant polar ice in the Early Cretaceous the outsized grains are interpreted to have been deposited from a combination of melting, dirty anchor, and fast ice. The mud fraction, which forms the bulk of the sediment, is interpreted to have been deposited from melting, sediment-laden frazil ice, and fast ice. After deposition sediments were partially reworked by bottom currents generated by brine rejection during sea ice formation. Sympagic organisms, grazing on algae and bacteria both within and below the ice, pelleted the sediment. Bioturbation, which varies through the succession, indicates that sedimentation probably occurred beneath a predominantly oxic or dysoxic water column. In this setting productivity was fueled by nutrients released from melting sea ice in the marginal ice zone. The good petroleum source potential of these mudstones is attributed to high organic productivity coupled to episodic and rapid sedimentation rather than existence of bottom-water anoxia linked to upwelling. Because sea-ice rafting was probably the dominant sediment transport mechanism it is not appropriate to use sequence stratigraphic methodology to predict lithofacies variability in this environment. Copyright ?? 2005, SEPM (Society for Sedimentary Geology).

Journal of Sedimentary Research

Confirmation of the southwest continuation of the Cat Square terrane, southern Appalachian Inner Piedmont, with implications for middle Paleozoic collisional orogenesis

Detailed geologic mapping, U-Pb zircon geochronology and whole-rock geochemical analyses were conducted to test the hypothesis that the southwestern extent of the Cat Square terrane continues from the northern Inner Piedmont (western Carolinas) into central Georgia. Geologic mapping revealed the Jackson Lake fault, a ∼15 m-thick, steeply dipping sillimanite-grade fault zone that truncates lithologically distinct granitoids and metasedimentary units, and roughly corresponds with a prominent aeromagnetic lineament hypothesized to represent the southern continuation of the terrane-bounding Brindle Creek fault. Results of U-Pb SHRIMP geochronology indicate Late Ordovician to Silurian granitoids (444–439 Ma) occur exclusively northwest of the fault, whereas Devonian (404–371 Ma) granitoids only occur southeast of the fault. The relatively undeformed Indian Springs granodiorite (three individual bodies dated 317–298 Ma) crosscuts the fault and occurs on both sides, which indicates the Jackson Lake fault is a pre-Alleghanian structure. However, detrital zircon signatures from samples southeast of the Jackson Lake fault reveal dominant Grenville provenance, in contrast to Cat Square terrane detrital zircon samples from the northern Inner Piedmont, which include peri-Gondwanan (600–500 Ma) and a prominent Ordovician-Silurian (∼430 Ma) signature. We interpret the rocks southeast of the Jackson Lake fault to represent the southwestern extension of the Cat Square terrane primarily based on the partitioning of granitoid ages and lithologic distinctions similar to the northern Inner Piedmont. Data suggest Cat Square terrane metasedimentary rocks were initially deposited in a remnant ocean basin setting and developed into an accretionary prism in front of the approaching Carolina superterrane, ultimately overridden by it in Late Devonian to Early Mississippian time. Burial to >20 km resulted in migmatization of lower plate rocks, forming an infrastructure beneath the Carolina superterrane suprastructure. Provenance patterns support ∼250 km of Devonian dextral translation of the composite Inner Piedmont, which places the northern portion of the Inner Piedmont adjacent to a suite of ∼430 Ma plutons in the Virginia Blue Ridge during deposition. The megascopic thrust-nappe structural style of the northern Inner Piedmont, combined with southwest-directed lateral extrusion at mid-crustal depths, may reconcile differences in timing of metamorphism between the Carolina and central Georgia Inner Piedmont and structural contrasts between the Brindle Creek and Jackson Lake faults.

American Journal of Science

Algal blooms and "Marine snow": Mechanisms that enhance preservation of organic carbon in ancient fine-grained sediments

Combined petrographic and geochemical methods are used to investigate the microfabrics present in thin sections prepared from representative organic carbon-rich mudstones collected from three successions (the Kimmeridge Clay Formation, the Jet Rock Member of the Whitby Mudstone Formation, and the pebble shale and Hue Shale). This study was initiated to determine how organic carbon-rich materials were being delivered to the sediment–water interface, and what happened to them after deposition, prior to deep burial. Analyses of the fabrics present shows that they exhibit many common attributes. In particular they are all: (1) highly heterogeneous on the scale of a thin section, (2) organized into thin beds (< 10 mm thick) composed mainly of mineral mixtures of fine-grained siliciclastic detritus and carbonate materials, and (3) contain significant concentrations of organic carbon, much of which is organized into laminasets that contain abundant organomineralic aggregates and pellets. In addition, framboidal pyrite (range of sizes from < 20 μm to < 1 μm) and abundant agglutinated foraminifers are present in some units. The individual beds are commonly sharp-based and overlain by thin, silt lags. The tops of many of the beds have been homogenized and some regions of the pelleted laminasets contain small horizontal burrows. The organomineralic aggregates present in these mudstones are interpreted to be ancient examples of marine snow. This marine snow likely formed in the water column, particularly during phytoplankton blooms, and was then transported rapidly to the seafloor. The existence of the thin beds with homogenized tops and an in-situ infauna indicates that between blooms there was sufficient oxygen and time for a mixed layer to develop as a result of sediment colonization by diminutive organisms using either aerobic or dysaerobic metabolic pathways. These textures suggest that the constituents of these mudstones were delivered neither as a continuous rain of sediment nor were the bottom waters persistently anoxic. In addition, the presence of thin lags and sharp-based beds suggests that the seafloor was being episodically reworked during deposition. These fabrics indicate that conditions in the water columns and at the seafloors while these rocks were being deposited were very dynamic, and episodic fluxes of high concentrations of organic carbon to the seafloor, during phytoplankton blooms, likely enhanced preservation of organic carbon.

Journal of Sedimentary Research

Evidence for multiple mechanisms of crustal contamination of magma from compositionally zoned plutons and associated ultramafic intrusions of the Alaska Range

Models of continental crustal magmagenesis commonly invoke the interaction of mafic mantle-derived magma and continental crust to explain geochemical and petrologic characteristics of crustal volcanic and plutonic rocks. This interaction and the specific mechanisms of crustal contamination associated with it are poorly understood. An excellent opportunity to study the progressive effects of crustal contamination is offered by the composite plutons of the Alaska Range, a series of nine early Tertiary, multiply intruded, compositionally zoned (Peridotite to granite) plutons. Large initial Sr and Nd isotopic contrasts between the crustal country rock and likely parental magmas allow evaluation of the mechanisms and extents of crustal contamination that accompanied the crystallization of these ultra-mafic through granitic rocks. Three contamination processes are distinguished in these plutons. The most obvious of these is assimilation of crustal country rock concurrent with magmatic fractional crystallization (AFC), as indicated by a general trend toward crustal-like isotopic signatures with increasing differentiation. Second, many ultramafic and mafic rocks have late-stage phenocryst reaction and orthocumulate textures that suggest interaction with felsic melt. These rocks also have variable and enriched isotopic compositions that suggest that this felsic melt was isotopically enriched and probably derived from crustal country rock. Partial melt from the flysch country rock may have reacted with and contaminated these partly crystalline magmas following the precipitation and accumulation of the cumulus phenocrysts but before complete solidification of the magma. This suggests that in magmatic mush (especially of ultramafic composition) crystallizing in continental crust, a second distinct process of crustal contamination may be super imposed on AFC or magma mixing involving the main magma body. Finally, nearly all rocks, including mafic and ultramafic rocks, have ( 87 Sr/ 86 Sr) i that are too high, and ε(T) Nd that are too low, to represent the expected isotopic composition of typical depleted mantle. However, gabbro xenoliths with typical depicted-mantle isotopic compositions are found in the plutons. This situation requires either an additional enriched mantle component to provide the parental magma for these plutons, or some mechanism of crustal contamination of the parent magma that did not cause significant crystallization and differentiation of the magma to more felsic compositions. Thermodynamic modeling indicates that assimilation of alkali-and water-rich partial melt of the metapelite country rock by fractionating, near-liquidus basaltic magma could cause significant contamination while suppressing significant crystallization and differentiation.

Journal of Petrology

Overview of the Mars Pathfinder Mission: Launch through landing, surface operations, data sets, and science results

Mars Pathfinder successfully landed at Ares Vallis on July 4, 1997, deployed and navigated a small rover about 100 m clockwise around the lander, and collected data from three science instruments and ten technology experiments. The mission operated for three months and returned 2.3 Gbits of data, including over 16,500 lander and 550 rover images, 16 chemical analyses of rocks and soil, and 8.5 million individual temperature, pressure and wind measurements. Path‐finder is the best known location on Mars, having been clearly identified with respect to other features on the surface by correlating five prominent horizon features and two small craters in lander images with those in high‐resolution orbiter images and in inertial space from two‐way ranging and Doppler tracking. Tracking of the lander has fixed the spin pole of Mars, determined the precession rate since Viking 20 years ago, and indicates a polar moment of inertia, which constrains a central metallic core to be between 1300 and ∼2000 km in radius. Dark rocks appear to be high in silica and geochemically similar to anorogenic andesites; lighter rocks are richer in sulfur and lower in silica, consistent with being coated with various amounts of dust. Rover and lander images show rocks with a variety of morphologies, fabrics and textures, suggesting a variety of rock types are present. Rounded pebbles and cobbles on the surface as well as rounded bumps and pits on some rocks indicate these rocks may be conglomerates (although other explanations are also possible), which almost definitely require liquid water to form and a warmer and wetter past. Air‐borne dust is composed of composite silicate particles with a small fraction of a highly magnetic mineral, interpreted to be most likely maghemite; explanations suggest iron was dissolved from crustal materials during an active hydrologic cycle with maghemite freeze dried onto silicate dust grains. Remote sensing data at a scale of a kilometer or greater and an Earth analog correctly predicted a rocky plain safe for landing and roving with a variety of rocks deposited by catstrophic floods, which are relatively dust free. The surface appears to have changed little since it formed billions of years ago, with the exception that eolian activity may have deflated the surface by ∼3–7 cm, sculpted wind tails, collected sand into dunes, and eroded ventifacts (fluted and grooved rocks). Pathfinder found a dusty lower atmosphere, early morning water ice clouds, and morning near‐surface air temperatures that changed abruptly with time and height. Small scale vortices, interpreted to be dust devils, were observed repeatedly in the afternoon by the meteorology instruments and have been imaged.

Journal of Geophysical Research E: Planets

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in ??34S for sulfur species within and between the low-sulfur and high-sulfur coal. The ??34S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the ??34S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the ??34S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of ??34S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in ??34S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition. The ??34S values for fly ash from the high-sulfur Springfield coal (averaging 9.7???) are greatly enriched in 34S relative to those in the parent coal (averaging 2.2???). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the ??34S values for fly-ash samples from the low-sulfur Danville coal average 10.2???, only slightly enriched in 34S relative to those from the parent coal (average 7.5???). The ??34S values for bulk S determined directly from the fly-ash samples show close correspondence with the ??34S values for SO4- 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion. ?? 2007 Elsevier B.V. All rights reserved.

International Journal of Coal Geology

Integrated provenance analysis of a complex orogenic terrane: Mesozoic uplift of the Bogda Shan and Inception of the Turpan-Hami Basin, NW China

We employ petrographic and advanced geochemical techniques to better document the evolution of the Turpan–Hami basin based on the unique geologic histories of the arc terranes that served as potential sources of Turpan–Hami deposits. First, a provenance study of Permian through Cretaceous sandstone of the Turpan–Hami basin reveals temporal and spatial changes in dominant source terranes that provided detritus to the basin. Volcanic-lithic-rich Upper Permian sandstone (mean Qm 19 F 18 Lt 63 ; Qp 7 Lvm 89 Lsm 4 ; Qm 48 P 39 K 13 ) followed by more quartzose compositions in Triassic sandstone (mean Qm 41 F 19 Lt 40 ; Qp 20 Lvm 75 Lsm 5 ; Qm 68 P 21 K 11 ) indicate progressive unroofing of the extinct northern and central Tian Shan arc terranes to the south of Turpan–Hami. A sharp change to sedimentary-lithic-rich Lower Jurassic sandstone (mean Qm 47 F 16 Lt 37 ; Qp 16 Lvm 42 Lsm 42 ; Qm 75 P 12 K 13 ) overlain by a return to volcanic–lithic-rich Middle Jurassic sandstone (mean Qm 39 F 21 Lt 40 ; Qp 14 Lvm 51 Lsm 35 ; Qm 65 P 21 K 14 ) points to the initial uplift and unroofing of the largely andesitic Bogda Shan to the north, which first shed its sedimentary cover as it emerged to become the partition between the Turpan–Hami and southern Junggar basins. Second, geochronological, trace-element, and Sm-Nd isotopic variations among granitoids in the late Paleozoic Tian Shan orogenic belt provide a further test of Mesozoic uplift of the Bogda Shan. On the basis of previous models of crustal compositions throughout the South, Central, and North Tian Shan, Bogda Shan, and East and West Junggar terranes, we infer that isotopically enriched granitic cobbles (average εNd i = −0.50, n = 6) contained in Lower Triassic deposits in the north-central Turpan–Hami basin were derived from the continental crustal Central Tian Shan terrane, south of Turpan–Hami, and not from the more oceanic North Tian Shan, Bogda Shan, and East and West Junggar terranes, north of the Turpan–Hami basin. We therefore infer that the ancestral Bogda Shan had not been uplifted by the Early Triassic, and that prior to this time, a unified Junggar–Turpan–Hami basin existed during Late Permian deposition of extensive lacustrine deposits

Turpan-Hami Basin

Seismicity and fluid geochemistry at Lassen Volcanic National Park, California: Evidence for two circulation cells in the hydrothermal system

Seismic analysis and geochemical interpretations provide evidence that two separate hydrothermal cells circulate within the greater Lassen hydrothermal system. One cell originates south to SW of Lassen Peak and within the Brokeoff Volcano depression where it forms a reservoir of hot fluid (235–270°C) that boils to feed steam to the high-temperature fumarolic areas, and has a plume of degassed reservoir liquid that flows southward to emerge at Growler and Morgan Hot Springs. The second cell originates SSE to SE of Lassen Peak and flows southeastward along inferred faults of the Walker Lane belt (WLB) where it forms a reservoir of hot fluid (220–240°C) that boils beneath Devils Kitchen and Boiling Springs Lake, and has an outflow plume of degassed liquid that boils again beneath Terminal Geyser. Three distinct seismogenic zones (identified as the West , Middle , and East seismic clusters) occur at shallow depths (<6 km) in Lassen Volcanic National Park, SW to SSE of Lassen Peak and adjacent to areas of high-temperature (≤161°C) fumarolic activity (Sulphur Works, Pilot Pinnacle, Little Hot Springs Valley, and Bumpass Hell) and an area of cold, weak gas emissions (Cold Boiling Lake). The three zones are located within the inferred Rockland caldera in response to interactions between deeply circulating meteoric water and hot brittle rock that overlies residual magma associated with the Lassen Volcanic Center. Earthquake focal mechanisms and stress inversions indicate primarily N–S oriented normal faulting and E–W extension, with some oblique faulting and right lateral shear in the East cluster. The different focal mechanisms as well as spatial and temporal earthquake patterns for the East cluster indicate a greater influence by regional tectonics and inferred faults within the WLB. A fourth, deeper (5–10 km) seismogenic zone (the Devils Kitchen seismic cluster) occurs SE of the East cluster and trends NNW from Sifford Mountain toward the Devils Kitchen thermal area where fumarolic temperatures are ≤123°C. Lassen fumaroles discharge geothermal gases that indicate mixing between a N 2 -rich, arc-type component and gases derived from air-saturated meteoric recharge water. Most gases have relatively weak isotopic indicators of upper mantle or volcanic components, except for gas from Sulphur Works where δ 13 C–CO 2 , δ 34 S–H 2 S, and δ 15 N–N 2 values indicate a contribution from the mantle and a subducted sediment source in an arc volcanic setting.

California

Petrology, mineralogy and geochemistry of mined coals, western Venezuela

Upper Paleocene to middle Miocene coal samples collected from active mines in the western Venezuelan States of Táchira, Mérida and Zulia have been characterized through an integrated geochemical, mineralogical and petrographic investigation. Proximate, ultimate, calorific and forms of sulfur values, major and trace element, vitrinite reflectance, maceral concentrations and mineral matter content have been determined for 16 channel samples from 14 mines. Ash yield generally is low, ranging from < 1 to 17 wt.% (mean = 5 wt.%) on a dry basis (db). Total sulfur content is low to moderate, ranging from 1 to 6 wt.%, db (average = 1.7 wt.%). Calorific value ranges from 25.21 to 37.21 MJ/kg (10,840–16,000 Btu/lb) on a moist, mineral-matter-free basis (average = 33.25 MJ/kg, 14,300 Btu/lb), placing most of the coal samples in the apparent rank classification of high-volatile bituminous. Most of the coal samples exhibit favorable characteristics on the various indices developed to predict combustion and coking behavior and concentrations of possible environmentally sensitive elements (As, Be, Cd, Cr, Co, Hg, Mn, Ni, Pb, Sb, Se, Th and U) generally are similar to the concentrations of these elements in most coals of the world, with one or two exceptions. Concentrations of the liptinite maceral group range from < 1% to 70 vol.%. Five samples contain > 20 vol.% liptinite, dominated by the macerals bituminite and sporinite. Collotelinite dominates the vitrinite group; telinite was observed in quantities of ≤ 1 vol.% despite efforts to better quantify this maceral by etching the sample pellets in potassium permanganate and also by exposure in an oxygen plasma chamber. Inertinite group macerals typically represent < 10 vol.% of the coal samples and the highest concentrations of inertinite macerals are found in distantly spaced (> 400 km) upper Paleocene coal samples from opposite sides of Lago de Maracaibo, possibly indicating tectonic controls on subsidence related to construction of the Andean orogen. Values of maximum reflectance of vitrinite in oil ( R o max ) range between 0.42% and 0.85% and generally are consistent with the high-volatile bituminous rank classification obtained through ASTM methods. X-ray diffraction analyses of low-temperature ash residues indicate that kaolinite, quartz, illite and pyrite dominate the inorganic fraction of most samples; plagioclase, potassium feldspar, calcite, siderite, ankerite, marcasite, rutile, anatase and apatite are present in minor or trace concentrations. Semiquantitative values of volume percent pyrite content show a strong correlation with pyritic sulfur and some sulfide-hosted trace element concentrations (As and Hg). This work provides a modern quality dataset for the western Venezuela coal deposits currently being exploited and will serve as the foundation for an ongoing coal quality research program in Venezuela.

International Journal of Coal Geology