Catalytic effect of light illumination on bioleaching of chalcopyrite.

PubMed

Zhou, Shuang; Gan, Min; Zhu, Jianyu; Li, Qian; Jie, Shiqi; Yang, Baojun; Liu, Xueduan

2015-04-01

The influence of visible light exposure on chalcopyrite bioleaching was investigated using Acidithiobacillus ferrooxidans. The results indicated, in both shake-flasks and aerated reactors with 8500-lux light, the dissolved Cu was 91.80% and 23.71% higher, respectively, than that in the controls without light. The catalytic effect was found to increase bioleaching to a certain limit, then plateaued as the initial chalcopyrite concentration increased from 2% to 4.5%. Thus a balanced mineral concentration is highly amenable to bioleaching via offering increased available active sites for light adsorption while eschewing mineral aggregation and screening effects. Using semiconducting chalcopyrite, the light facilitated the reduction of Fe(3+) to Fe(2+) as metabolic substrates for A.ferrooxidans, leading to better biomass, lower pH and redox potential, which are conducive to chalcopyrite leaching. The light exposure on iron redox cycling was further confirmed by chemical leaching tests using Fe(3+), which exhibited higher Fe(2+) levels in the light-induced system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Bioleaching of two different genetic types of chalcopyrite and their comparative mineralogical assessment.

PubMed

Deng, Sha; Gu, Guohua; Ji, Jing; Xu, Baoke

2018-02-01

The bioleaching of two different genetic types of chalcopyrite by the moderate thermophile Sulfobacillus thermosulfidooxidans was investigated by leaching behaviors elucidation and their comparative mineralogical assessment. The leaching experiment showed that the skarn-type chalcopyrite (STC) revealed a much faster leaching rate with 33.34% copper extracted finally, while only 23.53% copper was bioleached for the porphyry-type chalcopyrite (PTC). The mineralogical properties were analyzed by XRD, SEM, XPS, and Fermi energy calculation. XRD indicated that the unit cell volume of STC was a little larger than that of PTC. SEM indicated that the surface of STC had more steps and ridges. XPS spectra showed that Cu(I) was the dominant species of copper on the surfaces of the two chalcopyrite samples, and STC had much more copper with lower Cu 2p 3/2 binding energy. Additionally, the Fermi energy of STC was much higher than that of PTC. These mineralogical differences were in good agreement with the bioleaching behaviors of chalcopyrite. This study will provide some new information for evaluating the oxidation kinetics of chalcopyrite.

Synthesis of nanoparticle emulsion collector HNP and its application in microfine chalcopyrite flotation

NASA Astrophysics Data System (ADS)

He, G. C.; Ding, J.; Huang, C. H.; Kang, Q.

2018-01-01

Hydrophobic polystyrene nanoparticles bearing thiazole groups named HNP were used as collectors to improve recovery of microfine chalcopyrite in flotation. HNP adsorbs onto microfine particles selectively, which were modified hydrophobically to induce flotation effectively. Particle size and scanning electron microscope analysis for HNP show that HNP is a spherical nano particles with small size, uniform distribution and good dispersion. Infrared spectrum analysis for HNP proved that functional monomer 2-mercapto styrene acrylic thiazole was bonded chemically onto styrene. Flotation test results indicate that HNP is the right collector of chalcopyrite. Especially, the recovery of chalcopyrite is higher than 95% in neutral and acid media. FTIR results reveal that the flotation selectivity of collector HNP is due to strong chemical absorption onto chalcopyrite surface. Zeta potential analysis shows that the zeta potential of chalcopyrite decreased more quickly after interaction with HNP with the increase of pulp pH value, confirming that collector HNP is an anionic collector. Scanning electron microscope conform that HNP has good selective adsorption on chalcopyrite.

Selective separation of pyrite and chalcopyrite by biomodulation.

PubMed

Chandraprabha, M N; Natarajan, K A; Modak, Jayant M

2004-09-01

Selective separation of pyrite from other associated ferrous sulphides at acidic and neutral pH has been a challenging problem. This paper discusses the utility of Acidithiobacillus ferrooxidans for the selective flotation of chalcopyrite from pyrite. Consequent to interaction with bacterial cells, pyrite remained depressed even in the presence of potassium isopropyl xanthate collector while chalcopyrite exhibited significant flotability. However, when the minerals were conditioned together, the selectivity achieved was poor due to the activation of pyrite surface by the copper ions in solution. The selectivity was improved when the sequence of conditioning with bacterial cells and collector was reversed, since the bacterial cells were able to depress collector interacted pyrite effectively, while having negligible effect on chalcopyrite. The observed behaviour is analysed and discussed in detail. The separation obtained was significant both at acidic and alkaline pH. This selectivity achieved was retained when the minerals were interacted with both bacterial cells and collector simultaneously.

Petrology and diagenetic history of the upper shale member of the Late Devonian-Early Mississippian Bakken Formation, Williston Basin, North Dakota

USGS Publications Warehouse

Neil S. Fishman,; Sven O. Egenhoff,; Boehlke, Adam; Lowers, Heather A.

2015-01-01

The organic-rich upper shale member of the upper Devonian–lower Mississippian Bakken Formation (Williston Basin, North Dakota, USA) has undergone significant diagenetic alteration, irrespective of catagenesis related to hydrocarbon generation. Alteration includes precipitation of numerous cements, replacement of both detrital and authigenic minerals, multiple episodes of fracturing, and compaction. Quartz authigenesis occurred throughout much of the member, and is represented by multiple generations of microcrystalline quartz. Chalcedonic quartz fills radiolarian microfossils and is present in the matrix. Sulfide minerals include pyrite and sphalerite. Carbonate diagenesis is volumetrically minor and includes thin dolomite overgrowths and calcite cement. At least two generations of fractures are observed. Based on the authigenic minerals and their relative timing of formation, the evolution of pore waters can be postulated. Dolomite and calcite resulted from early postdepositional aerobic oxidation of some of the abundant organic material in the formation. Following aerobic oxidation, conditions became anoxic and sulfide minerals precipitated. Transformation of the originally opaline tests of radiolaria resulted in precipitation of quartz, and quartz authigenesis is most common in more distal parts of the depositional basin where radiolaria were abundant. Because quartz authigenesis is related to the distribution of radiolaria, there is a link between diagenesis and depositional environment. Furthermore, much of the diagenesis in the upper shale member preceded hydrocarbon generation, so early postdepositional processes were responsible for occlusion of significant original porosity in the member. Thus, diagenetic mineral precipitation was at least partly responsible for the limited ability of these mudstones to provide porosity for storage of hydrocarbons.

Early-diagenetic processes in marine mangrove sediments from Guadeloupe, French West Indies

NASA Astrophysics Data System (ADS)

Crémière, Antoine; Sebilo, Mathieu; Strauss, Harald; Gros, Olivier; Laverman, Anniet M.

2014-05-01

Sediment and pore-water geochemistry were investigated in two short sediment cores from the Manche-à-eau lagoon (Guadeloupe, French Caribbean island) surrounded by mangroves trees. These sediments present high total organic carbon content, ranging between 10 to 18 % wt, mainly originating from mangrove litter fall. Oxygen is depleted in the first few millimetres of the sediment indicating active organic carbon degradation. Seawater sulphate is entirely consumed within the first 20 cm of the sediments and total organic carbon content decreases with depth pointing out that early-diagenetic degradation of organic matter occurs with sulphate reduction. Sulphide produced as the results of sulphate reduction partly reacts with detrital iron-bearing minerals and precipitates as pyrite which is consistent with high amounts of sulphur in the sediments (4-5 % wt). The sulphur isotopic composition (δ34S) of both dissolved sulphate and sulphide in pore-water increases with depth displaying a large apparent isotopic fractionation (Δ34S) between both species of 65-80o as a result of bacterial sulphate reduction. Scanning electron microscopy investigation reveals that a part of the carbonate alkalinity produced either by organic matter oxidation or anaerobic methane oxidation leads to authigenic carbonates precipitation. These results provide straightforward evidence that carbon and sulphur biogeochemical cycles are intimately governed by sedimentary microbial activity.

Cyclic, Early Diagenetic Dolomite Formation in Alkaline Lake Van

NASA Astrophysics Data System (ADS)

McCormack, J.; Bontognali, T. R. R.; Immenhauser, A.; Kwiecien, O.

2017-12-01

rapid Northern Hemisphere temperature oscillation (i.e. Greenland Interstadials). Lake Vańs dolomite record thus provides compelling arguments suggesting that early diagenetic dolomite formation within an alkaline environment can be highly sensitive to hydrological changes even on centennial timescales.

Morphological recognition of Globigerinoides ruber morphotypes and their susceptibility to diagenetic alteration in the eastern Mediterranean Sea

NASA Astrophysics Data System (ADS)

Kontakiotis, G.; Antonarakou, A.; Mortyn, P. G.; Drinia, H.; Anastasakis, G.; Zarkogiannis, S.; Möbius, J.

2017-10-01

Planktonic foraminiferal geochemistry presents a valuable archive for paleoceanographic reconstructions. However in high salinity and carbonate super-saturated settings, precipitation of inorganic calcite onto foraminiferal tests can potentially alter the primary geochemical signal, biasing Mg/Ca ratios and ensuing paleoceanographic reconstructions. Here we utilize test biometrics (specifically related to the compression and elongation of the last chambers) to identify four distinct morphotypes (labelled A-D) of the paleoceanographically important planktonic foraminifer species Globigerinoides ruber, and further evaluate their susceptibility to diagenetic alteration from a suite of surface sediments in the eastern Mediterranean Sea. The three distinguished morphotypes (A-C) correspond to previously recognized morphotypes ("Normal", "Platys", "Elongate" respectively) in the Mediterranean Sea, while the remaining (D or "Twin") was designated for the first time. We also compare Scanning Electron Microscopy (SEM) observations performed on four distinguished morphotypes, indicative of potential diagenetic alteration influence. We identified 3 different overgrowth stages (OGA1-OGA3), as a function of geography in the study area. The early diagenesis degrees (involving all the morphotypes) are only geographically distinct along the eastern Mediterranean (increasing to the south), since the morphology does not play a role in the likelihood of diagenetic alteration. Particularly, in the north Aegean Sea, SEM analyses reveal the absence or limited presence of an overgrowth imprint in all recognized morphotypes, while in the central-south Aegean and Levantine Seas they show higher amplitudes of diagenetic overprint supporting the general trend to advanced diagenetic alteration. The semi-enclosed oligotrophic nature and high salinity of this setting, in combination with the different degree of carbonate precipitation and calcite super-saturation between the sub-basins, could

PEaCH4 v.2.0: A modelling platform to predict early diagenetic processes in marine sediments with a focus on biogenic methane - Case study: Offshore Namibia

NASA Astrophysics Data System (ADS)

Arning, Esther T.; Häußler, Steffen; van Berk, Wolfgang; Schulz, Hans-Martin

2016-07-01

The modelling of early diagenetic processes in marine sediments is of interest in marine science, and in the oil and gas industry, here, especially with respect to methane occurrence and gas hydrate formation as resources. Early diagenesis in marine sediments evolves from a complex web of intertwining (bio)geochemical reactions. It comprises microbially catalysed reactions and inorganic mineral-water-gas interactions. A model that will describe and consider all of these reactions has to be complex. However, it should be user-friendly, as well as to be applicable for a broad community and not only for experts in the field of marine chemistry. The presented modelling platform PeaCH4 v.2.0 combines both aspects, and is Microsoft Excel©-based. The modelling tool is PHREEQC (version 2), a computer programme for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. The conceptual PEaCH4 model is based on the conversion of sediment-bound degradable organic matter. PEaCH4 v.2.0 was developed to quantify and predict early diagenetic processes in marine sediments with the focus on biogenic methane formation and its phase behaviour, and allows carbon mass balancing. In regard to the irreversible degradation of organic matter, it comprises a "reaction model" and a "kinetic model" to predict methane formation. Both approaches differ in their calculations and outputs as the "kinetic model" considers the modelling time to integrate temperature dependent biogenic methane formation in its calculations, whereas the "reaction model" simply relies on default organic matter degradation. With regard to the inorganic mineral-water-gas interactions, which are triggered by irreversible degradation of organic matter, PEaCH4 v.2.0 is based on chemical equilibrium thermodynamics, appropriate mass-action laws, and their temperature dependent equilibrium constants. The programme is exemplarily presented with the example of upwelling sediments off Namibia

Influence of the surface speciation on biofilm attachment to chalcopyrite by Acidithiobacillus thiooxidans.

PubMed

Lara, René H; García-Meza, J Viridiana; González, Ignacio; Cruz, Roel

2013-03-01

Surfaces of massive chalcopyrite (CuFeS2) electrodes were modified by applying variable oxidation potential pulses under growth media in order to induce the formation of different secondary phases (e.g., copper-rich polysulfides, S n(2-); elemental sulfur, S(0); and covellite, CuS). The evolution of reactivity (oxidation capacity) of the resulting chalcopyrite surfaces considers a transition from passive or inactive (containing CuS and S n(2-)) to active (containing increasing amounts of S(0)) phases. Modified surfaces were incubated with cells of sulfur-oxidizing bacteria (Acidithiobacillus thiooxidans) for 24 h in a specific culture medium (pH 2). Abiotic control experiments were also performed to compare chemical and biological oxidation. After incubation, the density of cells attached to chalcopyrite surfaces, the structure of the formed biofilm, and their exopolysaccharides and nucleic acids were analyzed by confocal laser scanning microscopy (CLSM) and scanning electron microscopy coupled to dispersive X-ray analysis (SEM-EDS). Additionally, CuS and S n(2-)/S(0) speciation, as well as secondary phase evolution, was carried out on biooxidized and abiotic chalcopyrite surfaces using Raman spectroscopy and SEM-EDS. Our results indicate that oxidized chalcopyrite surfaces initially containing inactive S n(2-) and S n(2-)/CuS phases were less colonized by A. thiooxidans as compared with surfaces containing active phases (mainly S(0)). Furthermore, it was observed that cells were partially covered by CuS and S(0) phases during biooxidation, especially at highly oxidized chalcopyrite surfaces, suggesting the innocuous effect of CuS phases during A. thiooxidans performance. These results may contribute to understanding the effect of the concomitant formation of refractory secondary phases (as CuS and inactive S n(2-)) during the biooxidation of chalcopyrite by sulfur-oxidizing microorganisms in bioleaching systems.

Current scenario of chalcopyrite bioleaching: a review on the recent advances to its heap-leach technology.

PubMed

Panda, Sandeep; Akcil, Ata; Pradhan, Nilotpala; Deveci, Haci

2015-11-01

Chalcopyrite is the primary copper mineral used for production of copper metal. Today, as a result of rapid industrialization, there has been enormous demand to profitably process the low grade chalcopyrite and "dirty" concentrates through bioleaching. In the current scenario, heap bioleaching is the most advanced and preferred eco-friendly technology for processing of low grade, uneconomic/difficult-to-enrich ores for copper extraction. This paper reviews the current status of chalcopyrite bioleaching. Advanced information with the attempts made for understanding the diversity of bioleaching microorganisms; role of OMICs based research for future applications to industrial sectors and chemical/microbial aspects of chalcopyrite bioleaching is discussed. Additionally, the current progress made to overcome the problems of passivation as seen in chalcopyrite bioleaching systems have been conversed. Furthermore, advances in the designing of heap bioleaching plant along with microbial and environmental factors of importance have been reviewed with conclusions into the future prospects of chalcopyrite bioleaching. Copyright © 2015 Elsevier Ltd. All rights reserved.

Bioleaching of chalcopyrite and bornite by moderately thermophilic bacteria: an emphasis on their interactions

NASA Astrophysics Data System (ADS)

Zhao, Hong-bo; Wang, Jun; Gan, Xiao-wen; Qin, Wen-qing; Hu, Ming-hao; Qiu, Guan-zhou

2015-08-01

Interactions between chalcopyrite and bornite during bioleaching by moderately thermophilic bacteria were investigated mainly by X-ray diffraction, scanning electron microscopy, and electrochemical measurements performed in conjunction with bioleaching experiments. The results showed that a synergistic effect existed between chalcopyrite and bornite during bioleaching by both Acidithiobacillus caldus and Leptospirillum ferriphilum and that extremely high copper extraction could be achieved when chalcopyrite and bornite coexisted in a bioleaching system. Bornite dissolved preferentially because of its lower corrosion potential, and its dissolution was accelerated by the galvanic current during the initial stage of bioleaching. The galvanic current and optimum redox potential of 390-480 mV vs. Ag/AgCl promoted the reduction of chalcopyrite to chalcocite (Cu2S), thus accelerating its dissolution.

Heterocoagulation of chalcopyrite and pyrite minerals in flotation separation.

PubMed

Mitchell, Timothy K; Nguyen, Anh V; Evans, Geoffrey M

2005-06-30

Heterocoagulation between various fine mineral particles contained within a mineral suspension with different structural and surface chemistry can interfere with the ability of the flotation processes to selectively separate the minerals involved. This paper examines the interactions between chalcopyrite (a copper mineral) and pyrite (an iron mineral often bearing gold) as they approach each other in suspensions with added chemicals, and relates the results to the experimental data for the flotation recovery and selectivity. The heterocoagulation was experimentally studied using the electrophoretic light scattering (ELS) technique and was modelled by incorporating colloidal forces, including the van der Waals, electrostatic double layer and hydrophobic forces. The ELS results indicated that pyrite has a positive zeta potential (zeta) up to its isoelectric point (IEP) at approximately pH 2.2, while chalcopyrite has a positive zeta up to its IEP at approximately pH 5.5. This produces heterocoagulation of chalcopyrite with pyrite between pH 2.2 and pH 5.5. The heterocoagulation was confirmed by the ELS spectra measured with a ZetaPlus instrument from Brookhaven and by small-scale flotation experiments.

Diagenetic Features in Yellowknife Bay, Gale Crater, Mars: Implications for Substrate Rheology and Potential Gas Release

NASA Technical Reports Server (NTRS)

Kah, L. C.; Stack, K; Siebach, K.; Grotzinger, J.; Summer, D.; Farien, A.; Oehler, D.; Schieber, J.; Leville, R.; Edgar, L;

Non-linear hydroxyl radical formation rate in dispersions containing mixtures of pyrite and chalcopyrite particles

NASA Astrophysics Data System (ADS)

Kaur, Jasmeet; Schoonen, Martin A.

2017-06-01

The formation of hydroxyl radicals was studied in mixed pyrite-chalcopyrite dispersions in water using the conversion rate of adenine as a proxy for hydroxyl radical formation rate. Experiments were conducted as a function of pH, presence of phosphate buffer, surface loading, and pyrite-to-chalcopyrite ratio. The results indicate that hydroxyl radical formation rate in mixed systems is non-linear with respect to the rates in the pure endmember dispersions. The only exception is a set of experiments in which phosphate buffer is used. In the presence of phosphate buffer, the hydroxyl radical formation is suppressed in mixtures and the rate is close to that predicted based on the reaction kinetics of the pure endmembers. The non-linear hydroxyl radical formation in dispersions containing mixtures of pyrite and chalcopyrite is likely the result of two complementary processes. One is the fact that pyrite and chalcopyrite form a galvanic couple. In this arrangement, chalcopyrite oxidation is accelerated, while pyrite passes electrons withdrawn from chalcopyrite to molecular oxygen, the oxidant. The incomplete reduction of molecular oxygen leads to the formation of hydrogen peroxide and hydroxyl radical. The galvanic coupling appears to be augmented by the fact that chalcopyrite generates a significant amount of hydrogen peroxide upon dispersal in water. This hydrogen peroxide is then available for conversion to hydroxyl radical, which appears to be facilitated by pyrite as chalcopyrite itself produces only minor amounts of hydroxyl radical. In essence, pyrite is a ;co-factor; that facilitates the conversion of hydrogen peroxide to hydroxyl radical. This conversion reaction is a surface-mediated reaction. Given that hydroxyl radical is one of the most reactive species in nature, the formation of hydroxyl radicals in aqueous systems containing chalcopyrite and pyrite has implications for the stability of organic molecules, biomolecules, the viability of microbes, and

Diagenetic effects of compaction on reservoir properties: The case of early callovian ``Dalle Nacrée'' formation (Paris basin, France)

NASA Astrophysics Data System (ADS)

Nader, Fadi H.; Champenois, France; Barbier, Mickaël; Adelinet, Mathilde; Rosenberg, Elisabeth; Houel, Pascal; Delmas, Jocelyne; Swennen, Rudy

2016-11-01

The impact of compaction diagenesis on reservoir properties is addressed by means of observations made on five boreholes with different burial histories of the Early Callovian ;Dalle Nacrée; Formation in the Paris Basin. Petrographic analyses were carried out in order to investigate the rock-texture, pore space type and volume, micro-fabrics, and cement phases. Based on the acquired data, a chronologically ordered sequence of diagenetic events (paragenesis) for each borehole was reconstructed taking the burial history into account. Point counting and a segmentation algorithm (Matlab) were used to quantify porosity, as well as the amounts of grain constituents and cement phases on scanned images of studied thin sections. In addition, four key samples were analyzed by 3D imaging using microfocus X-ray computer tomography. Basin margin grainstones display a different burial diagenesis when compared to basin centre grainstones and wackestones. The former have been affected by considerable cementation (especially by blocky calcite) prior to effective burial, in contrast to the basin centre lithologies where burial and compaction prevailed with relatively less cementation. Fracturing and bed-parallel stylolitization, observed especially in basinal wackestone facies also invoke higher levels of mechanical and chemical compaction than observed in basin marginal equivalents. Compaction fluids may have migrated at the time of burial from the basin centre towards its margins, affecting hence the reservoir properties of similar rock textures and facies and resulting in cross-basin spatial diagenetic heterogeneities.

Dehydroxylation and diagenetic variations in diatom oxygen isotope values

NASA Astrophysics Data System (ADS)

Dodd, Justin P.; Wiedenheft, Wilson; Schwartz, Joshua M.

2017-02-01

Numerous studies have documented changes in the dissolution and reactivity of biogenic silica as it is transferred from the water column to sediment archives; here we present the first experimental data that demonstrate a physical mechanism by which the oxygen isotope (δ18Osil) values of biogenic silica (diatoms) are altered during early diagenesis. The δ18Osil value of diatom silica cultured at 19.3 °C was +31.9‰ ± 0.2‰ (n = 6); the same silica experimentally aged in an artificial seawater media at near silica saturation at 85 °C had an average δ18Osil value of +27.1‰ ± 0.6‰ (n = 20). The most significant change in the δ18Osil value was coincident with an initial reduction in the total silanol abundance, indicating that the timing of dehydroxylation reactions in natural sedimentary environments is associated with diagenetic changes in the recorded δ18Osil values. The rate of change in the experimental aging environment at 85 °C was rapid, with significant changes in both silanol abundance and δ18Osil values. Additionally, the silica-water fractionation relationship recorded by the experimentally-aged samples approaches the equilibrium quartz-water fractionation factor. The linear rate law was used to estimate the timing of these changes in low temperature environments; the initial and most significant change in silica reactivity and δ18Osil values is likely to occur on the order of 10's of years at 4 °C. Published silica-water fractionation factors for sedimentary diatoms most likely represent a combination of growth and diagenetic environments, and the δ18O value of diagenetic water needs to be addressed when using δ18Osil values to reconstruct paleoceanographic and paleoenvironmental conditions.

Single-source precursors for ternary chalcopyrite materials, and methods of making and using the same

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K. (Inventor); Hepp, Aloysius F. (Inventor); Harris, Jerry D. (Inventor); Jin, Michael Hyun-Chul (Inventor); Castro, Stephanie L. (Inventor)

2006-01-01

A single source precursor for depositing ternary I-III-VI.sub.2 chalcopyrite materials useful as semiconductors. The single source precursor has the I-III-VI.sub.2 stoichiometry built into a single precursor molecular structure which degrades on heating or pyrolysis to yield the desired I-III-VI.sub.2 ternary chalcopyrite. The single source precursors effectively degrade to yield the ternary chalcopyrite at low temperature, e.g. below 500.degree. C., and are useful to deposit thin film ternary chalcopyrite layers via a spray CVD technique. The ternary single source precursors according to the invention can be used to provide nanocrystallite structures useful as quantum dots. A method of making the ternary single source precursors is also provided.

Structural, optical, electron paramagnetic, thermal and dielectric characterization of chalcopyrite.

PubMed

Prameena, B; Anbalagan, G; Gunasekaran, S; Ramkumaar, G R; Gowtham, B

2014-03-25

Chalcopyrite (CuFeS2) a variety of pyrite minerals was investigated through spectroscopic techniques and thermal analysis. The morphology and elemental analysis of the chalcopyrite have been done by high resolution SEM with EDAX. The lattice parameters were from the powder diffraction data (a=5.3003±0.0089 Å, c=10.3679±0.0289 Å; the volume of the unit cell=291.266 Å(3) with space group I42d (122)). The thermal decomposition behavior of chalcopyrite was studied by means of thermogravimetric analysis at three different heating rates 10, 15 and 20 °C/min. The values of effective activation energy (Ea), pre-exponential factor (ln A) for thermal decomposition have been measured at three different heating rates by employing Kissinger, Kim-Park and Flynn-Wall methods. Dielectric studies at different temperatures have also been carried out and it was found that both dielectric constant and dielectric loss decreases with the increase of frequency. Copyright © 2013 Elsevier B.V. All rights reserved.

A subtle diagenetic trap in the Cretaceous Glauconite Sandstone of Southwest Alberta

USGS Publications Warehouse

Meshri, I.D.; Comer, J.B.

1990-01-01

Despite the long history of research which documents many studies involving extensive diagenesis, there are a few examples of a fully documented diagenetic trap. In the context of this paper, a trap is a hydrocarbon-bearing reservoir with a seal; because a reservoir without a seal acts as a carrier bed. The difficulty in the proper documentation of diagenetic traps is often due to the lack of: (a) extensive field records on the perforation and production histories, which assist in providing the depth of separation between hydrocarbon production and non-hydrocarbon or water production; and (b) the simultaneous availability of core data from these intervals, which could be studied for the extent and nature of diagenesis. This paper provides documentation for the existence of a diagenetic trap, based on perforation depths, production histories and petrologic data from the cored intervals, in the context of the geologic and stratigraphic setting. Cores from 15 wells and SP logs from 45 wells were carefully correlated and the data on perforated intervals was also acquired. Extensive petrographic work on the collected cores led to the elucidation of a diagenetic trap that separates water overlying and updip from gas downdip. Amoco's Berrymore-Lobstick-Bigoray fields, located near the northeastern edge of the Alberta Basin, are prolific gas producers. The gas is produced from reservoir rock consisting of delta platform deposits formed by coalescing distributary mouth bars. The overlying rock unit is composed of younger distributary channels; although it has a good reservoir quality, it contains and produces water only. The total thickness of the upper, water-bearing and lower gas-bearing sandstone is about 40 ft. The diagenetic seal is composed of a zone 2 to 6 ft thick, located at the base of distributary channels. This zone is cemented with 20-30% ankerite cement, which formed the gas migration and is also relatively early compared to other cements formed in the water

A biodetrital coral mound complex: Key to early diagenetic processes in the mississippian bangor limestone

USGS Publications Warehouse

Haywick, D.W.; Kopaska-Merkel, D. C.; Bersch, M.G.

2009-01-01

diagenetic phase, dolomite, was the dominant event in the micrite/dolomicrite petrofacies, particularly just below an irregular surface overlain by a brecciated interval. The irregular surface is interpreted as an exposure surface. Three phases of dolomite occur below the exposure surface. The majority is finely crystalline, anhedral, and enriched in Si4+, criteria which support a supratidal or mixed hypersaline\\meteoric origin. Secondary phases of coarser euhedral non-ferroan and ferroan dolomite are restricted to fenestrae and other voids in the micrite/dolomicrite petrofacies and were precipitated during subsequent meteoric diagenesis. Diagenesis of the Bangor Limestone at the Moulton outcrop was dominated by synsedimentary and very early meteoric processes driven by periods of subaerial exposure. Large voids within the mound petrofacies were particularly important, as they remained open long enough to record a more detailed early meteoric cement stratigraphy that might not be evident in Bangor Limestone outcrops elsewhere in Alabama.

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

USGS Publications Warehouse

Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C.

2010-01-01

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

Selective depression mechanism of ferric chromium lignin sulfonate for chalcopyrite-galena flotation separation

NASA Astrophysics Data System (ADS)

Yu, Jin-sheng; Liu, Run-qing; Wang, Li; Sun, Wei; Peng, Hong; Hu, Yue-hua

2018-05-01

Selective recovery of chalcopyrite-galena ore by flotation remains a challenging issue. The development of highly efficient, low-cost, and environmentally friendly depressants for this flotation is necessary because most of available reagents (e.g., K2Cr2O4) are expensive and adversely affect the environment. In this study, ferric chromium lignin sulfonate (FCLS), which is a waste-product from the paper and pulp industry, was introduced as a selective depressant for galena with butyl xanthate (BX) as a collector. Results show that the residue recovery of Pb in Cu concentrate was substantially reduced to 4.73% using FCLS compared with 10.71% using the common depressant K2Cr2O4. The underlying mechanisms were revealed using zeta-potential measurements and X-ray photoelectron spectroscopy (XPS). Zeta-potential measurements revealed that FCLS was more efficiently absorbed onto galena than onto chalcopyrite. XPS measurements further suggested that FCLS enhanced the surface oxidation of galena but prevented that of chalcopyrite. Thus, FCLS could be a potential candidate as a depressant for chalcopyrite-galena flotation because of its low cost and its lack of detrimental effects on the environment.

Examining early-diagenetic processes as a chief sink for carbonate in the aftermath of the Triassic-Jurassic crisis: Hettangian concretions of Muller Canyon, NV, USA

NASA Astrophysics Data System (ADS)

Ritterbush, K. A.; Loyd, S. J.; Corsetti, F. A.; Bottjer, D. J.; Berelson, W.

2015-12-01

Tectonic, climate, and biotic changes across the Triassic-Jurassic transition appear to have resulted in a "carbonate gap" in the rock record of many shallow marine environments. Ecological state changes documented in near-shore settings in both Tethys and Panthassa show an earliest Jurassic switch to sponge-dominated biosiliceous sedimentation regimes. The Sunrise Formation exposed in the Gabbs Valley Range of Nevada (USA) records a peculiar juxtaposition of Hettangian carbonate-rich strata that contain demosponge spicules as the primary bioclast. It is unclear 1) why biocalcifiers were not recorded in higher abundance in this near-shore back-arc basin setting; 2) why carbonates formed following a biosiliceous regime; and 3) what the lithology indicates about post-extinction marine geochemical dynamics. Detailed sedimentological, paleontological, and geochemical analyses were applied to a 20-m thick sequence of limestone and chert in the Muller Canyon area, which is the Auxiliary Stratotype for the Triassic/Jurassic boundary. Concretion anatomy, bioclast microfacies, and oxygen and carbon isotopic signatures all indicate the Hettangian limestones are chiefly diagenetic concretions that all formed very shallowly, some essentially at the sediment-water interface. We infer that local bottom waters and/or pore waters were supersaturated with respect to calcium carbonate and that this contributed to widespread concretion sedimentation independent of biomineralization. Ecological incumbency of the demosponge meadows may have been supported by concurrent augmentation of marine silica concentration and this apparently proved inhospitable to re-colonization of benthic biocalcifying macrofauna. Together the biotic and lithologic consequences of the extinction represent million-year scale ecological restructuring and highlight early diagenetic precipitation as a major sink in long-term regional carbonate cycling. Perhaps the widespread 'carbonate gap' is actually a gap in

Comparative study on the selective chalcopyrite bioleaching of a molybdenite concentrate with mesophilic and thermophilic bacteria.

PubMed

Romano, P; Blázquez, M L; Alguacil, F J; Muñoz, J A; Ballester, A; González, F

2001-03-01

This study evaluates different bioleaching treatments of a molybdenite concentrate using mesophilic and thermophilic bacterial cultures. Further studies on the chemical leaching and the electrochemical behavior of the MoS(2) concentrate were carried out. Bioleaching tests showed a progressive removal of chalcopyrite from the molybdenite concentrate with an increase in temperature. Chemical leaching tests support the idea of an indirect attack of the concentrate. Electrochemical tests indicate that chalcopyrite dissolution is favored when molybdenite is present. Therefore, this type of bioleaching treatment could be applied to purify molybdenite flotation concentrates by selectively dissolving chalcopyrite.

Unravelling the depositional origins and diagenetic alteration of carbonate breccias

NASA Astrophysics Data System (ADS)

Madden, Robert H. C.; Wilson, Moyra E. J.; Mihaljević, Morana; Pandolfi, John M.; Welsh, Kevin

2017-07-01

Carbonate breccias dissociated from their platform top counterparts are little studied despite their potential to reveal the nature of past shallow-water carbonate systems and the sequential alteration of such systems. A petrographic and stable isotopic study allowed evaluation of the sedimentological and diagenetic variability of the Cenozoic Batu Gading Limestone breccia of Borneo. Sixteen lithofacies representing six facies groups have been identified mainly from the breccia clasts on the basis of shared textural and compositional features. Clasts of the breccia are representative of shallow carbonate platform top and associated flank to basinal deposits. Dominant inputs are from rocky (karstic) shorelines or localised seagrass environments, coral patch reef and larger foraminiferal-rich deposits. Early, pre-brecciation alteration (including micritisation, rare dissolution of bioclasts, minor syntaxial overgrowth cementation, pervasive neomorphism and calcitisation of bioclasts and matrix) was mainly associated with marine fluids in a near surface to shallow burial environment. The final stages of pre-brecciation diagenesis include mechanical compaction and cementation of open porosity in a shallow to moderate depth burial environment. Post-brecciation diagenesis took place at increasingly moderate to deep burial depths under the influence of dominantly marine burial fluids. Extensive compaction, circum-clast dissolution seams and stylolites have resulted in a tightly fitted breccia fabric, with some development of fractures and calcite cements. A degree of facies-specific controls are evident for the pre-brecciation diagenesis. Pervasive mineralogical stabilisation and cementation have, however, led to a broad similarity of diagenetic features in the breccia clasts thereby effectively preserving depositional features of near-original platform top and margin environments. There is little intra-clast alteration overprint associated with subsequent clast reworking

Diagenetic Mineralogy at Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Vaniman, David; Blake, David; Bristow, Thomas F.; Chipera, Steve; Gellert, Ralf; Ming, Douglas; Morris, Richard; Rampe, E. B.; Rapin, William

2015-01-01

Three years into exploration of sediments in Gale crater on Mars, the Mars Science Laboratory rover Curiosity has provided data on several modes and episodes of diagenetic mineral formation. Curiosity determines mineralogy principally by X-ray diffraction (XRD), but with supporting data from thermal-release profiles of volatiles, bulk chemistry, passive spectroscopy, and laser-induced breakdown spectra of targeted spots. Mudstones at Yellowknife Bay, within the landing ellipse, contain approximately 20% phyllosilicate that we interpret as authigenic smectite formed by basalt weathering in relatively dilute water, with associated formation of authigenic magnetite as in experiments by Tosca and Hurowitz [Goldschmidt 2014]. Varied interlayer spacing of the smectite, collapsed at approximately 10 A or expanded at approximately 13.2 A, is evidence of localized diagenesis that may include partial intercalation of metal-hydroxyl groups in the approximately 13.2 A material. Subsequent sampling of stratigraphically higher Windjana sandstone revealed sediment with multiple sources, possible concentration of detrital magnetite, and minimal abundance of diagenetic minerals. Most recent sampling has been of lower strata at Mount Sharp, where diagenesis is widespread and varied. Here XRD shows that hematite first becomes abundant and products of diagenesis include jarosite and cristobalite. In addition, bulk chemistry identifies Mg-sulfate concretions that may be amorphous or crystalline. Throughout Curiosity's traverse, later diagenetic fractures (and rarer nodules) of mm to dm scale are common and surprisingly constant and simple in Ca-sulfate composition. Other sulfates (Mg,Fe) appear to be absent in this later diagenetic cycle, and circumneutral solutions are indicated. Equally surprising is the rarity of gypsum and common occurrence of bassanite and anhydrite. Bassanite, rare on Earth, plays a major role at this location on Mars. Dehydration of gypsum to bassanite in the

Diagenetic silica enrichment and late-stage groundwater activity in Gale crater, Mars

USGS Publications Warehouse

Frydenvang, Jens; Gasda, Patrick J.; Hurowitz, Joel A.; Grotzinger, John P.; Wiens, Roger C.; Newsom, Horton E.; Edgett, Ken S.; Watkins, Jessica; Bridges, John C.; Maurice, Sylvestre; Fisk, Martin R.; Johnson, Jeffrey R.; Rapin, William; Stein, Nathan; Clegg, Sam M.; Schwenzer, S. P.; Bedford, C.; Edwards, P.; Mangold, Nicolas; Cousin, Agnes; Anderson, Ryan; Payre, Valerie; Vaniman, David; Blake, David; Lanza, Nina L.; Gupta, Sanjeev; Van Beek, Jason; Sautter, Violaine; Meslin, Pierre-Yves; Rice, Melissa; Milliken, Ralf; Gellert, Ralf; Thompson, Lucy; Clark, Ben C.; Sumner, Dawn Y.; Fraeman, Abigail A.; Kinch, Kjartan M; Madsen, Morten B.; Mitofranov, Igor; Jun, Insoo; Calef, Fred J.; Vasavada, Ashwin R.

2017-01-01

Diagenetic silica enrichment in fracture-associated halos that crosscut lacustrine and unconformably overlying aeolian sedimentary bedrock is observed on the lower north slope of Aeolis Mons in Gale crater, Mars. The diagenetic silica enrichment is colocated with detrital silica enrichment observed in the lacustrine bedrock yet extends into a considerably younger, unconformably draping aeolian sandstone, implying that diagenetic silica enrichment postdates the detrital silica enrichment. A causal connection between the detrital and diagenetic silica enrichment implies that water was present in the subsurface of Gale crater long after deposition of the lacustrine sediments and that it mobilized detrital amorphous silica and precipitated it along fractures in the overlying bedrock. Although absolute timing is uncertain, the observed diagenesis likely represents some of the most recent groundwater activity in Gale crater and suggests that the timescale of potential habitability extended considerably beyond the time that the lacustrine sediments of Aeolis Mons were deposited.

A Paleomagnetic and Diagenetic Study of the Woodford Shale, Oklahoma, U.S.A.: The Timing of Hydrothermal Alteration

NASA Astrophysics Data System (ADS)

Roberts, J.; Elmore, R. D.

2017-12-01

An oriented Woodford Shale core from the Ardmore Basin near the Ouachita thrust zone (Core B) was sampled to identify diagenetic events and interpret their origin, and to test if a magnetization was present that can be used to date the altering event(s). The shale is extensively altered, exhibiting a complex paragenesis with multiple fractures and brecciated intervals. Multiple hydrothermal minerals, including biotite, magnesite, norsethite, witherite, gorceixite, potassium feldspar, sphalerite, chalcopyrite, and saddle dolomite, are present in and around fractures and in the matrix. Vitrinite and bitumen reflectance measurements indicate VRo values of 1.82% ( 230°C). Two other Woodford Shale cores (A and C) from the Anadarko Basin also contain hydrothermal minerals. Vitrinite and bitumen reflectance data reveal trends between thermal maturity and the level of hydrothermal alteration, with Core A (0.80% VRo ( 125°C) displaying the lowest alteration, and Core C ( 1.5% VRo ( 210°C) displaying intermediate alteration compared to core B. Paleomagnetic analysis of Core B reveals the presence of a characteristic remanent magnetization (ChRM) with south-southeasterly declinations and shallow inclinations that is unblocked by 450°C and is interpreted to reside in magnetite. This ChRM is interpreted to be either a chemical remanent magnetization (CRM) or a thermochemical remanent magnetization (TCRM) acquired during the Late Permian based on the pole position. The presence of specimens with the CRM/TCRM in altered rock and high thermal maturities suggests that this CRM/TCRM originated from alteration by hydrothermal fluids. These results suggest that the Woodford Shale evolved into an open diagenetic system. In addition to causing heightened thermal maturities, these hydrothermal fluids both increased porosity through dissolution and decreased porosity through precipitation of minerals. The Late Permian timing agrees with the dating of hydrothermal alteration found

Percolation of diagenetic fluids in the Archaean basement of the Franceville basin

NASA Astrophysics Data System (ADS)

Mouélé, Idalina Moubiya; Dudoignon, Patrick; Albani, Abderrazak El; Cuney, Michel; Boiron, Marie-Christine; Gauthier-Lafaye, François

2014-01-01

-rich formations; a low-salinity fluid likely of meteoric origin migrating through the granitic basement; mineralizing fluids resulting from the mixing of fluids 1 and 3; high-temperature fluids resulting from the natural nuclear reactor environment (Mathieu et al., 2000). The present paper attempts to characterize the succession of alteration events that have affected the top of the basement below the Palaeoproterozoic sediment unconformity. Are these alterations related to early post-magmatic to hydrothermal events, to palaeoweathering, or to late infiltration of diagenetic brines from the overlying basin? Our study, carried out on drill core samples from Kiéné, is supported by petrographic investigation, new fluid inclusion data and U-Pb geochronology on monazite.

Diagenetic susceptibility of carbonate archives - an experimental approach

NASA Astrophysics Data System (ADS)

Pederson, C.; Purgstaller, B.; Mavromatis, V.; Dietzel, M.; Jöns, N.; Buhl, D.; Neuser, R. D.; Breitenbach, S. F. M.; Hoffmann, R.; Kwiecien, O.; Riechelmann, S.; Immenhauser, A.

2017-12-01

Carbonate sediments and biominerals can record environmental conditions during both deposition and subsequent diagenesis, making them important archives of within the geologic record. Therefore, the alteration processes of these paleoenvironmental proxies are important to understand if one is to deduce environmental conditions based on their petrographic and geochemical signature. This study uses an experimental approach in order to best indicate the controls and effects of the diagenesis of various carbonate archives. Samples are hydrothermally altered at known conditions including pore water chemistry (meteoric and brine fluids), and temperature (100-200°C), and are directly compared to an unaltered subsample (same specimen) for petrographic and geochemical alteration, allowing for reduced heterogeneity, and a quantitative and systematic approach to determine the type, extent, and controls of diagenesis. Initial results indicate little-no alteration at the lower temperature experiments (100°C), and almost complete alteration observed at higher temperatures (175-200°C), while intermediate temperature ranges (130-160°C) prove promising for the evaluation of both diagenetic mechanisms, as well as rate limiting factors controlling alteration. Initial results indicate partial recrystallization of the bivalve A. Islandica, as well as other carbonates (corals, bivalves, gastropods, ammonites, and speleothems), with a visually distinct recrystallization front for select specimens. Results indicate that the diagenetic pathway preferentially follows organic distribution, and internal structures within the organo-sediments and minerals, possibly formed during initial formation. Alteration also suggests preferential movement of intercrystalline organics in some sample types, where they appear to be pushed away from the diagenetic front, causing concentration of the water insoluble organics, and the production of visually darker areas surrounding diagenetic fluid pathways.

Community dynamics of attached and free cells and the effects of attached cells on chalcopyrite bioleaching by Acidithiobacillus sp.

PubMed

Yang, Hailin; Feng, Shoushuai; Xin, Yu; Wang, Wu

2014-02-01

The community dynamics of attached and free cells of Acidithiobacillus sp. were investigated and compared during chalcopyrite bioleaching process. In the mixed strains system, Acidithiobacillus ferrooxidans was the dominant species at the early stage while Acidithiobacillus thiooxidans owned competitive advantage from the middle stage to the end of bioprocess. Meanwhile, compared to A. ferrooxidans, more significant effects of attached cells on free biomass with A. thiooxidans were shown in either the pure or mixed strains systems. Moreover, the effects of attached cells on key chemical parameters were also studied in different adsorption-deficient systems. Consistently, the greatest reduction of key chemical ion was shown with A. thiooxidans and the loss of bioleaching efficiency was high to 50.5%. These results all demonstrated the bioleaching function of attached cells was more efficient than the free cells, especially with A. thiooxidans. These notable results would help us to further understand the chalcopyrite bioleaching. Copyright © 2013 Elsevier Ltd. All rights reserved.

Pressure-induced structural transition in chalcopyrite ZnSiP2

NASA Astrophysics Data System (ADS)

Bhadram, Venkata S.; Krishna, Lakshmi; Toberer, Eric S.; Hrubiak, Rostislav; Greenberg, Eran; Prakapenka, Vitali B.; Strobel, Timothy A.

2017-05-01

The pressure-dependent phase behavior of semiconducting chalcopyrite ZnSiP2 was studied up to 30 GPa using in situ X-ray diffraction and Raman spectroscopy in a diamond-anvil cell. A structural phase transition to the rock salt type structure was observed between 27 and 30 GPa, which is accompanied by soft phonon mode behavior and simultaneous loss of Raman signal and optical transmission through the sample. The high-pressure rock salt type phase possesses cationic disorder as evident from broad features in the X-ray diffraction patterns. The behavior of the low-frequency Raman modes during compression establishes a two-stage, order-disorder phase transition mechanism. The phase transition is partially reversible, and the parent chalcopyrite structure coexists with an amorphous phase upon slow decompression to ambient conditions.

Investigation of energy gene expressions and community structures of free and attached acidophilic bacteria in chalcopyrite bioleaching.

PubMed

Zhu, Jianyu; Jiao, Weifeng; Li, Qian; Liu, Xueduan; Qin, Wenqing; Qiu, Guanzhou; Hu, Yuehua; Chai, Liyuan

2012-12-01

In order to better understand the bioleaching mechanism, expression of genes involved in energy conservation and community structure of free and attached acidophilic bacteria in chalcopyrite bioleaching were investigated. Using quantitative real-time PCR, we studied the expression of genes involved in energy conservation in free and attached Acidithiobacillus ferrooxidans during bioleaching of chalcopyrite. Sulfur oxidation genes of attached A. ferrooxidans were up-regulated while ferrous iron oxidation genes were down-regulated compared with free A. ferrooxidans in the solution. The up-regulation may be induced by elemental sulfur on the mineral surface. This conclusion was supported by the results of HPLC analysis. Sulfur-oxidizing Acidithiobacillus thiooxidans and ferrous-oxidizing Leptospirillum ferrooxidans were the members of the mixed culture in chalcopyrite bioleaching. Study of the community structure of free and attached bacteria showed that A. thiooxidans dominated the attached bacteria while L. ferrooxidans dominated the free bacteria. With respect to available energy sources during bioleaching of chalcopyrite, sulfur-oxidizers tend to be on the mineral surfaces whereas ferrous iron-oxidizers tend to be suspended in the aqueous phase. Taken together, these results indicate that the main role of attached acidophilic bacteria was to oxidize elemental sulfur and dissolution of chalcopyrite involved chiefly an indirect bioleaching mechanism.

Diagenetic Crystal Clusters and Dendrites, Lower Mount Sharp, Gale Crater

NASA Technical Reports Server (NTRS)

Kah, L. C.; Kronyak, R.; Van Beek, J.; Nachon, M.; Mangold, N.; Thompson, L.; Wiens, R.; Grotzinger, J.; Farmer, J.; Minitti, M.;

Adsorption Mechanism of 4-Amino-5-mercapto-1,2,4-triazole as Flotation Reagent on Chalcopyrite.

PubMed

Yin, Zhigang; Hu, Yuehua; Sun, Wei; Zhang, Chenyang; He, Jianyong; Xu, Zhijie; Zou, Jingxiang; Guan, Changping; Zhang, Chenhu; Guan, Qingjun; Lin, Shangyong; Khoso, Sultan Ahmed

2018-04-03

A novel compound 4-amino-5-mercapto-1,2,4-triazole was first synthesized, and its selective adsorption mechanism on the surface of chalcopyrite was comprehensively investigated using UV-vis spectra, zeta-potential, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy measurements (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and first principles calculations. The experimental and computational results consistently demonstrated that AMT would chemisorb onto the chalcopyrite surface by the formation of a five-membered chelate ring. The first principles periodic calculations further indicated that AMT would prefer to adsorb onto Cu rather than Fe due to the more negative adsorption energy of AMT on Cu in the chalcopyrite (001) surface, which was further confirmed by the coordination reaction energies of AMT-Cu and AMT-Fe based on the simplified cluster models at a higher accuracy level (UB3LYP/Def2-TZVP). The bench-scale results indicated that the selective index improved significantly when using AMT as a chalcopyrite depressant in Cu-Mo flotation separation.

Overview of the diagenetic features analyzed by ChemCam onboard Curiosity

NASA Astrophysics Data System (ADS)

Mangold, N.; Forni, O.; Nachon, M.; Blaney, D. L.; Wiens, R. C.; Kah, L. C.; Kronyak, R. E.; Clegg, S. M.; Cousin, A.; Fisk, M. R.; Gasnault, O.; Grotzinger, J. P.; Lanza, N.; Lasue, J.; Le Deit, L.; Le Mouelic, S.; Maurice, S.; Meslin, P. Y.; Rapin, W.; Newsom, H. E.; Sumner, D. Y.

2015-12-01

The Curiosity rover has encountered a variety of sedimentary rocks with significant variations in both texture and composition. Most of the sandstones and mudstones are interpreted as having been deposited in a fluvio-lacustrine environment, as analyzed in details in the waypoints named Yellowknife Bay, Kimberley and Pahrump. All of these sediments have been crossed by diagenetic features of different composition. Light-toned Ca-sulfate veins observed initially at Yellowknife Bay were observed along the traverse, and in high density at the Pahrump location. As they appear in all sediments and show straight fractures, they correspond to late-stage diagenetic features, due to fluid circulation, with fractures probably due to hydraulic stress at depth. In contrast to light-toned veins, earlier-stage diagenetic features have shown variable composition in the three areas. At Yellowknife Bay, raised ridges display enriched Mg proportion, probably linked to Mg-clay whereas outcrops at Kimberley display fracture fills enriched in Mn and Zn. Pahrump displays a large variety of diagenetic features distinct from these previous examples. Mg-enriched concretions contain S and abundant Ni. Mg enrichments have also been observed in resistant zones along fractures and in resistant layers. Locally concretions also display high Fe, S-bearing material interpreted as Fe-sulfate, probably jarosite. A special location named Garden City at the top of the Parhump sequence displays a complex area with light-toned veins surrounded by darker veins. The latter display strong Ca signatures correlated with F, interpreted as fluorite. No C or S emissions were observed that could alternatively explain the high Ca abundance by carbonates or sulfates. The dark tone of the F-bearing minerals may be due to the presence of Fe. These specific dark veins could derive from the leaching of F-apatite, a mineral that has been observed both in the sandstones and in some of the igneous clasts analyzed by Chem

Diagenetic alteration of impact spherules in the Neoarchean Monteville layer, South Africa

USGS Publications Warehouse

Kohl, I.; Simonson, B.M.; Berke, M.

2006-01-01

Intercontinental correlation of distal Archean impact ejecta layers can be used to help create a global time-stratigraphic framework for early Earth events. For example, an impact spherule layer in the Neoarchean Monteville Formation (Griqualand West Basin, South Africa) may be correlated with layers in one or more formations in Western Australia. To help assess the degree to which diagenetic alteration would hinder such correlations, we performed a petrographic study of spherules in the Monteville layer. Most of the spherules in the Monteville layer have botryoidal rims composed of radial-fibrous K-feldspar, but compaction and replacement have greatly altered their appearance and mineralogy. Moreover, the Monteville spherule layer consists of three main subunits, and spherule compaction varies between subunits as well as across the Griqualand West region. Compaction is about three times greater in a medial spherulerich subunit as compared to a basal subunit rich in large intraclasts, resulting in better preservation of the shapes of melt particles in the latter. However, spherule rims have omparable numbers of fractures in both subunits, indicating the melt particles were fractured prior to compaction. Some spherules contain mica ribbons with a septarian geometry. Fracturing via rapid thermal quenching could help explain all of these features. f hot spherules possessing crystalline rims were thermally shocked when they hit the ocean, fractures would have the observed geometries and provide pathways for fluid infiltration and local replacement of glass by mica. Although heavily distorted, impact spherules in the Monteville layer are very similar to those in the Hesta occurrence of the Neoarchean Jeerinah spherule layer of the Hamersley Basin, even showing similar diagenetic histories. In this instance, diagenetic alteration may actually help rather than hinder intercontinental correlation of impact spherule layers. ??2006 Geological Society of America.

Pressure-induced structural transition in chalcopyrite ZnSiP 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhadram, Venkata S.; Krishna, Lakshmi; Toberer, Eric S.

The pressure-dependent phase behavior of semiconducting chalcopyrite ZnSiP 2 was studied up to 30 GPa using in situ X-ray diffraction and Raman spectroscopy in a diamond-anvil cell. A structural phase transition to the rock salt type structure was observed between 27 and 30 GPa, which is accompanied by soft phonon mode behavior and simultaneous loss of Raman signal and optical transmission through the sample. The high-pressure rock salt type phase possesses cationic disorder as evident from broad features in the X-ray diffraction patterns. The behavior of the low-frequency Raman modes during compression establishes a two-stage, order-disorder phase transition mechanism. Themore » phase transition is partially reversible, and the parent chalcopyrite structure coexists with an amorphous phase upon slow decompression to ambient conditions.« less

Diagenetic patterns and pore space distribution along a platform to outer-shelf transect (Urgonian limestone, Barremian-Aptian, SE France)

NASA Astrophysics Data System (ADS)

Léonide, Philippe; Fournier, François; Reijmer, John J. G.; Vonhof, Hubert; Borgomano, Jean; Dijk, Jurrien; Rosenthal, Maelle; van Goethem, Manon; Cochard, Jean; Meulenaars, Karlien

2014-06-01

The Urgonian limestones of Late Barremian/Early Aptian from Provence (SE, France) are characterized by the occurrence of microporous limestones at regional scale alternating with tight carbonates. This study, based on petrographical (sediment texture, facies) and diagenetical analyses (cement stratigraphy, porosity and isotope geochemistry) of more than 800 limestone samples provides insight into the parameters controlling the genesis, preservation or occlusion of microporosity along an inner platform to outer shelf transect. The tight and microporous Urgonian limestones from Provence can be grouped into 5 rock-types based on textures, associated depositional environments, porosity and pore-type, being: (1) tight inner-platform: TIP; (2) porous inner platform: PIP; (3) tight outer platform: TOP; (4) porous outer platform: POP and (5) tight outer shelf: TOS. In tight (TIP, TOP and TOS types) limestones intergranular and intragranular pore spaces were entirely occluded by early marine and/or early meteoric cementation, whereas in microporous (PIP, POP) limestones a significant fraction of the intergranular macroporosity was preserved during early and shallow burial diagenesis. Micrite neomorphism (hybrid Ostwald ripening process) occurred during meteoric shallow burial diagenesis in PIP and POP limestones during the regional Durancian Uplift event (Albian-Lower Cenomanian). This process resulted in microporosity enhancement and preservation. Circulation of meteoric fluids during exhumation produces intercrystalline microporosity enhancement and moldic porosity development. The present study documents the important role that both early diagenetic and depositional cycles and long-term tectonic processes have on pore space evolution and distribution in Mesozoic platform carbonates.

An insight into the mechanism of charge-transfer of hybrid polymer:ternary/quaternary chalcopyrite colloidal nanocrystals.

PubMed

Chawla, Parul; Singh, Son; Sharma, Shailesh Narain

2014-01-01

In this work, we have demonstrated the structural and optoelectronic properties of the surface of ternary/quaternary (CISe/CIGSe/CZTSe) chalcopyrite nanocrystallites passivated by tri-n-octylphosphine-oxide (TOPO) and tri-n-octylphosphine (TOP) and compared their charge transfer characteristics in the respective polymer: chalcopyrite nanocomposites by dispersing them in poly(3-hexylthiophene) polymer. It has been found that CZTSe nanocrystallites due to their high crystallinity and well-ordered 3-dimensional network in its pristine form exhibit a higher steric- and photo-stability, resistance against coagulation and homogeneity compared to the CISe and CIGSe counterparts. Moreover, CZTSe nanocrystallites display efficient photoluminescence quenching as evident from the high value of the Stern-Volmer quenching constant (K SV) and eventually higher charge transfer efficiency in their respective polymer P3HT:CZTSe composites. We modelled the dependency of the charge transfer from the donor and the charge separation mechanism across the donor-acceptor interface from the extent of crystallinity of the chalcopyrite semiconductors (CISe/CIGSe/CZTSe). Quaternary CZTSe chalcopyrites with their high crystallinity and controlled morphology in conjunction with regioregular P3HT polymer is an attractive candidate for hybrid solar cells applications.

A review of the structure, and fundamental mechanisms and kinetics of the leaching of chalcopyrite.

PubMed

Li, Y; Kawashima, N; Li, J; Chandra, A P; Gerson, A R

2013-09-01

Most investigators regard CuFeS2 as having the formal oxidation states of Cu(+)Fe(3+)(S(2-))2. However, the spectroscopic characterisation of chalcopyrite is clearly influenced by the considerable degree of covalency between S and both Fe and Cu. The poor cleavage of CuFeS2 results in conchoidal surfaces. Reconstruction of the fractured surfaces to form, from what was previously bulk S(2-), a mixture of surface S(2-), S2(2) and S(n)(2-) (or metal deficient sulfide) takes place. Oxidation of chalcopyrite in air (i.e. 0.2 atm of O2 equilibrated with atmospheric water vapour) results in a Fe(III)-O-OH surface layer on top of a Cu rich sulfide layer overlying the bulk chalcopyrite with the formation of Cu(II) and Fe(III) sulfate, and Cu(I)-O on prolonged oxidation. Cu2O and Cu2S-like species have also been proposed to form on exposure of chalcopyrite to air. S2(2-), S(n)(2-) and S(0) form on the chalcopyrite surface upon aqueous leaching. The latter two of these species along with a jarosite-like species are frequently proposed to result in surface leaching passivation. However, some investigators have reported the formation of S(0) sufficiently porous to allow ion transportation to and from the chalcopyrite surface. Moreover, under some conditions both S(n)(2-) and S(0) were observed to increase in surface concentration for the duration of the leach with no resulting passivation. The effect of a number of oxidants, e.g. O2, H2O2, Cu(2+), Cr(6+) and Fe(3+), has been examined. However, this is often accompanied by poor control of leach parameters, principally pH and E(h). Nevertheless, there is general agreement in the literature that chalcopyrite leaching is significantly affected by solution redox potential with an optimum E(h) range suggesting the participation of leach steps that involve both oxidation and reduction. Three kinetic models have generally been suggested by researchers to be applicable: diffusion, chemical reaction and a mixed model containing diffusion

Diagenetic gypsum related to sulfur deposits in evaporites (Libros Gypsum, Miocene, NE Spain)

NASA Astrophysics Data System (ADS)

Ortí, Federico; Rosell, Laura; Anadón, Pere

2010-07-01

The Libros Gypsum is the thickest evaporite unit of the Miocene infill of the Teruel Basin in NE Spain. During the deposition of this unit, intense bacterial sulfate-reducing (BSR) activity in the lake depocenter generated a native sulfur deposit. Diagenetic gypsum resulted from subsequent sulfur oxidation. The different processes involved in these transformations were first investigated by Anadón et al. (1992). The present paper is concerned with this diagenetic gypsum from the stratigraphic, petrographic, isotopic and genetic points of view. Diagenetic gypsum occurs mainly as continuous or discontinuous layers, individual levels or lenses, irregular masses, nodules and micronodules, and veins. Its main textures are coarse-crystalline anhedral and fine-grained (alabastrine), both of which can replace any former lithology (carbonate, gypsum, and sulfur). The following sequence of processes and mineral/textural transformations is deduced: primary gypsum deposition — BSR and biodiagenetic carbonate/H 2S production — growth of native sulfur — growth of diagenetic gypsum — partial recrystallization of the diagenetic gypsum textures. The gypsification of the native sulfur generated two types of banded structures in the diagenetic gypsum: (1) concentric structures of centripetal growth, and (2) expansive, roughly concentric structures. In the first type, the gypsification operated from the outer boundaries towards the inner parts. In the second type, part of the carbonate hosting the sulfur was also gypsified (replaced/cemented). In the diagenetic gypsum, the δ34S values are in agreement with a native sulfur and H 2S provenance. The δ18O sulfate values, however, enable us to differentiate two main groups of values: one with positive values and the other with negative values. In the group of positive values, interstitial (evaporated) solutions participated in the sulfur oxidation; this process presumably occurred in a first oxidation stage during shallow

Diagenetic alteration of biogenic silica oxygen isotope values: implications for use as a paleoenvironmental proxy

NASA Astrophysics Data System (ADS)

Dodd, J. P.; Abbott, T.; Scherer, R. P.

2016-12-01

formation in the early Pliocene Ross Sea may be driven by regional and global scale climate processes. Sedimentary diatoms most likely represent a combination of growth and diagenetic environments, and the δ18O value of diagenetic water needs to be addressed when reconstructing paleoceanographic and paleoenvironmental conditions.

FTIR studies of xanthate adsorption on chalcopyrite, pentlandite and pyrite surfaces

NASA Astrophysics Data System (ADS)

Zhang, Yahui; Cao, Zhao; Cao, Yongdan; Sun, Chuanyao

2013-09-01

The Fourier transform infrared (FTIR) spectra of sodium butyl xanthate, dibutyl dixanthogen, metal xanthate compounds and surfaces of chalcopyrite, pentlandite and pyrite treated with sodium butyl xanthate solution were systematically studied. The products of xanthate adsorpted on the three different minerals were characterized by comparing their FTIR spectra to those of dixanthogen and metal xanthate. Both metal xanthate and dixanthogen are formed on the surfaces of these minerals. However, the relative proportions of metal xanthate to dixanthogen on the minerals are different. In the cases of chalcopyrite and pentlandite, the quantity of metal xanthate is larger than that of dixanthogen. For pyrite, on the contrary, the quantity of dixanthogen is much greater than that of ferric xanthate. Therefore, the formation of dixanthogen is more essential for the flotation of pyrite.

Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

USGS Publications Warehouse

Ufnar, David F.; Gonzalez, Luis A.; Ludvigson, Greg A.; Brenner, Richard L.; Witzkes, Brian J.

2004-01-01

Meteoric sphaerosiderite lines (MSLs), defined by invariant ??18O and variable ??13C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre-scale FeCO3 nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well-preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO3) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca2+, Mg2+ and Mn2+ for Fe2+. Examples of diagenetically altered Cretaceous sphaerosiderite-bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic ??18O and ??13C values are preserved. All three units contain poikilotopic calcite cements with significantly different ??18O and ??13C values from the co-occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant ??18O vs. ??13C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric ??18O and ??13C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end-member compositions. Modelled hyperbolic fluid mixing curves for the

Biomining with bacteriophage: selectivity of displayed peptides for naturally occurring sphalerite and chalcopyrite.

PubMed

Curtis, Susan B; Hewitt, Jeff; Macgillivray, Ross T A; Dunbar, W Scott

2009-02-01

During mineral processing, concentrates of sulfide minerals of economic interest are formed by froth flotation of fine ore particles. The method works well but recovery and selectivity can be poor for ores with complex mineralogy. There is considerable interest in methods that improve the selectivity of this process while avoiding the high costs of using flotation chemicals. Here we show the first application of phage biotechnology to the processing of economically important minerals in ore slurries. A random heptapeptide library was screened for peptide sequences that bind selectively to the minerals sphalerite (ZnS) and chalcopyrite (CuFeS2). After several rounds of enrichment, cloned phage containing the surface peptide loops KPLLMGS and QPKGPKQ bound specifically to sphalerite. Phage containing the peptide loop TPTTYKV bound to both sphalerite and chalcopyrite. By using an enzyme-linked immunosorbant assay (ELISA), the phage was characterized as strong binders compared to wild-type phage. Specificity of binding was confirmed by immunochemical visualization of phage bound to mineral particles but not to silica (a waste mineral) or pyrite. The current study focused primarily on the isolation of ZnS-specific phage that could be utilized in the separation of sphalerite from silica. At mining sites where sphalerite and chalcopyrite are not found together in natural ores, the separation of sphalerite from silica would be an appropriate enrichment step. At mining sites where sphalerite and chalcopyrite do occur together, more specific phage would be required. This bacteriophage has the potential to be used in a more selective method of mineral separation and to be the basis for advanced methods of mineral processing.

Chemistry of diagenetic features analyzed by ChemCam at Pahrump Hills, Gale crater, Mars

USGS Publications Warehouse

Nachon, Marion; Mangold, Nicolas; Forni, Olivier; Kah, Linda C.; Cousin, Agnes; Wiens, Roger C.; Anderson, Ryan; Blaney, Diana L.; Blank, Jen G.; Calef, Fred J.; Clegg, Samuel M.; Fabre, Cecile; Fisk, Martin R.; Gasnault, Olivier; Grotzinger, John P.; Kronyak, Rachel; Lanza, Nina L.; Lasue, Jeremie; Le Deit, Laetitia; Le Mouelic, Stephane; Maurice, Sylvestre; Meslin, Pierre-Yves; Oehler, D. Z.; Payre, Valerie; Rapin, William; Schroder, Susanne; Stack, Katherine M.; Sumner, Dawn

2017-01-01

The Curiosity rover's campaign at Pahrump Hills provides the first analyses of lower Mount Sharp strata. Here we report ChemCam elemental composition of a diverse assemblage of post-depositional features embedded in, or cross-cutting, the host rock. ChemCam results demonstrate their compositional diversity, especially compared to the surrounding host rock: (i) Dendritic aggregates and relief enhanced features, characterized by a magnesium enhancement and sulfur detection, and interpreted as Mg-sulfates; (ii) A localized observation that displays iron enrichment associated with sulfur, interpreted as Fe-sulfate; (iii) Dark raised ridges with varying Mg- and Ca-enriched compositions compared to host rock; (iv) Several dark-toned veins with calcium enhancement associated with fluorine detection, interpreted as fluorite veins. (v) Light-toned veins with enhanced calcium associated with sulfur detection, and interpreted as Ca-sulfates. The diversity of the Pahrump Hills diagenetic assemblage suggests a complex post-depositional history for fine-grained sediments for which the origin has been interpreted as fluvial and lacustrine. Assessment of the spatial and relative temporal distribution of these features shows that the Mg-sulfate features are predominant in the lower part of the section, suggesting local modification of the sediments by early diagenetic fluids. In contrast, light-toned Ca-sulfate veins occur in the whole section and cross-cut all other features. A relatively late stage shift in geochemical conditions could explain this observation. The Pahrump Hills diagenetic features have no equivalent compared to targets analyzed in other locations at Gale crater. Only the light-toned Ca-sulfate veins are present elsewhere, along Curiosity's path, suggesting they formed through a common late-stage process that occurred at over a broad area.

Cement Distribution and Diagenetic Pathway of the Miocene Sediments on Kardiva Platform, Maldives.

NASA Astrophysics Data System (ADS)

Laya, J. C.; Prince, K.; Betzler, C.; Eberli, G. P.; Blättler, C. L.; Swart, P. K.; Reolid, J.; Alvarez Zarikian, C. A.; Reijmer, J.

2017-12-01

The Maldives archipelago is an ideal example for understanding the dynamics of isolated carbonate platforms. While previous sedimentological studies have focused on oceanographic and climatic controls on deposition, there have been limited studies on the diagenetic evolution of the Maldives archipelago. This project seeks to establish a relationship between the facies, cement distribution, and diagenetic evolution of the Kardiva Platform and associated diagenetic fluids. Samples from cores of IODP Expedition 359 at Sites U1645, U1469, and U1470 were analyzed for stable isotope geochemistry and detailed petrography including SEM, confocal and CL microscopy to investigate variations in facies, cements, porosity and diagenetic products. The facies analyzed consist mainly of planktonic and benthic foraminifers, red coralline algae, echinoderm, coral and skeletal fragments. The main facies include foraminifera grain/packstone, red algae rich grain/packstone, algal floatstone and coral floatstone. Those facies present a cyclic and general shallowing upwards trend. These facies are interpreted as shallow platform deposits on proximal areas to the margin associated with the oligophotic zone. Cement volume varies between 5% and 48%, and they have been classified as isopachous, bladed to fibrous (dog tooth), drusy and equant. Equant and drusy show recognizable growth bands with CL and confocal. Evidence of intense dissolution is shown by extensive moldic porosity within phreatic and limited vadose zones. In addition, dolomite appears as a replacement phase associated with red-algae-rich horizons and as cement on pore walls and voids. These deposits experienced a variety of diagenetic processes driven by the evolution of diagenetic fluid chemistry and by the nature of the skeletal components. Those processes can be tied to external controls such as climate (monsoonal effects), sea-level and currents.

Leaching of Chalcopyrite with Thiobacillus ferrooxidans: Effect of Surfactants and Shaking

PubMed Central

Duncan, D. W.; Trussell, P. C.; Walden, C. C.

1964-01-01

The rate of leaching of chalcopyrite by Thiobacillus ferrooxidans has been greatly accelerated by using shaken flasks in place of stationary bottles or percolators. A further increase in rate and extent of leaching was obtained by the use of Tween 20, 40, 60, and 80, Triton X-100, Quaker TT 5386, and Hyamine 2389. Tween 20 was the most effective surfactant. No individual component of the Tween molecule was responsible for the improved leaching. The Tween-to-chalcopyrite ratio is more important than the Tween-to-medium ratio. The effect of the surfactants is probably due to increased contact between the mineral surface and the organism, and shaking provides the necessary oxygen. Rates and yields obtained by use of surfactants and shaking as aids to microbiological leaching approach those obtained with acidified erric sulfate leaching. PMID:14131359

Diagenetic contrast of sandstones in hydrocarbon prospective Mesozoic rift basins (Ethiopia, UK, USA)

NASA Astrophysics Data System (ADS)

Wolela, A.

2014-11-01

Diagenetic studied in hydrocarbon-prospective Mesozoic rift basins were carried out in the Blue Nile Basin (Ethiopia), Ulster Basin (United Kingdom) and Hartford Basin (United States of America). Alluvial fan, single and amalgamated multistorey meandering and braided river, deep and shallow perennial lake, shallow ephemeral lake, aeolian and playa mud-flat are the prominent depositional environments. The studied sandstones exhibit red bed diagenesis. Source area geology, depositional environments, pore-water chemistry and circulation, tectonic setting and burial history controlled the diagenetic evolution. The diagenetic minerals include: facies-related minerals (calcrete and dolocrete), grain-coating clay minerals and/or hematite, quartz and feldspar overgrowths, carbonate cements, hematite, kaolinite, illite-smectite, smectite, illite, chlorite, actinolite, laumontite, pyrite and apatite. Diversity of diagenetic minerals and sequence of diagenetic alteration can be directly related to depositional environment and burial history of the basins. Variation in infiltrated clays, carbonate cements and clay minerals observed in the studied sandstones. The alluvial fan and fluviatile sandstones are dominated by kaolinite, illite calcite and ferroan calcite, whereas the playa and lacustrine sandstones are dominated by illite-smectite, smectite-chlorite, smectite, chlorite, dolomite ferroan dolomite and ankerite. Albite, pyrite and apatite are predominantly precipitated in lacustrine sandstones. Basaltic eruption in the basins modified mechanically infiltrated clays to authigenic clays. In all the studied sandstones, secondary porosity predominates over primary porosity. The oil emplacement inhabited clay authigenesis and generation of secondary porosity, whereas authigenesis of quartz, pyrite and apatite continued after oil emplacement.

Chalcopyrite dissolution: Scanning photoelectron microscopy examination of the evolution of sulfur species with and without added iron or pyrite

NASA Astrophysics Data System (ADS)

Li, Yubiao; Qian, Gujie; Brown, Paul L.; Gerson, Andrea R.

2017-09-01

Dissolution and oxidation of sulfide minerals play key roles in both acid and metalliferous rock drainage and supergene enrichment. Surface speciation heterogeneity, critical to understanding mechanisms of mineral sulfide dissolution, has to date largely not been considered. To this end synchrotron scanning photoelectron microscopy (SPEM) was employed to examine freshly fractured and partially dissolved chalcopyrite (CuFeS2) surfaces (pH 1.0 HClO4 solution, redox potential 650 mV relative to a standard hydrogen electrode, 75 °C). S2- (bulk), S22- and Sn2- were found to be present on all samples at varying concentrations. Oxidation was observed to take place heterogeneously at the sub-micron scale. As compared to chalcopyrite partially dissolved for 5 days, extended dissolution to 10 days did not show appreciably enhanced oxidation of surface species; however surface roughness increased markedly due to the growth/overlap of oxidised sulfur species. On addition of 4 mM iron both S0 and SO42- were observed but not SO32-, indicating that the greater Fe3+ activity/concentration promotes heterogeneous sulfur oxidation. On contact of pyrite (FeS2) with chalcopyrite, significantly greater chalcopyrite surface oxidation was observed than for the other systems examined, with S0, SO32- and SO42- being identified heterogeneously across the surface. It is proposed that chalcopyrite oxidative dissolution is enhanced by increasing its cathodic area, e.g. contacting with pyrite, while increased Fe3+ activity/concentration also contributes to increased dissolution rates. The high degree of surface heterogeneity of these surface products indicates that these surfaces are not passivated by their formation. These results suggest that chalcopyrite dissolution will be accelerated when in contact with pyrite at solution redox potential intermediate between the rest potentials of chalcopyrite and pyrite (560 mV and 660 mV, respectively) and/or iron rich acidic waters with resulting

X-PEEM, XPS and ToF-SIMS characterisation of xanthate induced chalcopyrite flotation: Effect of pulp potential

NASA Astrophysics Data System (ADS)

Kalegowda, Yogesh; Chan, Yuet-Loy; Wei, Der-Hsin; Harmer, Sarah L.

2015-05-01

Synchrotron-based X-ray photoemission electron microscopy (X-PEEM), X-ray photo-electron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and ultraviolet visible spectroscopy were used to characterize the flotation behaviour of chalcopyrite with xanthate at different processing conditions. The flotation recovery of chalcopyrite decreased from 97% under oxidative conditions (Eh ~ 385 mV SHE, pH 4) to 41% at a reductive potential of - 100 mV SHE (at pH 9). X-PEEM images constructed from the metal L3 absorption edges were used to produce near-edge X-ray absorption fine structure (NEXAFS) spectra from regions of interest, allowing the variability in mineral surface chemistry of each mineral particle to be analysed, and the effect of pulp potential (Eh) on the flotation of chalcopyrite to be determined. XPS, ToF-SIMS and NEXAFS analyses of chalcopyrite particles at oxidative conditions show that the surface was mildly oxidised and covered with adsorbed molecular CuEX. The Cu 2p XPS and Cu L2,3 NEXAFS spectra were dominated by CuI species attributed to bulk chalcopyrite and adsorbed CuEX. At a reductive potential of - 100 mV SHE, an increase in concentration of CuI and FeIII oxides and hydroxides was observed. X-PEEM analysis was able to show the presence of a low percentage of CuII oxides (CuO or Cu(OH)2) with predominantly CuI oxide (Cu2O) which is not evident in Cu 2p XPS spectra.

Diagenetic variation at the lamina scale in lacustrine organic-rich shales: Implications for hydrocarbon migration and accumulation

NASA Astrophysics Data System (ADS)

Liang, Chao; Cao, Yingchang; Liu, Keyu; Jiang, Zaixing; Wu, Jing; Hao, Fang

2018-05-01

Lacustrine carbonate-rich shales are well developed within the Mesozoic-Cenozoic strata of the Bohai Bay Basin (BBB) of eastern China and across southeast Asia. Developing an understanding of the diagenesis of these shales is essential to research on mass balance, diagenetic fluid transport and exchange, and organic-inorganic interactions in black shales. This study investigates the origin and distribution of authigenic minerals and their diagenetic characteristics, processes, and pathways at the scale of lacustrine laminae within the Es4s-Es3x shale sequence of the BBB. The research presented in this study is based on thin sections, field emission scanning electron microscope (FESEM) and SEM-catholuminescence (CL) observations of well core samples combined with the use of X-ray diffraction (XRD), energy dispersive spectroscopy, electron microprobe analysis, and carbon and oxygen isotope analyses performed using a laser microprobe mass spectrometer. The dominant lithofacies within the Es4s-Es3x sequence are a laminated calcareous shale (LCS-1) and a laminated clay shale (LCS-2). The results of this study show that calcite recrystallization1 is the overarching diagenetic process affecting the LCS-1, related to acid generation from organic matter (OM) thermal evolution. This evolutionary transition is the key factor driving the diagenesis of this lithofacies, while the transformation of clay minerals is the main diagenetic attribute of the LCS-2. Diagenetic differences occur within different laminae and at variable locations within the same lamina level, controlled by variations in mineral composition and the properties of laminae interfaces. The diagenetic fluid migration scale is vertical and responses (dissolution and replacement) are limited to individual laminae, between zero and 100 μm in width. In contrast, the dominant migration pathway for diagenetic fluid is lateral, along the abrupt interfaces between laminae boundaries, which leads to the vertical

Chemistry of diagenetic features analyzed by ChemCam at Pahrump Hills, Gale crater, Mars

DOE PAGES

Nachon, M.; Mangold, N.; Forni, O.; ...

2017-09-01

The Curiosity rover's campaign at Pahrump Hills provides the first analyses of lower Mount Sharp strata. We report ChemCam elemental composition of a diverse assemblage of post-depositional features embedded in, or cross-cutting, the host rock. ChemCam results demonstrate their compositional diversity, especially compared to the surrounding host rock: (i) Dendritic aggregates and relief enhanced features, characterized by a magnesium enhancement and sulfur detection, and interpreted as Mg-sulfates; (ii) A localized observation that displays iron enrichment associated with sulfur, interpreted as Fe-sulfate; (iii) Dark raised ridges with varying Mg- and Ca-enriched compositions compared to host rock; (iv) Several dark-toned veins withmore » calcium enhancement associated with fluorine detection, interpreted as fluorite veins. (v) Light-toned veins with enhanced calcium associated with sulfur detection, and interpreted as Ca-sulfates. The diversity of the Pahrump Hills diagenetic assemblage suggests a complex post-depositional history for fine-grained sediments for which the origin has been interpreted as fluvial and lacustrine. Assessment of the spatial and relative temporal distribution of these features shows that the Mg-sulfate features are predominant in the lower part of the section, suggesting local modification of the sediments by early diagenetic fluids. Conversely, light-toned Ca-sulfate veins occur in the whole section and cross-cut all other features. A relatively late stage shift in geochemical conditions could explain this observation. The Pahrump Hills diagenetic features have no equivalent compared to targets analyzed in other locations at Gale crater. Only the light-toned Ca-sulfate veins are present elsewhere, along Curiosity's path, suggesting they formed through a common late-stage process that occurred at over a broad area.« less

Chemistry of diagenetic features analyzed by ChemCam at Pahrump Hills, Gale crater, Mars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nachon, M.; Mangold, N.; Forni, O.

The Curiosity rover's campaign at Pahrump Hills provides the first analyses of lower Mount Sharp strata. We report ChemCam elemental composition of a diverse assemblage of post-depositional features embedded in, or cross-cutting, the host rock. ChemCam results demonstrate their compositional diversity, especially compared to the surrounding host rock: (i) Dendritic aggregates and relief enhanced features, characterized by a magnesium enhancement and sulfur detection, and interpreted as Mg-sulfates; (ii) A localized observation that displays iron enrichment associated with sulfur, interpreted as Fe-sulfate; (iii) Dark raised ridges with varying Mg- and Ca-enriched compositions compared to host rock; (iv) Several dark-toned veins withmore » calcium enhancement associated with fluorine detection, interpreted as fluorite veins. (v) Light-toned veins with enhanced calcium associated with sulfur detection, and interpreted as Ca-sulfates. The diversity of the Pahrump Hills diagenetic assemblage suggests a complex post-depositional history for fine-grained sediments for which the origin has been interpreted as fluvial and lacustrine. Assessment of the spatial and relative temporal distribution of these features shows that the Mg-sulfate features are predominant in the lower part of the section, suggesting local modification of the sediments by early diagenetic fluids. Conversely, light-toned Ca-sulfate veins occur in the whole section and cross-cut all other features. A relatively late stage shift in geochemical conditions could explain this observation. The Pahrump Hills diagenetic features have no equivalent compared to targets analyzed in other locations at Gale crater. Only the light-toned Ca-sulfate veins are present elsewhere, along Curiosity's path, suggesting they formed through a common late-stage process that occurred at over a broad area.« less

Fluid expulsion sites on the Cascadia accretionary prism: mapping diagenetic deposits with processed GLORIA imagery

USGS Publications Warehouse

Carson, Bobb; Seke, Erol; Paskevich, Valerie F.; Holmes, Mark L.

1994-01-01

Point-discharge fluid expulsion on accretionary prisms is commonly indicated by diagenetic deposition of calcium carbonate cements and gas hydrates in near-surface (<10 m below seafloor; mbsf) hemipelagic sediment. The contrasting clastic and diagenetic lithologies should be apparent in side scan images. However, sonar also responds to variations in bottom slope, so unprocessed images mix topographic and lithologic information. We have processed GLORIA imagery from the Oregon continental margin to remove topographic effects. A synthetic side scan image was created initially from Sea Beam bathymetric data and then was subtracted iteratively from the original GLORIA data until topographic features disappeared. The residual image contains high-amplitude backscattering that we attribute to diagenetic deposits associated with fluid discharge, based on submersible mapping, Ocean Drilling Program drilling, and collected samples. Diagenetic deposits are concentrated (1) near an out-of-sequence thrust fault on the second ridge landward of the base of the continental slope, (2) along zones characterized by deep-seated strikeslip faults that cut transversely across the margin, and (3) in undeformed Cascadia Basin deposits which overlie incipient thrust faults seaward of the toe of the prism. There is no evidence of diagenetic deposition associated with the frontal thrust that rises from the dècollement. If the dècollement is an important aquifer, apparently the fluids are passed either to the strike-slip faults which intersect the dècollement or to the incipient faults in Cascadia Basin for expulsion. Diagenetic deposits seaward of the prism toe probably consist dominantly of gas hydrates.

Sulfobacillus thermosulfidooxidans strain Cutipay enhances chalcopyrite bioleaching under moderate thermophilic conditions in the presence of chloride ion.

PubMed

Bobadilla-Fazzini, Roberto A; Cortés, Maria Paz; Maass, Alejandro; Parada, Pilar

2014-12-01

Currently more than 90% of the world's copper is obtained through sulfide mineral processing. Among the copper sulfides, chalcopyrite is the most abundant and therefore economically relevant. However, primary copper sulfide bioleaching is restricted due to high ionic strength raffinate solutions and particularly chloride coming from the dissolution of ores. In this work we describe the chalcopyrite bioleaching capacity of Sulfobacillus thermosulfidooxidans strain Cutipay (DSM 27601) previously described at the genomic level (Travisany et al. (2012) Draft genome sequence of the Sulfobacillus thermosulfidooxidans Cutipay strain, an indigenous bacterium isolated from a naturally extreme mining environment in Northern Chile. J Bacteriol 194:6327-6328). Bioleaching assays with the mixotrophic strain Cutipay showed a strong increase in copper recovery from chalcopyrite concentrate at 50°C in the presence of chloride ion, a relevant inhibitory element present in copper bioleaching processes. Compared to the abiotic control and a test with Sulfobacillus acidophilus DSM 10332, strain Cutipay showed an increase of 42 and 69% in copper recovery, respectively, demonstrating its high potential for chalcopyrite bioleaching. Moreover, a genomic comparison highlights the presence of the 2-Haloacid dehalogenase predicted-protein related to a potential new mechanism of chloride resistance in acidophiles. This novel and industrially applicable strain is under patent application CL 2013-03335.

Diagenetic Iron Cycling in Ancient Alkaline Saline Lacustrine Sedimentary Rocks: A Case Study on the Jurassic Brushy Basin Member of the Morrison Formation, Colorado Plateau, USA

NASA Astrophysics Data System (ADS)

Potter-McIntyre, S. L.; Chan, M. A.; McPherson, B. J. O. L.

2014-12-01

The upper part of the Brushy Basin Member in the Four Corners region of the U.S. was deposited in an ephemeral alkaline saline lake system with copious input of volcanic ash. The variegated shale formation provides a setting for the study of early diagenetic iron cycling that records the action of alkaline saline fluid chemistries reacting with volcaniclastic sediments in the presence of microbes. A bull's-eye pattern of authigenic minerals with increasing alteration towards the basinal center similar to modern alkaline saline lakes provides evidence for an extreme paleoenvironmental interpretation. The purpose of this research is to document specific factors, such as reactive sediments, microbial influences, and grain size that affect concretion formation and iron cycling in an ancient extreme environment. Three broad diagenetic facies are interpreted by color and associated bioturbation features: red, green and intermediate. Diagenetic facies reflect meter-scale paleotopography: red facies represent shallow water to subaerial, oxidizing conditions; green facies reflect saturated conditions and reducing pore water chemistry shortly after deposition, and intermediate facies represent a combination of the previous two conditions. Evidence of biotic influence is abundant and trace fossils exhibit patterns associated with the diagenetic facies. Red diagenetic facies typically contain burrows and root traces and green diagenetic facies exhibit restricted biotic diversity typically limited to algal molds (vugs). Microbial fossils are well-preserved and are in close proximity to specific iron mineral textures suggesting biotic influence on the crystal morphology. Three categories of concretions are characterized based on mineralogy: carbonate, iron (oxyhydr)oxide and phosphate concretions. Concretion mineralogy and size vary within an outcrop and even within a stratigraphic horizon such that more than one main category is typically present in an outcrop. Variation in

A Moderately Thermophilic Mixed Microbial Culture for Bioleaching of Chalcopyrite Concentrate at High Pulp Density

PubMed Central

Wang, Yuguang; Zeng, Weimin; Qiu, Guanzhou; Chen, Xinhua

2014-01-01

Three kinds of samples (acid mine drainage, coal mine wastewater, and thermal spring) derived from different sites were collected in China. Thereafter, these samples were combined and then inoculated into a basal salts solution in which different substrates (ferrous sulfate, elemental sulfur, and chalcopyrite) served as energy sources. After that, the mixed cultures growing on different substrates were pooled equally, resulting in a final mixed culture. After being adapted to gradually increasing pulp densities of chalcopyrite concentrate by serial subculturing for more than 2 years, the final culture was able to efficiently leach the chalcopyrite at a pulp density of 20% (wt/vol). At that pulp density, the culture extracted 60.4% of copper from the chalcopyrite in 25 days. The bacterial and archaeal diversities during adaptation were analyzed by denaturing gradient gel electrophoresis and constructing clone libraries of the 16S rRNA gene. The results show that the culture consisted mainly of four species, including Leptospirillum ferriphilum, Acidithiobacillus caldus, Sulfobacillus acidophilus, and Ferroplasma thermophilum, before adapting to a pulp density of 4%. However, L. ferriphilum could not be detected when the pulp density was greater than 4%. Real-time quantitative PCR was employed to monitor the microbial dynamics during bioleaching at a pulp density of 20%. The results show that A. caldus was the predominant species in the initial stage, while S. acidophilus rather than A. caldus became the predominant species in the middle stage. F. thermophilum accounted for the greatest proportion in the final stage. PMID:24242252

Quantification of diagenetic overprint processes deduced from fossil carbonate shells and laboratory-based hydrothermal alteration experiments

NASA Astrophysics Data System (ADS)

Griesshaber, Erika; Casella, Laura; Mavromatis, Vasileios; Dietzel, Martin; Immenhauser, Adrian; Schmahl, Wolfgang

2016-04-01

Benthic and nektonic marine biogenic carbonate archives represent the foundation of numerous studies aiming at reconstructions of past climate dynamics and environmental change. However, living organisms are not in thermodynamic equilibrium and create local chemical environments where physiologic processes such as biomineralization takes place. After the death of the organism the former physiologic disequilibrium conditions are not sustained any more and all biological tissues are altered by equilibration according to the surrounding environment: diagenesis. With increasing diagenetic alteration, the biogenic structure and fingerprint fades away and is replaced by inorganic features. Thus, recrystallization of organism-specific microstructure is a clear indicator for diagenetic overprint. Microstructural data, which mirror recrystallization, are of great value for interpreting geochemical proxies for paleo-environment reconstruction. Despite more than a century of research dealing with carbonate diagenesis, many of the controlling processes and factors are only understood in a qualitative manner. One of the main issues is that diagenetically altered carbonates are usually present as the product of a complex preceding diagenetic pathway with an unknown number of intermediate steps. In this contribution we present and discuss laboratory based alteration experiments with the aim to investigate time-series data sets in a controlled manner. We conducted hydrothermal alteration experiments with modern Arctica islandica (bivalvia) and Notosaria nigricans (brachiopoda) in order to mimic diagenetic overprint. We explore first the potential of electron backscattered diffraction (EBSD) measurements together with statistical data evaluation as a tool to quantify diagenetic alteration of carbonate skeletons. Subsequently, we compare microstructural patterns obtained from experimentally altered shell material with those of fossil specimens that have undergone variable degrees of

Giant calcite concretions in aeolian dune sandstones; sedimentological and architectural controls on diagenetic heterogeneity, mid-Cretaceous Iberian Desert System, Spain

NASA Astrophysics Data System (ADS)

Arribas, Maria Eugenia; Rodríguez-López, Juan Pedro; Meléndez, Nieves; Soria, Ana Rosa; de Boer, Poppe L.

2012-01-01

Aeolian dune sandstones of the Iberian erg system (Cretaceous, Spain) host giant calcite concretions that constitute heterogeneities of diagenetic origin within a potential aeolian reservoir. The giant calcite concretions developed in large-scale aeolian dune foresets, at the transition between aeolian dune toeset and damp interdune elements, and in medium-scale superimposed aeolian dune sets. The chemical composition of the giant concretions is very homogeneous. They formed during early burial by low Mg-calcite precipitation from meteoric pore waters. Carbonate components with yellow/orange luminescence form the nuclei of the poikilotopic calcite cement. These cements postdate earlier diagenetic features, characterized by early mechanical compaction, Fe-oxide cements and clay rims around windblown quartz grains resulting from the redistribution of aeolian dust over the grain surfaces. The intergranular volume (IGV) in friable aeolian sandstone ranges from 7.3 to 15.3%, whereas in cemented aeolian sandstone it is 18.6 to 25.3%. The giant-calcite concretions developed during early diagenesis under the influence of meteoric waters associated with the groundwater flow of the desert basin, although local (e.g. activity of fluid flow through extensional faults) and/or other regional controls (e.g. variations of the phreatic level associated with a variable water influx to the erg system and varying sea level) could have favoured the local development of giant-calcite concretions. The spatial distribution pattern of carbonate grains and the main bounding surfaces determined the spatial distribution of the concretions. In particular, the geometry of the giant calcite concretions is closely associated with main bounding aeolian surfaces. Thus, interdune, superimposition and reactivation surfaces exerted a control on the concretion geometries ranging from flat and tabular ones (e.g. bounded by interdunes) to wedge-shaped concretions at the dune foresets (e.g. bounded by

Structural and diagenetic evolution of deformation bands in contractional and extensional tectonic regimes

NASA Astrophysics Data System (ADS)

Eichhubl, P.; O'Brien, C. M.; Elliott, S. J.

2016-12-01

Mechanisms of brittle deformation of sediments and sedimentary rock change with burial because of increasing confining stress, change in pore fluid chemical and temperature conditions, and diagenetic state. In the field, these changes are observed in a transition from early non-cataclastic to later cataclastic deformation bands and to joint-based structures. Jurassic eolian sandstones in the San Rafael monocline and adjacent San Rafael Desert region, Utah, allow comparison of deformation band structures and their diagenetic attributes in contractional and extensional tectonic settings in close proximity. In the Entrada and Navajo Sandstones, we observe up to six generations of deformation bands, with earliest non-cataclastic bands having diffuse boundaries to host rock, and short and irregular traces. Later bands are cataclastic, more sharply defined, with long and straight traces. Cataclastic bands in the San Rafael monocline are interpreted to form as reverse faults during progressive rotation of the steeply dipping fold limb, resulting in an array of bands of varying dip. Bands in the San Rafael Desert form as normal faults with a narrower dip range. Although structural characteristics of bands differ in extensional and contractional tectonic regimes, cataclastic bands in either regime have comparable amount of porosity loss and quartz cementation indicating that tectonic regime does not influence band diagenesis. Abundance of quartz cement in bands, determined by point counting of SEM images, increases from earlier to later generations of bands and, within a single generation, with increasing slip along the band, reaching up to 24% of band volume. This trend is attributed to an increase in cataclasis with increasing host rock cementation and confining stress during burial, and, within the same generation, with increasing slip. Porosity loss by cementation tends to dominate over porosity loss by mechanical compaction. These findings demonstrate that quartz

Short communication: Adverse effect of surface-active reagents on the bioleaching of pyrite and chalcopyrite by Thiobacillus ferrooxidans.

PubMed

Huerta, G; Escobar, B; Rubio, J; Badilla-Ohlbaum, R

1995-09-01

Oxidation of Fe(II) iron and bioleaching of pyrite and chalcopyrite by Thiobacillus ferrooxidans was adversely affected by isopropylxanthate, a flotation agent, and by LIX 984, a solvent-extraction agent, each at ≤ 1 g/l. The reagents/l were adsorbed on the bacterial surface, decreasing the bacteria's development and preventing biooxidation. Both reagents inhibited the bioleaching of pyrite and LIX 984 also inhibited the bioleaching of chalcopyrite.

Early diagenetic processes of saline meromictic Lake Kai-ike, southwest Japan: III. Sulfur speciation and isotopes

NASA Astrophysics Data System (ADS)

Sakai, N.; Yamaguchi, K. E.; Oguri, K.

2014-12-01

., 2010; Palaeo3). Geochemical characteristics of sulfur in the uppermost part of Lake Kai-ike sediment were significantly modified during early diagenesis. Such diagenetic modification for sulfur isotopes should be fully taken into account to better reconstruct past anoxic environment such as Cretaceous OAEs and Archean oceans.

Local Bonding Influence on the Band Edge and Band Gap Formation in Quaternary Chalcopyrites.

PubMed

Miglio, Anna; Heinrich, Christophe P; Tremel, Wolfgang; Hautier, Geoffroy; Zeier, Wolfgang G

2017-09-01

Quaternary chalcopyrites have shown to exhibit tunable band gaps with changing anion composition. Inspired by these observations, the underlying structural and electronic considerations are investigated using a combination of experimentally obtained structural data, molecular orbital considerations, and density functional theory. Within the solid solution Cu 2 ZnGeS 4- x Se x , the anion bond alteration parameter changes, showing larger bond lengths for metal-selenium than for metal-sulfur bonds. The changing bonding interaction directly influences the valence and conduction band edges, which result from antibonding Cu-anion and Ge-anion interactions, respectively. The knowledge of the underlying bonding interactions at the band edges can help design properties of these quaternary chalcopyrites for photovoltaic and thermoelectric applications.

What do we really know about early diagenesis of non-marine carbonates?

NASA Astrophysics Data System (ADS)

De Boever, Eva; Brasier, Alexander T.; Foubert, Anneleen; Kele, Sándor

2017-11-01

Non-marine carbonate rocks including cave, spring, stream, calcrete and lacustrine-palustrine sediments, are susceptible to early diagenetic processes. These can profoundly alter the carbonate fabric and affect paleoclimatic proxies. This review integrates recent insights into diagenesis of non-marine carbonates and in particular the variety of early diagenetic processes, and presents a conceptual framework to address them. With ability to study at smaller and smaller scales, down to nanometers, one can now observe diagenesis taking place the moment initial precipitates have formed, and continuing thereafter. Diagenesis may affect whole rocks, but it typically starts in nano- and micro-environments. The potential for diagenetic alteration depends on the reactivity of the initial precipitate, commonly being metastable phases like vaterite, Ca-oxalates, hydrous Mg-carbonates and aragonite with regard to the ambient fluid. Furthermore, organic compounds commonly play a crucial role in hosting these early transformations. Processes like neomorphism (inversion and recrystallization), cementation and replacement generally result in an overall coarsening of the fabric and homogenization of the wide range of complex, primary microtextures. If early diagenetic modifications are completed in a short time span compared to the (annual to millennial) time scale of interest, then recorded paleoenvironmental signals and trends could still acceptably reflect original, depositional conditions. However, even compact, non-marine carbonate deposits may behave locally and temporarily as open systems to crystal-fluid exchange and overprinting of one or more geochemical proxies is not unexpected. Looking to the future, relatively few studies have examined the behaviour of promising geochemical records, such as clumped isotope thermometry and (non-conventional) stable isotopes, in well-constrained diagenetic settings. Ongoing and future in-vitro and in-situ experimental approaches will

Insights into the diagenetic environment of fossil marine vertebrates of the Pisco Formation (late Miocene, Peru) from mineralogical and Sr-isotope data

NASA Astrophysics Data System (ADS)

Gioncada, A.; Petrini, R.; Bosio, G.; Gariboldi, K.; Collareta, A.; Malinverno, E.; Bonaccorsi, E.; Di Celma, C.; Pasero, M.; Urbina, M.; Bianucci, G.

2018-01-01

The late Miocene Pisco Formation of Peru is an outstanding example of richness and high-quality preservation of fossil marine vertebrates. In order to reconstruct the fossilization path, we present new textural, mineralogical and Sr-isotope data of diagenetic minerals formed in correspondence of fossil specimens such as marine vertebrates and mollusks. These fossil specimens were found at Cerro los Quesos, in the Ica Desert, within the diatomaceous strata of the Pisco Formation. Dolomite, gypsum, anhydrite and Mn minerals are the main phases found, while the calcium carbonate originally forming the mollusk valves is replaced by gypsum. An early formation of dolomite and of Mn minerals, triggered by the modifications of the geochemical environment due to organic matter degradation, is suggested by the textural relationships and is confirmed by the Sr isotopic ratio of dolomite, which agrees with that of seawater at the time of sedimentation. Instead, gypsum Sr isotopic ratios indicate a pre-Miocene seawater-derived brine circulating within the sedimentary sequence as a source for Sr. Oxidation of diagenetic sulfide causing a lowering of the pH of porewater is proposed as an explanation for Ca-carbonate dissolution. The diagenetic chemical environment was, nevertheless, favorable to bone preservation.

Raman hyperspectral imaging as an effective and highly informative tool to study the diagenetic alteration of fossil bones.

PubMed

Dal Sasso, Gregorio; Angelini, Ivana; Maritan, Lara; Artioli, Gilberto

2018-03-01

Retrieving the pristine chemical or isotopic composition of archaeological bones is of great interest for many studies aiming to reconstruct the past life of ancient populations (i.e. diet, mobility, palaeoenvironment, age). However, from the death of the individual onwards, bones undergo several taphonomic and diagenetic processes that cause the alteration of their microstructure and composition. A detailed study on bone diagenesis has the double purpose to assess the preservation state of archaeological bones and to understand the alteration pathways, thus providing evidence that may contribute to evaluate the reliability of the retrieved information. On these bases, this research aims to explore the effectiveness of Raman hyperspectral imaging to detect types, extent and spatial distribution of diagenetic alteration at the micro-scale level. An early-Holocene bone sample from the Al Khiday cemetery (Khartoum, Sudan) was here analysed. Parameters related to the collagen content, bioapatite crystallinity and structural carbonate content, and to the occurrence of secondary mineral phases were calculated from Raman spectra. The acquired data provided spatially-resolved information on both the preservation state of bone constituents and the diagenetic processes occurring during burial. Given the minimal sample preparation, the easy and fast data acquisition and the improvement of system configurations, micro-Raman spectroscopy can be extensively applied as a screening method on a large set of samples in order to characterise the preservation state of archaeological bones. This technique can be effectively applied to identify suitable and well preserved portions of the analysed sample on which perform further analyses. Copyright © 2017 Elsevier B.V. All rights reserved.

Hg concentrations from Late Triassic and Early Jurassic sedimentary rocks: first order similarities and second order depositional and diagenetic controls

NASA Astrophysics Data System (ADS)

Yager, J. A.; West, A. J.; Bergquist, B. A.; Thibodeau, A. M.; Corsetti, F. A.; Berelson, W.; Bottjer, D. J.; Rosas, S.

2016-12-01

Mercury concentrations in sediments have recently gained prominence as a potential tool for identifying large igneous province (LIP) volcanism in sedimentary records. LIP volcanism coincides with several mass extinctions during the Phanerozoic, but it is often difficult to directly tie LIP activity with the record of extinction in marine successions. Here, we build on mercury concentration data reported by Thibodeau et al. (Nature Communications, 7:11147, 2016) from the Late Triassic and Early Jurassic of New York Canyon, Nevada, USA. Increases in Hg concentrations in that record were attributed to Central Atlantic Magmatic Province (CAMP) activity in association with the end-Triassic mass extinction. We expand the measured section from New York Canyon and report new mercury concentrations from Levanto, Peru, where dated ash beds provide a discrete chronology, as well as St. Audrie's Bay, UK, a well-studied succession. We correlate these records using carbon isotopes and ammonites and find similarities in the onset of elevated Hg concentrations and Hg/TOC in association with changes in C isotopes. We also find second order patterns that differ between sections and may have depositional and diagenetic controls. We will discuss these changes within a sedimentological framework to further understand the controls on Hg concentrations in sedimentary records and their implications for past volcanism.

Dynamic depositional and early diagenetic processes in a deep-water shelf setting, upper cretaceous Austin Chalk, North Texas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hovorka, S.D.; Nance, H.S.

1994-12-31

The Austin Chalk of north Texas was deposited on a deep-water shelf north of the Sea Marcos Platform during a worldwide Coniacian and Santonian sea-level highstand. Transgressive (lowermost lower Austin Chalk), highstand (uppermost lower Austin Chalk), and regressive (middle and upper Austin Chalk) phases of cyclic chalk and marl sedimentation are recognized in excavations and tunnels created in Ellis County for the Superconducting Super Collider provide new evidence of sediment transport during Austin Chalk deposition. During transgression, bottom currents syndepositionally reworked nannoplankton oozes, incising channels as much as 120 ft across and 8 ft deep. Weakly burrowed channel fills havingmore » preservation of fine lamination document rapid infilling. Channel fills are composed of pyritized and carbonized wood and Inoceramus lag deposits, pellets, echinoderm fragments, and globigerinid grainstones, and coccolith ooze. During maximum highstand, bottom reworking was suppressed. Detrital content of highstand marls is low (>20 percent); organic content is high (1.4 to 3.5 percent). Coccolith preservation is excellent because of minimal diagenetic alteration. Regression is marked by resumed channel cutting and storm-bed winnowing in the middle and upper Austin Chalk. Suppressed resistivity log response and recessive weathering characteristics of the middle Austin Chalk are not primarily related to depositional environment but rather to increased input of volcanic ash during the accumulation of this interval. Early stabilization of ash produced clay-coated microfabrics in sediments that are otherwise similar to the transgressive deposits.« less

Isolation and characterization of Ferroplasma thermophilum sp. nov., a novel extremely acidophilic, moderately thermophilic archaeon and its role in bioleaching of chalcopyrite.

PubMed

Zhou, H; Zhang, R; Hu, P; Zeng, W; Xie, Y; Wu, C; Qiu, G

2008-08-01

To isolate Ferroplasma thermophilum L1(T) from a low pH environment and to understand its role in bioleaching of chalcopyrite. Using serial dilution method, a moderately thermophilic and acidophilic ferrous iron-oxidizing archaeon, named L1(T), was isolated from a chalcopyrite-leaching bioreactor. The morphological, biochemical and physiological characteristics of strain L1(T) and its role in bioleaching of chalcopyrite were studied. Strain L1(T) was a nonmotile coccus that lacked cell wall. Strain L1(T) had a temperature optimum of 45 degrees C and the optimum pH for growth was 1.0. Strain L1(T) was capable of chemomixotrophic growth on ferrous iron and yeast extract. Results of fatty acid analysis, DNA-DNA hybridization, G+C content, and analysis based on 16S rRNA gene sequence indicated that strain L1(T) should be grouped in the genus Ferroplasma, and represented a new species, Ferroplasma thermophilum. Ferroplasma thermophilum in combination with Acidithiobacillus caldus and Leptospirillum ferriphilum could improve the copper dissolution in bioleaching of chalcopyrite. A novel extremely acidophilic, moderately thermophilic archaeon isolated from a bioleaching reactor has been identified as F. thermophilum that played an important role in bioleaching of chalcopyrite at low pH. This study contributes to understand the characteristics of F. thermophilum L1(T) and its role in bioleaching of sulfide ores.

Sedimentological and diagenetic patterns of anhydrite deposits in the Badenian evaporite basin of the Carpathian Foredeep, southern Poland

NASA Astrophysics Data System (ADS)

Kasprzyk, Alicja

2003-05-01

Anhydrite deposits are widely distributed in the Middle Miocene Badenian evaporite basin of Poland, including the marginal sulphate platform and adjacent salt depocenter. Particular sedimentological, petrographic and geochemical characteristics of these anhydrite deposits and especially common pseudomorphic features, inherited from the precursor gypsum deposits, allow the interpretation of the original sedimentary facies. The observed facies distribution and succession (lower and upper members) reveal three distinct facies associations that record a range of depositional environments from nearshore to deeper basinal settings. Platform sulphates were deposited in subaerial and shallow-marine environments (shoreline and inner platform-lagoon system) mainly as autochthonous selenitic gypsum. This was reworked and redistributed into deeper waters (outer platform-lagoon, slope and the proximal basin floor system) to form resedimented facies composed mostly of allochthonous clastic gypsum and minor anhydrite. The general variation in petrographic and geochemical compositions of anhydrite lithofacies of the lower and upper members reflects the brine evolution, as the result of interactions between seawater, meteoric runoff and highly saline, residual pore fluids. The results indicate the importance of synsedimentary and diagenetic anhydritisation processes in formation of the Badenian anhydrite lithofacies, all of which preserve the original depositional features of the former gypsum. This also applies to the basinal anhydrite previously interpreted to have a depositional genesis. Two different genetic patterns of anhydrite have been reinforced by this study: (1) synsedimentary anhydritisation of gypsum deposits by highly concentrated brines or elevated temperatures in surficial to shallow-burial environments (lower member), and (2) successive phases (syndepositional de novo growth, early diagenetic to late diagenetic replacement of former gypsum) of anhydrite formation

Insights to the effects of free cells on community structure of attached cells and chalcopyrite bioleaching during different stages.

PubMed

Feng, Shoushuai; Yang, Hailin; Wang, Wu

2016-01-01

The effects of free cells on community structure of attached cells and chalcopyrite bioleaching by Acidithiobacillus sp. during different stages were investigated. The attached cells of Acidithiobacillus thiooxidans owned the community advantage from 14thd to the end of bioprocess in the normal system. The community structure of attached cells was greatly influenced in the free cells-deficient systems. Compared to A. thiooxidans, the attached cells community of Acidithiobacillus ferrooxidans had a higher dependence on its free cells. Meanwhile, the analysis of key biochemical parameters revealed that the effects of free cells on chalcopyrite bioleaching in different stages were diverse, ranging from 32.8% to 64.3%. The bioleaching contribution of free cells of A. ferrooxidans in the stationary stage (8-14thd) was higher than those of A. thiooxidans, while the situation was gradually reversed in the jarosite passivation inhibited stage (26-40thd). These results may be useful in guiding chalcopyrite bioleaching. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nanocrystalline Chalcopyrite Materials (CuInS2 and CuInSe2) via Low-Temperature Pyrolysis of Molecular Single-Source Precursors

NASA Technical Reports Server (NTRS)

Castro, Stephanie L.; Bailey, Sheila G.; Raffaelle, Ryne P.; Banger, Kulbinder K.; Hepp, Aloysius F.

2003-01-01

Nanometer sized particles of the chalcopyrite compounds CuInS2 and CuInSe2 were synthesized by thermal decomposition of molecular single-source precursors (PPh3)2CuIn(SEt)4 and (PPh3)2CuIn(SePh)4, respectively, in the non-coordinating solvent dioctyl phthalate at temperatures between 200 and 300 C. The nanoparticles range in size from 3 - 30 nm and are aggregated to form roughly spherical clusters of about 500 nm in diameter. X-ray diffraction of the nanoparticle powders shows greatly broadened lines indicative of very small particle sizes, which is confirmed by TEM. Peaks present in the XRD can be indexed to reference patterns for the respective chalcopyrite compounds. Optical spectroscopy and elemental analysis by energy dispersive spectroscopy support the identification of the nanoparticles as chalcopyrites.

Selective excitation of window and buffer layers in chalcopyrite devices and modules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glynn, Stephen; Repins, Ingrid L.; Burst, James M.

Window and buffer layers in chalcopyrite devices are well known to affect junctions, conduction, and photo-absorption properties of the device. Some of these layers, particularly 'buffers,' which are deposited directly on top of the absorber, exhibit metastable effects upon exposure to light. Thus, to understand device performance and/or metastability, it is sometimes desirable to selectively excite different layers in the device stack. Absorption characteristics of various window and buffer layers used in chalcopyrite devices are measured. These characteristics are compared with emission spectra of common and available light sources that might be used to optically excite such layers. Effects ofmore » the window and buffer absorption on device quantum efficiency and metastability are discussed. For the case of bath-deposited Zn(O,S) buffers, we conclude that this layer is not optically excited in research devices or modules. Furthermore, this provides a complimentary mechanism to the chemical differences that may cause long time constants (compared to devices with CdS buffers) associated with reaching a stable 'light-soaked' state.« less

Selective excitation of window and buffer layers in chalcopyrite devices and modules

DOE PAGES

Glynn, Stephen; Repins, Ingrid L.; Burst, James M.; ...

2018-02-02

Window and buffer layers in chalcopyrite devices are well known to affect junctions, conduction, and photo-absorption properties of the device. Some of these layers, particularly 'buffers,' which are deposited directly on top of the absorber, exhibit metastable effects upon exposure to light. Thus, to understand device performance and/or metastability, it is sometimes desirable to selectively excite different layers in the device stack. Absorption characteristics of various window and buffer layers used in chalcopyrite devices are measured. These characteristics are compared with emission spectra of common and available light sources that might be used to optically excite such layers. Effects ofmore » the window and buffer absorption on device quantum efficiency and metastability are discussed. For the case of bath-deposited Zn(O,S) buffers, we conclude that this layer is not optically excited in research devices or modules. Furthermore, this provides a complimentary mechanism to the chemical differences that may cause long time constants (compared to devices with CdS buffers) associated with reaching a stable 'light-soaked' state.« less

Effect of pH values on the extracellular polysaccharide secreted by Acidithiobacillus ferrooxidans during chalcopyrite bioleaching

NASA Astrophysics Data System (ADS)

Yu, Run-lan; Liu, Jing; Tan, Jian-xi; Zeng, Wei-min; Shi, Li-juan; Gu, Guo-hua; Qin, Wen-qing; Qiu, Guan-zhou

2014-04-01

The pH value plays an important role in the bioleaching of sulphide minerals. The effect of pH values on the extracellular polysaccharide secreted by Acidithiobacillus ferrooxidans was investigated in different phases of bacterial growth during chalcopyrite bioleaching. It is found that extracellular polysaccharide secretion from the cells attached to chalcopyrite is more efficiently than that of the free cells in the bioleaching solution. Three factors, pH values, the concentration of soluble metal ions, and the bacterial growth and metabolism, affect extracellular polysaccharide secretion in the free cells, and are related to the bacterial growth phase. Extracellular polysaccharide secretion from the attached cells is mainly dependent on the pH value of the bacterial culture.

Remote detection of fluid-related diagenetic mineralogical variations in the Wingate Sandstone at different spatial and spectral resolutions

NASA Astrophysics Data System (ADS)

Okyay, Unal; Khan, Shuhab D.

2016-02-01

Well-exposed eolian units of the Jurassic system on the Colorado Plateau including the Wingate Sandstone, show prominent color variations throughout southeastern Utah due to diagenetic changes that include precipitation and/or removal of iron oxide, clay, and carbonate cement. Spatially variable characteristic diagenetic changes suggest fluid-rock interactions through the sandstone. Distinctive spectral signatures of diagenetic minerals can be used to map diagenetic mineral variability and possibly fluid-flow pathways. The main objective of this work was to identify characteristic diagenetic minerals, and map their spatial variability from regional to outcrop scale in Wingate Sandstone exposures of Lisbon Valley, Utah. Laboratory reflectance spectroscopy analysis of the samples facilitated identification of diagnostic spectral characteristics of the common diagenetic minerals and their relative abundances between altered and unaltered Wingate Sandstone. Comparison of reflectance spectroscopy with satellite, airborne, and ground-based imaging spectroscopy data provided a method for mapping and evaluating spatial variations of diagenetic minerals. The Feature-oriented Principal Component Selection method was used on Advanced Spaceborne Thermal Emission and Reflection Radiometer data so as to map common mineral groups throughout the broader Wingate Sandstone exposure in the area. The Minimum Noise Fraction and Spectral Angle Mapper methods were applied on airborne HyMap and ground-based hyperspectral imaging data to identify and map mineralogical changes. The satellite and airborne data showed that out of 25.55 km2 total exposure of Wingate Sandstone in Lisbon Valley, unaltered sandstone cover 12.55 km2, and altered sandstone cover 8.90 km2 in the northwest flank and 5.09 km2 in the southern flank of the anticline. The ground-based hyperspectral data demonstrated the ability to identify and map mineral assemblages with two-dimensional lateral continuity on near

The diagenetic fate of taraxer-14-ene and oleanene isomers

NASA Astrophysics Data System (ADS)

ten Haven, H. L.; Rullkötter, J.

1988-10-01

The extractable organic matter in Holocene to early Miocene deep-sea sediments from Site 645 (ODP Leg 105) in Baffin Bay contains almost exclusively biological markers of terrigenous origin. Pentacyclic triterpenoids of the α-(ursene) and β-amyrin (oleanene) type often occur as the most abundant compounds in the aliphatic hydrocarbon, ketone and alcohol fractions of the sediment extract. A specific diagenetic reaction involves the conversion of taraxer-14-ene into olean-12-ene in the upper 700 metres of the sedimentary sequence. The taraxerene-to-oleanene conversion is complete before the onset of isomerisation of diasterenes at C-20. In the sediment as well as in laboratory simulation experiments, olean-12-ene further isomerises to olean-13(18)-ene and olean-18-ene, the latter of which may be the direct precursor of 18β(H)- and 18α(H)-oleanane found in sediments containing more mature organic matter and in crude oils. The subsurface interconversion of these triterpenoid skeletons indicate that oleanane does not necessarily start life as an oleanoid.

Hydrothermal and Diagenetic Mineralization on Mars

NASA Astrophysics Data System (ADS)

Ehlmann, B. L.; Quinn, D. P.

2015-12-01

Predicted by geophysical modeling, the mineraolgic record of early Mars groundwater has only recently been discovered. First, rover exploration in sedimentary basins reveals diagenesis. At Meridiani, sandstone porosity is occluded by precipitation of secondary sulfates, hematite, and silica. Multiple alteration episodes are indicated by crystal vugs, disruption of preexisting textures by hematite concretions, and grain coatings (e.g. McLennan et al., 2005). At Gale crater, raised ridges in mudstones, interpreted to be early diagenetic features, are crossed by later-emplaced hydrated calcium sulfate veins (e.g. Grotzinger et al., 2014). Waters in Gale were likely circumneutral while jarosite mineralogy at Meridiani implies acidic waters. Second, systems of raised ridges at 100-m scale are observed from orbit in multiple Martian sedimentary rock units. An outstanding example is sulfate-bearing sediments exhumed at the northern margin of the Syrtis Major lavas (e.g. Quinn & Ehlmann, 2015). Polygonal and with no clearly preferred orientation, the ridges rise 5-30 m above the surrounding terrain. Parallel light-toned grooves with dark interiors (indicative of isopachous fills) and jarosite in ridge mineralogy point to mineralization by acidic waters. Third, some mineral assemblages observed from orbit represent the products of subsurface aqueous alteration at elevated temperatures (Ehlmann et al., 2011). These are globally distributed, exposed in scarps and by impact cratering. Mineral assemblages variously include (a) serpentine and carbonate; (b) prehnite and chlorite, and (c) zeolites. Collectively, these datasets indicate that groundwaters were spatially widespread on ancient Mars, contributing to the sustenance of lakes and to the alteration of bedrock to >1 km depths. While the Martian surface may have always been relatively inhospitable, a warmer, wetter subsurface provided a long-term potentially habitable environment. Key outstanding questions remaining include

Compaction bands in high temperature/pressure diagenetically altered unconventional shale gas reservoirs

NASA Astrophysics Data System (ADS)

Regenauer-Lieb, K.; Veveakis, M.; Poulet, T.

2014-12-01

Unconventional energy and mineral resources are typically trapped in a low porosity/permeability environment and are difficult to produce. An extreme end-member is the shale gas reservoir in the Cooper Basin (Australia) that is located at 3500-4000 m depth and ambient temperature conditions around 200oC. Shales of lacustrine origin (with high clay content) are diagenetically altered. Diagenesis involves fluid release mineral reactions of the general type Asolid ↔ Bsolid +Cfluid and switches on suddenly in the diagenetic window between 100-200oC. Diagenetic reactions can involve concentrations of smectite, aqueous silica compound, illite, potassium ions, aqueous silica, quartz, feldspar, kerogen, water and gas . In classical petroleum engineering such interlayer water/gas release reactions are considered to cause cementation and significantly reduce porosity and permeability. Yet in contradiction to the expected permeability reduction gas is successfully being produced. We propose that the success is based on the ductile equivalent of classical compaction bands in solid mechanics. The difference being that that the rate of the volumetric compaction is controlled by the diagenetic reactions. Ductile compaction bands are forming high porosity fluid channels rather than low porosity crushed grains in the solid mechanical equivalent. We show that this new type of volumetric instability appears in rate-dependent heterogenous materials as Cnoidal waves. These are nonlinear and exact periodic stationary waves, well known in the shallow water theory of fluid mechanics. Their distance is a direct function of the hydromechanical diffusivities. These instabilities only emerge in low permeability environment where the fluid diffusivity is about an order of magnitude lower than the mechanical loading. The instabilities are expected to be of the type as shown in the image below. The image shows a CT-scan of a laboratory experiment kindly provided by Papamichos (pers

Electrochemical and spectroscopic study of interfacial interactions between chalcopyrite and typical flotation process reagents

NASA Astrophysics Data System (ADS)

Urbano, Gustavo; Lázaro, Isabel; Rodríguez, Israel; Reyes, Juan Luis; Larios, Roxana; Cruz, Roel

2016-02-01

Comparative voltammetry and differential double-layer capacitance studies were performed to evaluate interfacial interactions between chalcopyrite (CuFeS2) and n-isopropyl xanthate (X) in the presence of ammonium bisulfite/39wt% SO2 and caustic starch at different pH values. Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, contact angle measurements, and microflotation tests were used to establish the type and extent of xanthate adsorption as well as the species involved under different mineral surface conditions in this study. The results demonstrate that the species that favor a greater hydrophobicity of chalcopyrite are primarily CuX and S0, whereas oxides and hydroxides of Cu and Fe as well as an excess of starch decrease the hydrophobicity. A conditioning of the mineral surface with ammonium bisulfite/39wt% SO2 at pH 6 promotes the activation of surface and enhances the xanthate adsorption. However, this effect is diminished at pH ≥ 8, when an excess of starch is added during the preconditioning step.

Ionic liquids for metal extraction from chalcopyrite: solid, liquid and gas phase studies.

PubMed

Kuzmina, O; Symianakis, E; Godfrey, D; Albrecht, T; Welton, T

2017-08-16

We studied leaching of Cu and Fe from naturally occurring chalcopyrite ore using aqueous solutions of ionic liquids (ILs) based on imidazolium and ethylammonium cations and hydrogensulfate, nitrate, acetate or dicyanamide anions. Liquid, solid and gas phases of the leaching systems were characterised. We have shown that nonoxidative leaching is greatly dependant not only on temperature and pH, but on the anion species of the IL. Solutions of 1-butylimidazolium hydrogen sulfate exhibited the best leaching performance among hydrogen sulphate ILs. We have suggested that the formation of an oxide layer in some ILs may be responsible for a reduced leaching ability. The analysis of the gas phase showed the production of CO 2 and CS 2 in all leached samples. Our results suggested that the CS 2 produced upon leaching could be responsible for decreasing the sulfur, but not oxide, layer on the surface of chalcopyrite samples and therefore more efficient leaching. This is the first study, to our knowledge, to provide a systematic comparison of the leaching performance of ILs composed of different anions and cations and without added oxidants.

Presentation on mechanisms and applications of chalcopyrite and pyrite bioleaching in biohydrometallurgy - a presentation.

PubMed

Tao, Huang; Dongwei, Li

2014-12-01

This review outlines classic and current research, scientific documents and research achievements in bioleaching, particularly in respect of the bioleaching of chalcopyrite and pyrite. The diversity and commonality of the microbial leaching process can be easily studied through comparing the bioleaching mechanism and the application of these two metal sulfides. The crystal, electronic and surface structures of chalcopyrite and pyrite are summarized in detail in this paper. It determines the specific and complicated interaction pathways, kinetics of the atmospheric/aqueous oxidation, and the control process of bioleaching of the minerals as the precondition. Bioleaching of metal sulfides is performed by a diverse group of microorganisms and microbial communities. The species of the bacteria which have a significant effect on leaching ores are miraculously diverse. The newly identified acidophilic microorganisms with unique characteristics for efficient bioleaching of sulfidic minerals are increasing sharply. The cell-to-cell communication mechanisms, which are still implicit, elusive and intangible at present day, have gradually become a research hotspot. The different mineralogy characteristics and the acid solubility of the metal sulfides (e.g., chalcopyrite and pyrite) cause two different dissolution pathways, the thiosulfate and the polysulfide pathways. The bioleaching mechanisms are categorized by contact (an electrostatic attachment) and noncontact (planktonic) process, with emphasis on the produce of extracellular polymeric substances and formation of biofilm on the surface of the metal sulfides in this paper. The division of the direct and indirect effect are not adopted due to the redox chain, the reduction of the ferric iron and oxidation of the ferrous iron. The molecular oxygen is reduced by the electrons extracted from the specific metal sulfide, via a redox chain forming a supercomplex spanning the periplasmic space and connecting both outer and inner

Full potential calculations on the electron bandstructures of Sphalerite, Pyrite and Chalcopyrite

NASA Astrophysics Data System (ADS)

Edelbro, R.; Sandström, Å.; Paul, J.

2003-02-01

The bulk electronic structures of Sphalerite, Pyrite and Chalcopyrite have been calculated within an ab initio, full potential, density functional approach. The exchange term was approximated with the Dirac exchange functional, the Vosko-Wilk-Nusair parameterization of the Cepler-Alder free electron gas was used for correlation and linear combinations of Gaussian type orbitals were used as basis functions. The Sphalerite (zinc blende) band gap was calculated to be direct with a width of 2.23 eV. The Sphalerite valence band was 5.2 eV wide and composed of a mixture of sulfur and zinc orbitals. The band below the valence band located around -6.2 eV was mainly composed of Zn 3d orbitals. The S 3s orbitals gave rise to a band located around -12.3 eV. Pyrite was calculated to be a semiconductor with an indirect band gap of 0.51 eV, and a direct gap of 0.55 eV. The valence band was 1.25 eV wide and mainly composed of non-bonding Fe 3d orbitals. The band below the valence band was 4.9 eV wide and composed of a mixture of sulfur and iron orbitals. Due to the short inter-atomic distance between the sulfur dumbbells, the S 3s orbitals in Pyrite were split into a bonding and an anti-bonding range. Chalcopyrite was predicted to be a conductor, with no band-crossings at the Fermi level. The bands at -13.2 eV originate from the sulfur 3s orbitals and were quite similar to the sulfur 3s bands in Sphalerite, though somewhat shifted to lower energy. The top of the valence band consisted of a mixture of orbitals from all the atoms. The lower part of the same band showed metal character. Computational modeling as a tool for illuminating the flotation and leaching processes of Pyrite and Chalcopyrite, in connection with surface science experiments, is discussed.

An ore genetic model for the Lubin—Sieroszowice mining district, Poland

NASA Astrophysics Data System (ADS)

Wodzicki, A.; Piestrzyński, A.

1994-04-01

The Lubin-Sieroszowice mining district is a world-class copper-silver, stratabound ore deposit that lies near the Lower-Upper Permian boundary. It transgresses the Werra dolomite, the Kupferschiefer organicrich shale and the Weissliegendes sandstone, which overlie barren Rotliegendes sandstone. On the basis of underground and microscope observations and light stable isotope data, and thermodynamic calculations, a new ore genesis model is proposed whereby ore minerals were deposited in the following stages: Stage 0 was synsedimentary or earliest diagenetic and contains 100s ppm of base metals trapped by clay minerals, and minor sulphides. Stage I was early diagenetic and contains 1000s ppm base metals. It is characterized by bornite and overlying chalcopyrite + pyrite that lie a short distance above the Rotliegendes/Weissliegendes contact. The sulphides were deposited near the interface between an overlying, buffered, reducing fluid (1), largely derived from the Kupferschiefer, and an oxidizing fluid (2) in the Rotliegendes. Stage II is the main ore-forming stage. This stage is late diagenetic, peneconcordant, lies near the Kupferschiefer/Weissliegendes contact, and contains several percent base metals.It is associated with the hematite-bearing Rote Fäule facies and is characterized by vertical zonation. A central chalcocite zone is flanked above and below by bornite and chalcopyrite. Silver occurs with all the above sulphides. Galena and sphalerite occur mainly just above copper zone, whereas pyrite is usually present in the upper part of the copper zone and together with galena and sphalerite. Metals were transported in a copper-rich oxidizing fluid (3), which probably originated deep in the Permian basin, reacted with organic matter in the Kupferschiefer, and mixed with reducing fluid (1) in the Weissliegendes, resulting in the observed mineral zonation. Stage III is late diagenetic, discordant and is represented by massive and dispersed chalcocite ore present

Diagenetic controls on reservoir heterogeneity in St. Peter Sandstone, deep Michigan basin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnes, D.A.; Turmelle, T.M.; Adam, R.

1989-03-01

The St. Peter Sandstone is a highly productive gas and condensate reservoir throughout the central part of the Michigan basin. Production occurs in several intervals: a laterally continuous zone at the top of the formation typified in the Woodville, Falmouth, and Rose City fields and less continuous intervals lower in the formation typified in the Ruwe Gulf zone of the Reed City field. Porosity is not limited to hydrocarbon productive zones, however. Diagenesis has dramatically modified primary mineralogy and textures in the formation. Dominant diagenetic components are quartz, dolomite, and clay authigenic cements, extensive chemical compaction, and pervasive mineral leaching.more » Their model for sandstone diagenesis is consistent throughout the basin. Variation in the significance of these diagenetic components is strongly templated by stratigraphically predictable facies variations within the St. Peter Sandstone.« less

Pressure leaching of chalcopyrite concentrate

NASA Astrophysics Data System (ADS)

Aleksei, Kritskii; Kirill, Karimov; Stanislav, Naboichenko

2018-05-01

The results of chalcopyrite concentrate processing using low-temperature and high-temperature sulfuric acid pressure leaching are presented. A material of the following composition was used, 21.5 Cu, 0.1 Zn, 0.05 Pb, 0.04 Ni, 26.59 S, 24.52 Fe, 16.28 SiO2 (in wt.%). The influence of technological parameters on the degree of copper and iron extraction into the leach solution was studied in the wide range of values. The following conditions were suggested as the optimal for the high-temperature pressure leaching: t = 190 °C, PO2 = 0.5 MPa, CH2SO4 = 15 g/L, L:S = 6:1. At the mentioned parameters, it is possible to extract at least 98% Cu from concentrate into the leaching solution during 100 minutes. The following conditions were suggested as optimal for the low-temperature pressure leaching: t = 105 °C, PO2 = 1.3-1.5 MPa, CH2SO4 = 90 g/L, L:S = 10:1. At the mentioned parameters, it is possible to extract up to 83% Cu from the concentrate into the leach solution during 300-360 minutes.

Effects of pyrite and sphalerite on population compositions, dynamics and copper extraction efficiency in chalcopyrite bioleaching process.

PubMed

Xiao, Yunhua; Liu, Xueduan; Dong, Weiling; Liang, Yili; Niu, Jiaojiao; Gu, Yabing; Ma, Liyuan; Hao, Xiaodong; Zhang, Xian; Xu, Zhen; Yin, Huaqun

2017-07-01

This study used an artificial microbial community with four known moderately thermophilic acidophiles (three bacteria including Acidithiobacillus caldus S1, Sulfobacillus thermosulfidooxidans ST and Leptospirillum ferriphilum YSK, and one archaea, Ferroplasma thermophilum L1) to explore the variation of microbial community structure, composition, dynamics and function (e.g., copper extraction efficiency) in chalcopyrite bioleaching (C) systems with additions of pyrite (CP) or sphalerite (CS). The community compositions and dynamics in the solution and on the ore surface were investigated by real-time quantitative PCR (qPCR). The results showed that the addition of pyrite or sphalerite changed the microbial community composition and dynamics dramatically during the chalcopyrite bioleaching process. For example, A. caldus (above 60%) was the dominant species at the initial stage in three groups, and at the middle stage, still dominated C group (above 70%), but it was replaced by L. ferriphilum (above 60%) in CP and CS groups; at the final stage, L. ferriphilum dominated C group, while F. thermophilum dominated CP group on the ore surface. Furthermore, the additions of pyrite or sphalerite both made the increase of redox potential (ORP) and the concentrations of Fe 3+ and H + , which would affect the microbial community compositions and copper extraction efficiency. Additionally, pyrite could enhance copper extraction efficiency (e.g., improving around 13.2% on day 6) during chalcopyrite bioleaching; on the contrary, sphalerite restrained it.

A High-Yield Synthesis of Chalcopyrite CuIn S 2 Nanoparticles with Exceptional Size Control

DOE PAGES

Sun, Chivin; Gardner, Joseph S.; Shurdha, Endrit; ...

2009-01-01

We repormore » t high-yield and efficient size-controlled syntheses of Chalcopyrite CuIn S 2 nanoparticles by decomposing molecular single source precursors (SSPs) via microwave irradiation in the presence of 1,2-ethanedithiol at reaction temperatures as low as 100 ° C and times as short as 30 minutes. The nanoparticles sizes were 1.8 nm to 10.8 nm as reaction temperatures were varied from 100 ° C to 200 ° C with the bandgaps from 2.71 eV to 1.28 eV with good size control and high yields (64%–95%). The resulting nanoparticles were analyzed by XRD, UV-Vis, ICP-OES, XPS, SEM, EDS, and HRTEM. Titration studies by 1 H NMR using SSP 1 with 1,2-ethanedithiol and benzyl mercaptan were conducted to elucidate the formation of Chalcopyrite CuIn S 2 nanoparticles.« less

Integrated diagenetic and sequence stratigraphy of a late Oligocene-early Miocene, mixed-sediment platform (Austral Basin, southern Patagonia): Resolving base-level and paleoceanographic changes, and paleoaquifer characteristics

NASA Astrophysics Data System (ADS)

Dix, George R.; Parras, Ana

2014-06-01

A condensed (~ 20-m-thick) marine transgressive-highstand succession comprises the upper San Julián Formation (upper Oligocene-lower Miocene) of the northern retroarc Austral Basin, southern Patagonia. Mixed-sediment facies identify a shelf-interior setting, part of an overall warm-temperate regional platform of moderate energy. Giant oyster-dominated skeletal-hiatal accumulations along the maximum flooding surface and forming high-energy event beds in the highstand succession preserve relict micrite in protected shelter porosity, and identify periods of reduced sediment accumulation. The stratigraphic distribution of marine-derived glaucony and diagenetic carbonates is spatially related to sequence development. Depositional siderite coincides with prominent marine transgression, defining transient mixing of marine and meteoric waters across coastal-plain deposits. Chemically evolved autochthonous glaucony coincides with periods of extended seafloor exposure and transgressions that bracket the marine succession, and within the oyster-dominated skeletal accumulations. Seafloor cement, likely once magnesian calcite, formed in association with an encrusting/boring biota along the maximum flooding surface in concert with incursion of cool (11-13 °C) water. The cement is present locally in skeletal event beds in the highstand succession suggesting a possible association with high-order base-level change and cooler water. As the highstand succession coincides with elevated global sea level in the late Oligocene-early Miocene, the locally marine-cemented glauconitic skeletal event beds in the highstand succession may identify higher order glacio-eustatic control. Local stratal condensation, however, is best explained by regional differences in basement subsidence. In the burial realm, carbonate diagenesis produced layers of phreatic calcrete coincident with skeletal-rich deposits. Zeolite (clinoptilolite-K) cement is restricted to the lowermost marine transgressive

Depositional and diagenetic variability within the Cambrian Mount Simon Sandstone: Implications for carbon dioxide sequestration

USGS Publications Warehouse

Bowen, B.B.; Ochoa, R.I.; Wilkens, N.D.; Brophy, J.; Lovell, T.R.; Fischietto, N.; Medina, C.R.; Rupp, J.A.

2011-01-01

The Cambrian Mount Simon Sandstone is the major target reservoir for ongoing geologic carbon dioxide (CO2) sequestration demonstrations throughout the midwest United States. The potential CO2 reservoir capacity, reactivity, and ultimate fate of injected CO2 depend on textural and compositional properties determined by depositional and diagenetic histories that vary vertically and laterally across the formation. Effective and efficient prediction and use of the available pore space requires detailed knowledge of the depositional and diagenetic textures and mineralogy, how these variables control the petrophysical character of the reservoir, and how they vary spatially. Here, we summarize the reservoir characteristics of the Mount Simon Sandstone based on examination of geophysical logs, cores, cuttings, and analysis of more than 150 thin sections. These samples represent different parts of the formation and depth ranges of more than 9000 ft (>2743 m) across the Illinois Basin and surrounding areas. This work demonstrates that overall reservoir quality and, specifically, porosity do not exhibit a simple relationship with depth, but vary both laterally and with depth because of changes in the primary depositional facies, framework composition (i.e., feldspar concentration), and diverse diagenetic modifications. Diagenetic processes that have been significant in modifying the reservoir include formation of iron oxide grain coatings, chemical compaction, feldspar precipitation and dissolution, multiple generations of quartz overgrowth cementation, clay mineral precipitation, and iron oxide cementation. These variables provide important inputs for calculating CO2 capacity potential, modeling reactivity, and are also an important baseline for comparisons after CO2 injection. Copyright ??2011. The American Association of Petroleum Geologists/Division of Environmental Geosciences. All rights reserved.

Rare earth elements in Japan Sea sediments and diagenetic behavior of Ce/Ce∗: results from ODP Leg 127

USGS Publications Warehouse

Murray, R.; Buchholtz ten Brink, Marilyn R.; Brumsack, Hans-Juergen; Gerlach, David C.; Russ III, G. Price

1991-01-01

Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlated slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and L(ln/Ybnsuggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

Geologic setting, sedimentary architecture, and paragenesis of the Mesoproterozoic sediment-hosted Sheep Creek Cu-Co-Ag deposit, Helena embayment, Montana

USGS Publications Warehouse

Graham, Garth; Hitzman, Murray W.; Zieg, Jerry

2012-01-01

The northern margin of the Helena Embayment contains extensive syngenetic to diagenetic massive pyrite horizons that extend over 25 km along the Volcano Valley-Buttress fault zone and extend up to 8 km basinward (south) within the Mesoproterozoic Newland Formation. The Sheep Creek Cu-Co deposit occurs within a structural block along a bend in the fault system, where replacement-style chalcopyrite mineralization is spatially associated mostly with the two stratigraphically lowest massive pyrite zones. These mineralized pyritic horizons are intercalated with debris flows derived from synsedimentary movement along the Volcano Valley-Buttress fault zone. Cominco American Inc. delineated a geologic resource of 4.5 Mt at 2.5% Cu and 0.1% Co in the upper sulfide zone and 4 Mt at 4% Cu within the lower sulfide zone. More recently, Tintina Resources Inc. has delineated an inferred resource of 8.48 Mt at 2.96% Cu, 0.12% Co, and 16.4 g/t Ag in the upper sulfide zone. The more intact upper sulfide zone displays significant thickness variations along strike thought to represent formation in at least three separate subbasins. The largest accumulation of mineralized sulfide in the upper zone occurs as an N-S–trending body that thickens southward from the generally E trending Volcano Valley Fault and probably occupies a paleograben controlled by normal faults in the hanging wall of the Volcano Valley Fault. Early microcrystalline to framboidal pyrite was accompanied by abundant and local barite deposition in the upper and lower sulfide zones, respectively. The sulfide bodies underwent intense (lower sulfide zone) to localized (upper sulfide zone) recrystallization and overprinting by coarser-grained pyrite and minor marcasite that is intergrown with and replaces dolomite. Silicification and paragenetically late chalcopyrite, along with minor tennantite in the upper sulfide zone, replaces fine-grained pyrite, barite, and carbonate. The restriction of chalcopyrite to inferred

Diagenetic pathways in deposits of cool- and cold-water carbonate factories

NASA Astrophysics Data System (ADS)

Frank, T. D.; James, N. P.

2017-12-01

This investigation integrates sedimentological, petrographic, and geochemical observations from modern and ancient heterozoan carbonate deposits that formed at temperate to polar latitudes with the aim of evaluating diagenetic pathways characteristic of these systems. These factories operate under conditions distinct from those of photozoan counterparts. Lower temperatures, higher trophic resources, lower carbonate saturation states, and strong seasonality govern not only the nature of carbonate communities, but also how deposits translate into the rock record. In these settings, carbonate production is entirely biogenic, assemblages are of low diversity, and there are no significant calcareous phototrophs. Aragonitic taxa may be present in living communities, but allochems rapidly disappear via dissolution. Carbonate producers are not capable of building rigid frameworks, so their deposits accumulate as sands and gravels and are prone to winnowing and reworking. Low production rates lead to long seafloor residence times (1000s of years) for grains, which undergo physical reworking, dissolution, and repeated infestation by endolithic borers. Microborings remain empty, increasing grain susceptibility to disintegration. Intergranular cementation on the seafloor is rare and restricted to hardgrounds. Periods of subaerial exposure do not leave traces of meteoric alteration. Results show that the deposits of heterozoan carbonate factories tend enter the geologic record as taphonomic remnants, namely reworked, unconsolidated sands and gravels with low diagenetic potential. During burial, physical and chemical compaction produce limestones with tightly packed, grain-supported fabrics, often with grains in sutured contact. Significant cementation is associated with the deep burial realm. Results reveal a dramatically different diagenetic pathway than is typical for deposits of tropical photozoan factories, in which significant recrystallization and lithification occur on

Visible scintillation photodetector device incorporating chalcopyrite semiconductor crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stowe, Ashley C.; Burger, Arnold

2017-04-04

A photodetector device, including: a scintillator material operable for receiving incident radiation and emitting photons in response; a photodetector material coupled to the scintillator material operable for receiving the photons emitted by the scintillator material and generating a current in response, wherein the photodetector material includes a chalcopyrite semiconductor crystal; and a circuit coupled to the photodetector material operable for characterizing the incident radiation based on the current generated by the photodetector material. Optionally, the scintillator material includes a gamma scintillator material and the incident radiation received includes gamma rays. Optionally, the photodetector material is further operable for receiving thermalmore » neutrons and generating a current in response. The circuit is further operable for characterizing the thermal neutrons based on the current generated by the photodetector material.« less

Chemistry of diagenetically altered tuffs at a potential nuclear waste repository, Yucca Mountain, Nye County, Nevada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Broxton, D.E.; Warren, R.G.; Hagan, R.C.

1986-10-01

The chemistry of diagenetically altered tuffs at a potential nuclear waste repository, Yucca Mountain, Nevada is described. These tuffs contain substantial amounts of zeolites that are highly sorptive of certain radionuclides. Because of their widespread distribution, the zeolitic tuffs could provide important barriers to radionuclide migration. Physical properties of these tuffs and of their constituent zeolites are influenced by their chemical compositions. This study defines the amount of chemical variability within diagenetically altered tuffs and within diagenetic minerals at Yucca Mountain. Zeolitic tuffs at Yucca Mountain formed by diagenetic alteration of rhyolitic vitric tuffs. Despite their similar starting compositions, thesemore » tuffs developed compositions that vary both vertically and laterally. Widespread chemical variations were the result of open-system chemical diagenesis in which chemical components of the tuffs were mobilized and redistributed by groundwaters. Alkalies, alkaline earths, and silica were the most mobile elements during diagenesis. The zeolitic tuffs can be divided into three compositional groups: (1) calcium- and magnesium-rich tuffs associated with relatively thin zones of alteration in the unsaturated zone; (2) tuffs in thick zones of alteration at and below the water table that grade laterally from sodic compositions on the western side of Yucca Mountain to calcic compositions on the eastern side; and (3) potassic tuffs at the north end of Yucca Mountain. Physical properties of tuffs and their consistuent zeolites at Yucca Mountain may be affected by variations in compositions. Properties important for assessment of repository performance include behavior and ion exchange.« less

Uranium accumulation in modern and ancient Fe-oxide sediments: Examples from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and Yubileynoe massive sulfide deposit (South Urals, Russia)

NASA Astrophysics Data System (ADS)

Ayupova, N. R.; Melekestseva, I. Yu.; Maslennikov, V. V.; Tseluyko, A. S.; Blinov, I. A.; Beltenev, V. E.

2018-05-01

Fe-oxyhydroxide sediments (gossans) from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and hematite-carbonate-quartz rocks (gossanites) from the Yubileynoe Cu-Zn VHMS deposit (South Urals) are characterized by anomalously high U contents (up to 352 ppm and 73 ppm, respectively). In gossans from the Ashadze-2 hydrothermal sulfide field, rare isometric anhedral uraninite grains (up to 2 μm) with outer P- and Ca-rich rims, and numerous smaller (<1 μm) grains, occur in Fe-oxyhydroxides and sepiolite, associated with pyrite, isocubanite, chalcopyrite, galena, atacamite and halite. In gossanites from the Yubileynoe deposit, numerous uraninite particles (<3 μm) are associated with apatite, V-rich Mg-chlorite, micro-nodules of pyrite, Se-bearing galena, hessite and acanthite in a hematite-carbonate-quartz matrix. Small (1-3 μm) round grains of uraninite, which locally coalesce to large grains up to 10 μm in size, are associated with authigenic chalcopyrite. The similar diagenetic processes of U accumulation in modern and ancient Fe-oxyhydroxide sediments were the result of U fixation from seawater during the oxidation of sulfide minerals. Uraninite in gossanites was mainly deposited from diagenetic pore fluids, which circulated in the sulfide-hyaloclast-carbonate sediments.

Flotation performances and surface properties of chalcopyrite with xanthate collector added before and after grinding

NASA Astrophysics Data System (ADS)

Peng, Huiqing; Wu, Di; Abdelmonem, Mohamed

In this study, effects of the collector added before grinding and after grinding on the subsequent flotation and mineral surface properties were investigated. The pH was controlled at 10 during the grinding and flotation processes opened to the atmosphere. With enough amounts of sodium butyl xanthate addition, adding the collector before grinding recovered more chalcopyrite than adding it after grinding in single mineral flotation. The Eh of each ground pulp before and after conditioning were measured and it was found that adding collector before grinding obtained higher and relatively suitable pulp potential for chalcopyrite flotation. Particle size analyses of the flotation products indicate that the different flotation recoveries occurred due to the different flotation losses in fine particles (<20 μm). XPS analyses focused on the fine particles of flotation feedings and found that more carbon and oxygen, and less iron were remained on mineral surfaces when the collector was added before grinding, due to the higher collector adsorption capacity, larger free oxygen adsorbance and less iron oxide/hydroxide species.

Novel integration strategy for enhancing chalcopyrite bioleaching by Acidithiobacillus sp. in a 7-L fermenter.

PubMed

Feng, Shoushuai; Yang, Hailin; Zhan, Xiao; Wang, Wu

2014-06-01

An integrated strategy (additional energy substrate-three stage pH control-fed batch) was firstly proposed for efficiently improving chalcopyrite bioleaching by Acidithiobacillus sp. in a 7-L fermenter. The strain adaptive-growing phase was greatly shortened from 8days into 4days with the supplement of additional 2g/L Fe(2+)+2g/L S(0). Jarosite passivation was effectively weakened basing on higher biomass via the three-stage pH-stat control (pH 1.3-1.0-0.7). The mineral substrate inhibition was attenuated by fed-batch fermentation. With the integrated strategy, the biochemical reaction was promoted and achieved a better balance. Meanwhile, the domination course of A. thiooxidans in the microbial community was shortened from 14days to 8days. As the results of integrated strategy, the final copper ion and productivity reached 89.1mg/L and 2.23mg/(Ld), respectively, which was improved by 52.8% compared to the uncontrolled batch bioleaching. The integrated strategy could be further exploited for industrial chalcopyrite bioleaching. Copyright © 2014 Elsevier Ltd. All rights reserved.

Compositional controls on early diagenetic pathways in fine-grained sedimentary rocks: Implications for predicting unconventional reservoir attributes of mudstones

USGS Publications Warehouse

Keller, Margaret A.; Macquaker, Joe H.S.; Taylor, Kevin G.; Polya, David

2014-01-01

Diagenesis significantly impacts mudstone lithofacies. Processes operating to control diagenetic pathways in mudstones are poorly known compared to analogous processes occurring in other sedimentary rocks. Selected organic-carbon-rich mudstones, from the Kimmeridge Clay and Monterey Formations, have been investigated to determine how varying starting compositions influence diagenesis.The sampled Kimmeridge Clay Formation mudstones are organized into thin homogenous beds, composed mainly of siliciclastic detritus, with some constituents derived from water-column production (e.g., coccoliths, S-depleted type-II kerogen, as much as 52.6% total organic carbon [TOC]) and others from diagenesis (e.g., pyrite, carbonate, and kaolinite). The sampled Monterey Formation mudstones are organized into thin beds that exhibit pelleted wavy lamination, and are predominantly composed of production-derived components including diatoms, coccoliths, and foraminifera, in addition to type-IIS kerogen (as much as 16.5% TOC), and apatite and silica cements.During early burial of the studied Kimmeridge Clay Formation mudstones, the availability of detrital Fe(III) and reactive clay minerals caused carbonate- and silicate-buffering reactions to operate effectively and the pore waters to be Fe(II) rich. These conditions led to pyrite, iron-poor carbonates, and kaolinite cements precipitating, preserved organic carbon being S-depleted, and sweet hydrocarbons being generated. In contrast, during the diagenesis of the sampled Monterey Formation mudstones, sulfide oxidation, coupled with opal dissolution and the reduced availability of both Fe(III) and reactive siliciclastic detritus, meant that the pore waters were poorly buffered and locally acidic. These conditions resulted in local carbonate dissolution, apatite and silica cements precipitation, natural kerogen sulfurization, and sour hydrocarbons generation.Differences in mud composition at deposition significantly influence subsequent

The Transfiguration continental red-bed Cu-Pb-Zn-Ag deposit, Quebec Appalachians, Canada

NASA Astrophysics Data System (ADS)

Cabral, Alexandre Raphael; Beaudoin, Georges; Taylor, Bruce E.

2009-04-01

The Transfiguration Cu-Pb-Zn-Ag deposit, enclosed within reduced grey sandstone, is associated with continental red beds of the Lower Silurian Robitaille Formation in the Quebec Appalachians, Canada. The Robitaille Formation rests unconformably on foliated Cambro-Ordovician rocks. The unconformity is locally cut by barite veins. The basal unit of the Robitaille Formation comprises green wacke and pebble conglomerate, which locally contain calcite nodules. The latter have microstructures characteristic of alpha-type calcretes, such as “floating” fabrics, calcite-filled fractures (crystallaria) and circumgranular cracks. Massive, grey sandstone overlies the basal green wacke and pebble conglomerate unit, which is overlain, in turn, by red, fine-grained sandstone. Mineralisation occurred underneath the red sandstone unit, chiefly in the grey sandstone unit, as disseminated and veinlet sulphides. Chalcopyrite, the most abundant Cu sulphide, replaced early pyrite. Calcrete, disseminated carbonate and vein carbonate have stable isotope ratios varying from -7.5‰ to -1.1‰ δ13C and from 14.7‰ to 21.3‰ δ18O. The negative δ13C values indicate the oxidation of organic matter in a continental environment. Sulphur isotope ratios for pyrite, chalcopyrite and galena vary from -19‰ to 25‰ δ34S, as measured on mineral concentrates by a conventional SO2 technique. Laser-assisted microanalyses (by fluorination) of S isotopes in pyrite show an analogous range in δ34S values, from -21‰ to 25‰. Negative and positive δ34S values are compatible with bacterial sulphate reduction (BSR) in systems open and closed with respect to sulphate. We interpret similarly high δ34S values for sulphide concentrates (25.1‰) and for vein barite (26.2‰) to result from rapid and complete thermochemical reduction of pore-water sulphate. Two early to late diagenetic stages of mineralisation best explain the origin of the Transfiguration deposit. The first stage was characterised

Evaporite geometries and diagenetic traps, lower San Andres, Northwest shelf, New Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keller, D.R.

An east-west-trending belt of lower San Andres oil fields extends 80 mi across southeastern New Mexico from the Pecos River near Roswell to the Texas-New Mexico border. These fields are along a porosity pinch-out zone where porous carbonates grade laterally into bedded anhydrite and halite. The lower San Andres traps are associated with pre-Tertiary structural or stratigraphic traps. Oil and water production relationships from these fields are not consistent with present-day structure. These fields have been commonly interpreted to be hydrodynamic traps created by the eastern flow of fresh surface water that enters the lower San Andres outcrops west ofmore » Pecos River. There is no evidence, however, that surface water has moved through the lower San Andres in this area. This conclusion is supported by the fact that formation-water resistivities are uniform throughout the producing trend, no significant dissolution of carbonates or evaporites has occurred, and there has been no increase in biogradation of oils adjacent to the lower San Andres outcrops. These fields actually are diagenetic traps created by porosity occlusion in the water column beneath the oil accumulations. Hydrocarbons originally were trapped in pre-Tertiary structural and structural-stratigraphic traps. Bedded evaporites were effective barriers to vertical and lateral hydrocarbon migration. Eastward tilting of the Northwest shelf during the Tertiary opened these traps, but the oil remained in these structurally unfavorable positions because of the diagenetic sealing. The gas-solution drive in these reservoirs is a result of this sealing. The sequence of events leading to diagenetic entrapment include (1) Triassic and Jurassic migration of hydrocarbons into broad, low-relief post-San Andres structural and structural-stratigraphic traps; (2) rapid occlusion of porosity in the water column beneath oil reservoirs, and (3) Tertiary tilt-out traps.« less

Diagenetic history of the Surma Group sandstones (Miocene) in the Surma Basin, Bangladesh

NASA Astrophysics Data System (ADS)

Rahman, M. Julleh Jalalur; McCann, Tom

2012-02-01

This study examines the various diagenetic controls of the Miocene Surma Group sandstones encountered in petroleum exploration wells from the Surma Basin, which is situated in the northeastern part of the Bengal Basin, Bangladesh. The principal diagenetic minerals/cements in the Surma Group sandstones are Fe-carbonates (with Fe-calcite dominating), quartz overgrowths and authigenic clays (predominantly chlorite, illite-smectite and minor kaolin). The isotopic composition of the carbonate cement revealed a narrow range of δ 18O values (-10.3‰ to -12.4‰) and a wide range of δ 13C value (+1.4‰ to -23.1‰). The δ 13C VPDB and δ 18O VPDB values of the carbonate cements reveal that carbon was most likely derived from the thermal maturation of organic matter during burial, as well as from the dissolution of isolated carbonate clasts and precipitated from mixed marine-meteoric pore waters. The relationship between the intergranular volume (IGV) versus cement volume indicates that compaction played a more significant role than cementation in destroying the primary porosity. However, cementation also played a major role in drastically reducing porosity and permeability in sandstones with poikilotopic, pore-filling blocky cements formed in early to intermediate and deep burial areas. In addition to Fe-carbonate cements, various clay minerals including illite-smectite and chlorite occur as pore-filling and pore-lining authigenic phases. Significant secondary porosity has been generated at depths from 2500 m to 4728 m. The best reservoir rocks found at depths of 2500-3300 m are well sorted, relatively coarse grained; more loosely packed and better rounded sandstones having good porosities (20-30%) and high permeabilities (12-6000 mD). These good quality reservoir rocks are, however, not uniformly distributed and can be considered to be compartmentalized as a result of interbedding with sandstone layers of low to moderate porosities, low permeabilities owing to poor

Experimental evidence for an effect of early-diagenetic interaction between labile and refractory marine sedimentary organic matter on nitrogen dynamics

NASA Astrophysics Data System (ADS)

Turnewitsch, Robert; Domeyer, Bettina; Graf, Gerhard

2007-05-01

In most natural sedimentary systems labile and refractory organic material (OM) occur concomitantly. Little, however, is known on how different kinds of OM interact and how such interactions affect early diagenesis in sediments. In a simple sediment experiment, we investigated how interactions of OM substrates of different degradability affect benthic nitrogen (N) dynamics. Temporal evolution of a set of selected biogeochemical parameters was monitored in sandy sediment over 116 days in three experimental set-ups spiked with labile OM (tissue of Mytilus edulis), refractory OM (mostly aged Zostera marina and macroalgae), and a 1:1 mixture of labile and refractory OM. The initial amounts of particulate organic carbon (POC) were identical in the three set-ups. To check for non-linear interactions between labile and refractory OM, the evolution of the mixture system was compared with the evolution of the simple sum of the labile and refractory systems, divided by two. The sum system is the experimental control where labile and refractory OM are virtually combined but not allowed to interact. During the first 30 days there was evidence for net dissolved-inorganic-nitrogen (DIN) production followed by net DIN consumption. (Here 'DIN' is the sum of ammonium, nitrite and nitrate.) After ˜ 30 days a quasi steady state was reached. Non-linear interactions between the two types of OM were reflected by three main differences between the early-diagenetic evolutions of nitrogen dynamics of the mixture and sum (control) systems: (1) In the mixture system the phases of net DIN production and consumption commenced more rapidly and were more intense. (2) The mixture system was shifted towards a more oxidised state of DIN products [as indicated by increased (nitrite + nitrate)/(ammonium) ratios]. (3) There was some evidence that more OM, POC and particulate nitrogen were preserved in the mixture system. That is, in the mixture system more particulate OM was preserved while a higher

Scientific communications: Re-Os sulfide (bornite, chalcopyrite, and pyrite) systematics of the carbonate-hosted copper deposits at ruby creek, southern brooks range, Alaska

USGS Publications Warehouse

Selby, D.; Kelley, K.D.; Hitzman, M.W.; Zieg, J.

2009-01-01

New Re-Os data for chalcopyrite, bornite, and pyrite from the carbonate-hosted Cu deposit at Ruby Creek (Bornite), Alaska, show extremely high Re abundances (hundreds of ppb, low ppm) and contain essentially no common Os. The Re-Os data provide the first absolute ages of ore formation for the carbonate-hosted Ruby Creek Cu-(Co) deposit and demonstrate that the Re-Os systematics of pyrite, chalcopyrite, and bornite are unaffected by greenschist metamorphism. The Re-Os data show that the main phase of Cu mineralization pre dominantly occurred at 384 ?? 4.2 Ma, with an earlier phase possibly at ???400 Ma. The Re-Os data are consistent with the observed paragenetic sequence and coincide with zircon U-Pb ages from igneous rocks within the Ambler metallogenic belt, some of which are spatially and genetically associated with regional volcanogenic massive sulfide deposits. The latter may suggest a temporal link between regional magmatism and hydrothermal mineralization in the Ambler district. The utility of bornite and chalcopyrite, in addition to pyrite, contributes to a new understanding of Re-Os geochronology and permits a refinement of the genetic model for the Ruby Creek deposit. ?? 2009 Society of Economices Geologists, Inc.

Co-culture microorganisms with different initial proportions reveal the mechanism of chalcopyrite bioleaching coupling with microbial community succession.

PubMed

Ma, Liyuan; Wang, Xingjie; Feng, Xue; Liang, Yili; Xiao, Yunhua; Hao, Xiaodong; Yin, Huaqun; Liu, Hongwei; Liu, Xueduan

2017-01-01

The effect of co-culture microorganisms with different initial proportions on chalcopyrite bioleaching was investigated. Communities were rebuilt by six typical strains isolated from the same habitat. The results indicated, by community with more sulfur oxidizers at both 30 and 40°C, the final copper extraction rate was 19.8% and 6.5% higher, respectively, than that with more ferrous oxidizers. The variations of pH, redox potential, ferrous and copper ions in leachate also provided evidences that community with more sulfur oxidizers was more efficient. Community succession of free and attached cells revealed that initial proportions played decisive roles on community dynamics at 30°C, while communities shared similar structures, not relevant to initial proportions at 40°C. X-ray diffraction analysis confirmed different microbial functions on mineral surface. A mechanism model for chalcopyrite bioleaching was established coupling with community succession. This will provide theoretical basis for reconstructing an efficient community in industrial application. Copyright © 2016 Elsevier Ltd. All rights reserved.

Geochemistry of ferromanganese nodules from DOMES site a, Northern Equatorial Pacific: Multiple diagenetic metal sources in the deep sea

USGS Publications Warehouse

Calvert, S.E.; Piper, D.Z.

1984-01-01

The major and minor element composition of ferromanganese nodules from DOMES Site A has been determined by X-ray fluorescence methods. Three phases appear to control the bulk compositions: Mn and Fe oxyhydroxides and aluminosilicates. Relatively wide compositional variations are evident throughout the area. Nodules with high Mn/Fe ratios, high Cu, Mg, Mo, Ni and Zn concentrations and high todorokite/??-MnO2 ratios have granular surface textures and are confined to an east-west trending depression with thin Quaternary sediment cover. Nodules with low Mn/Fe ratios, high concentrations of As, Ca, Ce, Co, La, P, Sr, Ti, V, Y and Zr and low todorokite/??-MnO2 ratios have smooth surfaces and are confined to shallower areas with relatively thick Quaternary sediment to the north and south of the depression. All nodules in the area have compositions which are influenced by diagenesis, but those with the most marked diagenetic signature (high Mn/Fe and Cu/Ni ratios, low Ce/La ratios and more todorokite) are found in areas of very slow or non-existent sedimentation; many of these nodules are actually in contact with outcropping Tertiary sediment. This paradox may be resolved by postulating, by analogy with some shallow-water occurrences, that the nodules accrete from bottom waters which have enhanced particulate and dissolved metal contents derived from diagenetic reaction in areas remote from the site of nodule formation. The metals are supplied in a bottom flow (probably Antarctic Bottom Water) which also erodes, or prevents modern sedimentation in, the depression. Nodules on the flanks of the depression are not evidently affected by this flow and derive at least pan of their constituent metals from diagenetic reaction in the underlying Quaternary sediment. Apparently, abyssal diagenetic nodules can have an immediate and a remote diagenetic metal source. Metal fluxes derived from pore water dissolved metal gradients may not be relevant to particular accreting nodules if a

Diagenetic evaluation of Pannonian lacustrine deposits in the Makó Trough, southeastern Hungary

NASA Astrophysics Data System (ADS)

Szőcs, Emese; Milovský, Rastislav; Gier, Susanne; Hips, Kinga; Sztanó, Orsolya

2017-04-01

The Makó Trough is the deepest sub-basin of the Pannonian Basin. As a possible shale gas and tight gas accumulation the area was explored by several hydrocarbon companies. In this study, we present the preliminary results on the diagenetic history and the porosity evolution of sandstones and shales. Petrographic (optical microscopy, CL, blue light microscopy) and geochemical methods (SEM-EDX, WDX, O and C stable isotopes) were applied on core samples of Makó-7 well (3408- 5479 m). Processes which influenced the porosity evolution of the sandstones were compaction, cementation, mineral replacement and dissolution. The most common diagenetic minerals are carbonates (non-ferroan and Fe-bearing calcite, dolomite and ankerite), clay minerals (kaolinite, mixed layer illite-smectite and chlorite) and other silicates (quartz and feldspar). Initial clay mineral and ductile grain content also influences reservoir quality. The volumetrically most significant diagenetic minerals are calcite and clay minerals. The petrography of calcite is variable (bright orange to dull red luminescence color, pore-filling cement, replacive phases which are occasionally scattered in the matrix). The δ13 C-PDB values of calcite range from 1.7 ‰ to -5.5 ‰, while δ18 O-PDB values range from 0.5 ‰ to -9.1 ‰, no depth related trend was observed. These data suggest that calcite occurs in more generations, i.e. eogenetic pre-compactional and mesogenetic post-compactional. Kaolinite is present in mottles in size similar to detrital grains, where remnants of feldspars can be seen. This indicates feldspar alteration via influx of water rich in organic derived carbon dioxide. Secondary porosity can be observed in carbonates and feldspars at some levels, causing the improvement of the reservoir quality.

Influence of Organic Solvents on Chalcopyrite Oxidation Ability of Thiobacillus ferrooxidans

PubMed Central

Torma, Arpad E.; Itzkovitch, Irwin J.

1976-01-01

It has been shown that organic solvents used primarily for the extraction of metals from aqueous leach liquors decrease both the surface tension of the aqueous phase and the chalcopyrite oxidation ability of Thiobacillus ferrooxidans. For the reagents and modifiers investigated, the order of inhibition was found to be LIX 70 < LIX 73 < LIX 71 < LIX 64N < LIX 65N < TBP ∼ isodecanol ∼ nonylphenol < LIX 63 <<< D2EHPA ∼ Kelex 100 < Kelex 120 <<< Alamine 336 ∼ Alamine 308 ∼ Alamine 310 < Alamine 304 < Adogen 381 ∼ Aliquat 336 < Adogen 364. To avoid limitation in bacterial activity, organic matter should be removed from the recycling liquor prior to leaching. PMID:16345164

Chemical Composition of Diagenetic Features at Lower Aeolis Mons, Mars as Measured by Curiosity's APXS

NASA Astrophysics Data System (ADS)

Berger, J. A.; Schmidt, M. E.; Gellert, R.; Boyd, N.; Campbell, J. L.; Desouza, E.; Fisk, M. R.; Perrett, G. M.; Thompson, L. M.; VanBommel, S.; Yen, A. S.

2015-12-01

Curiosity's APXS investigation of the Murray Fm. (sols 755 - 950) at lower Aeolis Mons (Mt. Sharp) in Gale Crater, Mars has revealed (Mg, Ni)-sulfate diagenetic features and dark gray Ca-rich veins. The (Mg, Ni)-sulfate features occur as ~2 cm wide dendritic and botryoidal concretions that stand out in relief ~1 cm above the mudstone surface. APXS rasters over the features (Moenkopi, Mammoth, Morrison, Rosamond, Potatoe; sols 758 - 810) resulted in 1:1 molar variation of S and Mg consistent with a MgSO4 phase. The sulfate is not pure; the features are a mixture of 10 - 15% MgSO4 with the host mudstone. This mixture suggests the sulfates precipitated within pre-existing pore spaces, or were partially dissolved and replaced by sediment, preserving the crystal morphology. The sulfate features are enriched in Ni (2000 - 4250 ppm), indicating Ni-sulfate. The Murray Fm. mudstones that host the diagenetic features range to high SiO2 (60-73 wt%) and have bulk elemental signatures that are consistent with alteration by acid leaching. Low MgO (3.0 wt%) and low Ni (100 - 300 ppm) in the most apparently altered (highest SiO2) mudstones may link the acidic alteration with the fluids that formed the (Mg, Ni)-sulfates. Diagenetic Ca-sulfate-bearing veins that were abundant across Aeolis Palus persist at lower Aeolis Mons. A new vein type containing dark gray material as a separate crystalline phase within white Ca-sulfate veins was discovered in a cluster of veins in the Murray Fm. (Coalville, Alvord Mt., Amboy; sols 930 - 948). APXS rasters of the dark-toned material indicate high CaO (20 - 30 wt%) without concomitant increases in SO3. Ge (up to 650 ppm; 6.5X surrounding bedrock) and MnO (up to 1.0 wt%; 4X surrounding bedrock) are both enriched in the dark veins. These chemical observations are consistent with fluorite, although F (L.O.D. >5%) is not detectable in APXS spectra. The diagenetic features indicate that Ca, Mg, and Ni were mobilized with S in aqueous fluids, and that

Origin and diagenetic transformations of C 25 and C 30 highly branched isoprenoid sulphur compounds: Further evidence for the formation of organically bound sulphur during early diagenesis

NASA Astrophysics Data System (ADS)

Kohnen, M. E. L.; Damsté, J. S. Slnninghe; Kock-van Dalen, A. C.; Haven, H. L. Ten; Rullkötter, J.; De Leeuw, J. W.

1990-11-01

A number of C 25 and C 30 highly branched isoprenoid (HBI) sulphur compounds (E.G., thiolanes, 1-oxo-thiolanes, thiophenes, and benzo[ b]thiophenes) with 2,6,10,14-tetramethyl-7-(3-methylpentyl)pentadecane and 2,6,10,14,18-pentamethyl-7-(3-methylpentyl)nonadecane carbon skeletons were identified in sediments, ranging from Holocene to Upper Cretaceous. These identifications are based on mass spectral characterisation, desulphurisation, and, in some cases, by comparison of mass spectral and relative retention time data with those of authentic standards. The presence of unsaturated C 25 and C 30 HBI thiolanes in a Recent sediment from the Black Sea (age 3-6 × 10 3 a) strongly supports their formation during early diagenesis. The co-occurrence of HBI polyenes (C 25 and C 30) and unsaturated HBI thiolanes (C 25 and C 30) possessing two double bonds less than the corresponding HBI polyenes, in this Recent sediment, testifies to the formation of unsaturated HBI thiolanes by a reaction of inorganic sulphur species with double bonds of the HBI polyenes. Furthermore, a diagenetic scheme for HBI sulphur compounds is proposed based on the identification of HBI sulphur compounds in sediment samples with different maturity levels.

Geochemistry of pyrite and chalcopyrite from an active black smoker in 49.6°E Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Yuan, Bo; Yang, Yaomin; Yu, Hongjun; Zhao, Yuexia; Ding, Qingfeng; Yang, Jichao; Tang, Xin

2017-06-01

Active hydrothermal chimneys, as the product of submarine hydrothermal activity, can be used to determine the fluid evolution and formation process of potential volcanic-hosted massive sulfide deposits. A hard-won specimen from an active hydrothermal chimney was collected in the 49.6°E ultraslow-spreading Southwest Indian Ridge (SWIR) field through a television-guided grab. A geochemical study of prominent sulfide (e.g., pyrite and chalcopyrite) included in this sample was performed using laser ablation inductively coupled plasma mass spectroscopy. The early sulfides produced at low temperature are of disseminated fine-grained anhedral morphology, whereas the late ones with massive, coarse euhedral features precipitated in a high-temperature setting. The systematic variations in the contents of minor and trace elements are apparently related to the crystallization sequence, as well as to texture. Micro-disseminated anhedral sulfides rich in Pb, As, Ni, Ba, Mn, Mo, U, and V were formed during the initial chimney wall growth, whereas those rich in Sn, Se, and Co with massive, coarse euhedral morphology were formed within the late metallogenic stage. The hydrothermal fluid composition has experienced a great change during the chimney growth. Such a conclusion is consistent with that indicated by using principal component analysis, which is a powerful statistical analysis method widely used to project multidimensional datasets (e.g., element contents in different mineral phases) into a few directions. This distribution pattern points to crystallographic controls on minor and trace element uptake during chimney growth, occurring with concomitant variations in the fluid composition evolutionary history. In this pyrite-chalcopyrite-bearing active hydrothermal chimney at the SWIR, the metal concentration and precipitation of sulfides largely occurred at the seafloor as a result of mixing between the upwelling hot hydrothermal fluid and cold seawater. Over the course of

Parameterization of biogeochemical sediment-water fluxes using in-situ measurements and a steady-state diagenetic model

EPA Science Inventory

Diagenetic processes are important drivers of water column biogeochemistry in coastal areas. For example, sediment oxygen consumption can be a significant contributor to oxygen depletion in hypoxic systems, and sediment–water nutrient fluxes support primary productivity in ...

Raised Ridges in the Sheepbed Member as Evidence for Early Subaqueous Diagenesis at Yellowknife Bay, Gale Crater, Mars

NASA Astrophysics Data System (ADS)

Siebach, K. L.; Grotzinger, J. P.; Kah, L. C.; Stack, K.; Leveille, R. J.; Sumner, D. Y.; Edgar, L. A.; Team, M.

2013-12-01

Spatially restricted clusters of erosion-resistant, ridged fracture fills have been found throughout the fine-grained clay-rich Sheepbed member of the Yellowknife Bay Formation where the Mars Science Laboratory rover recently drilled. These 'raised ridge' features are characterized by 1-6 mm thick fractures filled with 2-4 subparallel resistant ridges. The ridges have been mapped throughout the Sheepbed member on Mastcam mosaics from sols 137 to 194 and are shown to be constrained to relatively dense, spatially localized clusters within the unit. The ridges have highly variable attitudes, ranging in dip from vertical to sub-horizontal, and striking in all directions, indicating that the original fractures formed in a mechanically isotropic setting. The fractures are generally short (<50 cm), have spindle-shaped terminations, and do not form regular polygons. The individual ridges are approximately a millimeter across and separated by at least a millimeter of less-resistant material. Based on the geometry of these features and lateral fabric variability within the unit, these are interpreted as early diagenetic synaeresis cracks, likely formed by gas expansion prior to final lithification of the Sheepbed member. Based on the isopachous nature of both the resistant and less-resistant fracture fills, the fracture-filling also occurred subaqueously, in the phreatic zone, and was likely a very early diagenetic process. This is supported by the observation that later diagenetic features, including light-toned sulfate-rich veins, cross-cut raised ridges. Investigation into the characteristics and distribution of these features, and comparison with synaeresis cracks on Earth, provide insight into the formation of the Sheepbed member and early aqueous and diagenetic processes in Gale Crater.

Photochemical dissolution of organic matter from resuspended sediments: Impact of source and diagenetic state on photorelease

NASA Astrophysics Data System (ADS)

Helms, J. R.; Glinski, D. A.; Mead, R. N.; Southwell, M.; Avery, G. B., Jr.; Kieber, R. J.; Skrabal, S. A.

2015-12-01

Resuspended sediments exposed to simulated solar radiation release dissolved organic carbon (DOC). However, it is unclear how the provenance of sedimentary organic matter (OM) impacts this photorelease. In the first geographically extensive study of this phenomenon, twenty three size fractionated, fine grained sediments (< ca. 10-20 μm) from a variety of drainage basins were resuspended (at suspended solid loading of 29- 255 mg/l) and exhibited a net photochemical DOC release ranging from 2 to 178 μmol/g/h. There was a logarithmic increase in photoreleased DOC vs. the proportion of sedimentary OC (%), most likely due to photon limitation at high sedimentary OC loading (i.e. high mass-specific absorption limiting light penetration). Sediment source and quality - determined using lipid biomarkers - had a significant effect on DOC photorelease. The fatty acid terrestrial aquatic ratio (TARFA) indicated that terrestrially derived sediments exhibited relatively greater DOC photorelease. The long chain carbon preference index (CPI24-34) indicated that diagenetically unaltered terrestrial OM photoreleased more DOC than diagenetically altered terrestrial OM. The short chain carbon preference index (CPI14-22) demonstrated that sediments containing diagenetically altered planktonic or algal derived OM had a greater photorelease rate of DOC than fresh algal OM. This suggests that humic substances (humus and/or adsorbed humic and fulvic acids) play an important role in the photochemical dissolution of OC regardless of whether or not they are imported from upstream (i.e. terrestrial humics) or generated within the depositional or sedimentary environment (i.e. humification of algal dissolved OM).

Diagenetic changes in the elemental composition of unrecrystallized mollusk shells

USGS Publications Warehouse

Ragland, P.C.; Pilkey, O.H.; Blackwelder, B. W.

1979-01-01

The Mg, Sr, Mn, Fe, Na and K contents were determined for 230 apparently unrecrystallized mollusk shells (gastropods and bivalves) ranging in age from late Cretaceous to Holocene. Consistent differences between the Holocene and fossil shells with respect to concentrations of all these elements are attributed to postburial diagenetic changes. Fossil-Holocene shell comparisons are made on the intergeneric level, a more severe test of compositional differences than was previous work involved with few species. The observed differences re-emphasize the need for extreme caution in the use of the many geochemical tools which assume that no compositional changes have taken place prior to recrystallization of calcareous materials. ?? 1979.

Composition, diagenetic transformation and alkalinity potential of oil shale ash sediments.

PubMed

Mõtlep, Riho; Sild, Terje; Puura, Erik; Kirsimäe, Kalle

2010-12-15

Oil shale is a primary fuel in the Estonian energy sector. After combustion 45-48% of the oil shale is left over as ash, producing about 5-7 Mt of ash, which is deposited on ash plateaus annually almost without any reuse. This study focuses on oil shale ash plateau sediment mineralogy, its hydration and diagenetic transformations, a study that has not been addressed. Oil shale ash wastes are considered as the biggest pollution sources in Estonia and thus determining the composition and properties of oil shale ash sediment are important to assess its environmental implications and also its possible reusability. A study of fresh ash and drillcore samples from ash plateau sediment was conducted by X-ray diffractometry and scanning electron microscopy. The oil shale is highly calcareous, and the ash that remains after combustion is derived from the decomposition of carbonate minerals. It is rich in lime and anhydrite that are unstable phases under hydrous conditions. These processes and the diagenetic alteration of other phases determine the composition of the plateau sediment. Dominant phases in the ash are hydration and associated transformation products: calcite, ettringite, portlandite and hydrocalumite. The prevailing mineral phases (portlandite, ettringite) cause highly alkaline leachates, pH 12-13. Neutralization of these leachates under natural conditions, by rainwater leaching/neutralization and slow transformation (e.g. carbonation) of the aforementioned unstable phases into more stable forms, takes, at best, hundreds or even hundreds of thousands of years. Copyright © 2010 Elsevier B.V. All rights reserved.

Fatty acids in sparry calcite fracture fills and microsparite cement of septarian diagenetic concretions

NASA Astrophysics Data System (ADS)

Pearson, M. J.; Hendry, J. P.; Taylor, C. W.; Russell, M. A.

2005-04-01

Sparry calcite fracture fills and concretion body cements in concretions from the Flodigarry Shale Member of the Staffin Shale Formation, Isle of Skye, Scotland, entrap and preserve mineral and organic materials of sedimentary and diagenetic origin. Fatty acids are a major component of the lipids recovered by decarbonation and comprise mainly n-alkanoic and α-ω dicarboxylic acids. Two generations of fracture-fill calcite (early brown and later yellow) and the concretion body microspar yield significantly different fatty acid profiles. Early brown calcites yield mainly medium-chain n-alkanoic acids with strong even predominance; later yellow calcites are dominated by α-ω dicarboxylic acids with no even predominance. Both fracture fills lack the long-chain n-alkanoic and α-ω dicarboxylic acids additionally recovered from the concretion bodies. The absence of longer chain acids in the calcite spar fracture fills is inferred to result from the transport of fatty acids by septarian mineralising fluids whereby low-aqueous solubility of longer chain acids or their salts accounts for their relative immobility. Comparative experiments have been carried out using conventional solvent extraction on the concretion body and associated shales, both decarbonated and untreated. Extracted lipid yields are higher, but the fatty acids probably derive from mixed locations in the rock including both kerogen- and carbonate-associated lipid pools. Only experiments involving decarbonation yielded α-ω dicarboxylic acids in molecular distributions probably controlled mainly by fluid transport. Alkane biomarker ratios indicate very low thermal maturity has been experienced by the concretions and their host sediments. Septarian cracks lined by brown calcite formed during early burial. Microbial CO 2 from sulphate-reducing bacteria was probably the main source of mineralising carbonate. Emplacement of the later septarian fills probably involved at least one episode of fluid invasion.

Quantifying the effect of diagenetic recrystallization on the Mg isotopic composition of marine carbonates

NASA Astrophysics Data System (ADS)

Chanda, Piyali; Fantle, Matthew S.

2017-05-01

The Mg and Sr isotopic compositions (δ26Mg and 87Sr/86Sr) of pore fluids and bulk carbonates from Ocean Drilling Project Site 1171 (South Tasman Rise; 2148.2 m water depth) are reported, in order to evaluate the potential of diagenesis to alter carbonate-based geochemical proxies in an open marine system. Given the trace amounts of Mg in marine carbonates relative to coexisting pore fluids, diagenesis can alter carbonate δ26Mg, a promising proxy for seawater δ26Mg that may help elucidate long-term changes in the global Mg cycle. Constraints on the effect of diagenetic recrystallization on carbonate δ26Mg are therefore critical for accurate proxy interpretations. This study provides context for assessing the fidelity of geochemical proxy-reconstructions using the primary components (i.e., foraminiferal tests and nannofossils) of bulk carbonate sediments. We find that pore fluid δ26Mg values (on the DSM3 scale) at Site 1171 increase systematically with depth (from -0.72‰ to -0.39‰ in the upper ∼260 m), while the δ26Mg of bulk carbonates decrease systematically with depth (from -2.23‰ to -5.00‰ in the upper ∼260 m). This variability is ascribed primarily to carbonate recrystallization, with a small proportion of the variability due to down-hole changes in nannofossil and foraminiferal species composition. The inferred effect of diagenesis on bulk carbonate δ26Mg correlates with down-core changes in Mg/Ca, Sr/Ca, Na/Ca, and 87Sr/86Sr. A depositional reactive-transport model is employed to validate the hypothesis that calcite recrystallization in this system can generate sizeable shifts in carbonate δ26Mg. Model fits to the data suggest a fractionation factor and a partition coefficient that are consistent with previous work, assuming calcite recrystallization rates of ⩽7%/Ma constrained by Sr geochemistry. In addition, either partial dissolution or a distinctly different previous diagenetic regime must be invoked in order to explain aspects of the

Early diagenesis driven by widespread meteoric infiltration of a Central European carbonate ramp: A reinterpretation of the Upper Muschelkalk

NASA Astrophysics Data System (ADS)

Adams, Arthur; Diamond, Larryn W.

2017-12-01

Meteoric diagenesis of carbonate ramps is often difficult to interpret and can commonly be confused with other coinciding diagenetic processes. The Middle Triassic Upper Muschelkalk of Switzerland provides an insightful case in which the effects of several overprinting diagenetic environments, including matrix dolomitization, can be clearly unravelled. Previous studies suggested that diagenesis took place in connate marine waters, with later meteoric waters being invoked to explain recrystallization of dolomite. In this study, diagenetic analyses (C-O stable isotope ratios, thin-section point counting, cathodoluminescence and UV-fluorescence microscopy) of calcitic bioclastic samples have revealed that early diagenesis (pre-stylolitization) and the accompanying porosity evolution did not occur exclusively in the presence of marine fluids. Five sequential stages of diagenesis have been identified: marine, shallow burial, mixing-zone, meteoric and dolomitization. Marine diagenesis induced precipitation of bladed and inclusion-rich syntaxial cements that fluoresce strongly under UV-light. Both cements account for a mean 7.5 vol% reduction in the porosity of bioclastic beds. Shallow burial diagenesis likely induced mouldic porosity and associated fluorescent dog-tooth cementation. Based on light oxygen isotope and elevated strontium isotope ratios, matrix aragonite-calcite neomorphism is interpreted to have occurred in a mixture of marine and meteoric fluids. The combination of shallow burial and mixing-zone processes reduced porosity on average by 4.8 vol%. Evidence for subsequent meteoric diagenesis is found in abundant dog-tooth and blocky calcite cements that have mean δ18OVPDB of - 9.36‰ and no signs of recrystallization. These meteoric cements reduced porosity by a further 13.4 vol%. Percolation of meteoric water through the ramp was driven by hydraulic gradients on an adjacent basement high, which was exposed by a cycle of early Ladinian regressions

Development and Application of a Paleomagnetic/Geochemical Method for Constraining the Timing of Burial Diagenetic and Fluid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elmore, Richard D.; Engel, Michael H.

2005-03-10

Studies of diagenesis caused by fluid migration or other events are commonly hindered by a lack of temporal control. Our results to date demonstrate that a paleomagnetic/geochemical approach can be used to date fluid migration as well as burial diagenetic events. Our principal working hypothesis is that burial diagenetic processes (e.g., maturation of organic-rich sediments and clay diagenesis) and the migration of fluids can trigger the authigenesis of magnetic mineral phases. The ages of these events can be constrained by comparing chemical remanent magnetizations (CRMs) to independently established Apparent Polar Wander Paths. While geochemical (e.g. stable isotope and organic analyses)more » and petrographic studies provide important clues for establishing these relationships, the ultimate test of this hypothesis requires the application of independent dating methods to verify the paleomagnetic ages. Towards this end, we have used K-Ar dating of illitization as an alternative method for constraining the ages of magnetic mineral phases in our field areas.« less

Depositional and diagenetic history and petroleum geology of the Jurassic Norphlet Formation of the Alabama coastal waters area and adjacent federal waters area

USGS Publications Warehouse

Kugler, R.L.; Mink, R.M.

1999-01-01

to a combination of factors, including a lack of sources of cement components and lack of pervasive early cement, so that fluid-flow pathways remained open during burial. Below the dominantly quartz-cemented tight zone near the top of the Norphlet, pyrobitumen is a major contributor to reduction in reservoir quality in offshore Alabama. The highest reservoir quality occurs in those wells where the present gas-water contact is below the paleohydrocarbon-water contact. Thiz zone of highest reservoir quality is between the lowermost occurrence of pyrobitumen and the present gas-water contact.The Upper Jurassic Norphlet Formation sediment was deposited in an arid environment in alluvial fans, alluvial plains, and wadis in undip areas. In downdip areas, the Norphlet was deposited in a broad desert plain, with erg development in some areas. Marine transgression, near the end of Norphlet deposition resulted in reworking of the upper part of the formation. he present framework grain assemblage of the Norphlet is dominantly diagenetic, owing to albitization and dissolution of feldspar. Despite the simple framework composition, the diagenetic character of the Norphlet is complex.

Rare earth elements in Japan Sea sediments and diagenetic behavior of Ce/Ce∗: Results from ODP Leg 127

NASA Astrophysics Data System (ADS)

Murray, Richard W.; Buchholtzten Brink, Marilyn R.; Brumsack, Hans J.; Gerlach, David C.; Russ, G. Price

1991-09-01

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (ΣREE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu∗ values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu∗ with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. ΣREE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce∗ profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce∗ record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce∗ correlates slightly better with depth than with age. The downhole increase in Ce

Impact of diagenetic alteration on sea urchin (Echinodermata) magnesium isotope signatures: Comparison of experimental and fossil data

NASA Astrophysics Data System (ADS)

Riechelmann, Sylvia; Mavromatis, Vasileios; Buhl, Dieter; Dietzel, Martin; Hoffmann, René; Jöns, Niels; Eisenhauer, Anton; Immenhauser, Adrian

2017-04-01

Due to their thermodynamically instable high-Mg calcite mineralogy, the skeletal elements of echinoderms are often regarded as unreliable archives of Phanerozoic marine climate dynamics. Nevertheless, traditional and non-traditional isotope and elemental proxy data from echinoderms have been used to reconstruct global changes in palaeoseawater composition (Sandberg-cycles). Recently, these data and the interpretation have been controversially discussed in context with ancient seawater properties. This paper tests the sensitivity of echinoderm skeletal hardparts, specifically sea urchin spines to diagenetic alteration based on magnesium isotope data. We apply a dual approach by: (i) performing hydrothermal alteration experiments using meteoric, marine, and burial reactive fluids; and (ii) comparing these data with fossil sea urchin hardparts. The degree of alteration of experimentally altered and fossil sea urchin hardparts is assessed by a combination of optical (fluorescence, cathodoluminescence (CL), scanning electron microscopy (SEM)) and geochemical tools (elemental distribution, carbon, oxygen and magnesium isotopes). Although initial fluid chemistry of the experiments did not allow the detection of diagenetic overprint by elemental distribution (Fe, Mn) and cathodoluminescence, other tools such as fluorescence, SEM, delta18O, Mg concentration and delta26Mg display alteration effects, which respond to differential fluid temperature, chemistry, and experiment duration time. At experiments run under meteoric conditions with no Mg in the initial fluid, the solid is enriched in the heavier Mg isotopomer due to preferential dissolution of the lighter isotope. In contrast, initial burial and marine fluids have medium to high Mg concentrations. There, the Mg concentration and the delta26Mg values of the altered sea urchin spines increase. Fossil sea urchin hardparts display partly very strong diagenetic overprint as observed by their elemental distribution

Petrography and geochemistry of the Permian-Triassic boundary interval, Yangou section, South China: Implications for early Griesbachian seawater δ13CDIC gradient with depth

NASA Astrophysics Data System (ADS)

Li, Rong

2017-04-01

The carbon isotopic composition (δ13Ccarb) recorded in shelf carbonates has been widely used as a proxy for the isotopic composition (δ13CDIC) of surface ocean water to establish paleocean chemistry and circulation patterns. However, δ13Ccarb values do not necessarily preserve the δ13CDIC, due to post-depositional diagenetic alteration. In order to examine the early Griesbachian surface-to-deep δ13CDIC gradient with depth, the diagenetic features of the Permian-Triassic boundary interval (beds 18 to 35) from Yangou section, located in the Yangtze carbonate platform interior, South China, are delineated to compare with those of the slope GSSP Meishan section. The petrographic and geochemical observations show that the early Griesbachian carbonates in the Yangou section underwent pervasive dolomitization in its early diagenetic history. Three types of early replacement dolomites and one type of dolomite cement are present. The dolomite crystals display internal zonation, with high-Ca calcian dolomite (HCD) core being encased successively by calcite and an outermost Fe-rich HCD cortex. The initial dolomitization took place in anoxic seawater, and underwent subsequent diagenetic system involved with meteoric water. The two most negative δ13C values in claystones of Beds 21-3 and 35 are probably related to meteoric diagenesis. Above and/or below the meteorically influenced beds, the dolomite and calcite have uniformly positive δ13C values. The primary carbon isotopic compositions are probably preserved in the early Griesbachian carbonate from the platform Yangou section, which could probably be related to the poor formation of the outermost Fe-rich HCD cortex. Compared to the slope carbonate from the Meishan section, the platform carbonate from the Yangou section has lower primary δ13Ccarb values. It is estimated that the δ13CDIC gradient with depth between Yangou and Meishan is less than the previously suggested. The results highlight the need for evaluation

Electronic modification of Cu-based chalcopyrite semiconductors induced by lattice deformation and composition alchemy

NASA Astrophysics Data System (ADS)

Jiang, F. D.; Feng, J. Y.

2008-02-01

Using first principles calculation, we systematically investigate the electronic modification of Cu-based chalcopyrite semiconductors induced by lattice deformation and composition alchemy. It is shown that the optical band gap Eg is remarkably sensitive to the anion displacement μ, resulting from the opposite shifts of conduction band minimum and valence band maximum. Meanwhile, the dependence of structural parameters of alloyed compounds on alloy composition x is demonstrated for both cation and anion alloying. The d orbitals of group-III cations are found to be of great importance in the calculation. Abnormal changes in the optical band gap Eg induced by anion alloying are addressed.

Spray Chemical Vapor Deposition of Single-Source Precursors for Chalcopyrite I-III-VI2 Thin-Film Materials

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Banger, Kulbinder K.; Jin, Michael H.-C.; Harris, Jerry D.; McNatt, Jeremiah S.; Dickman, John E.

2008-01-01

Thin-film solar cells on flexible, lightweight, space-qualified substrates provide an attractive approach to fabricating solar arrays with high mass-specific power. A polycrystalline chalcopyrite absorber layer is among the new generation of photovoltaic device technologies for thin film solar cells. At NASA Glenn Research Center we have focused on the development of new single-source precursors (SSPs) for deposition of semiconducting chalcopyrite materials onto lightweight, flexible substrates. We describe the syntheses and thermal modulation of SSPs via molecular engineering. Copper indium disulfide and related thin-film materials were deposited via aerosol-assisted chemical vapor deposition using SSPs. Processing and post-processing parameters were varied in order to modify morphology, stoichiometry, crystallography, electrical properties, and optical properties to optimize device quality. Growth at atmospheric pressure in a horizontal hotwall reactor at 395 C yielded the best device films. Placing the susceptor closer to the evaporation zone and flowing a more precursor-rich carrier gas through the reactor yielded shinier-, smoother-, and denser-looking films. Growth of (112)-oriented films yielded more Cu-rich films with fewer secondary phases than growth of (204)/(220)-oriented films. Post-deposition sulfur-vapor annealing enhanced stoichiometry and crystallinity of the films. Photoluminescence studies revealed four major emission bands and a broad band associated with deep defects. The highest device efficiency for an aerosol-assisted chemical vapor deposited cell was one percent.

Rapid thermal processing for production of chalcopyrite thin films for solar cells: Design, analysis, and experimental implementation

NASA Astrophysics Data System (ADS)

Lovelett, Robert J.

The direct conversion of solar energy to electricity, or photovoltaic energy conversion, has a number of environmental, social, and economic advantages over conventional electricity generation from fossil fuels. Currently, the most commonly-used material for photovoltaics is crystalline silicon, which is now produced at large scale and silicon-based devices have achieved power conversion efficiencies over 25% However, alternative materials, such as inorganic thin films, offer a number of advantages including the potential for lower manufacturing costs, higher theoretical efficiencies, and better performance in the field. One of these materials is the chalcopyrite Cu(InGa)(SeS) 2, which has demonstrated module efficiencies over 17% and cell efficiencies over 22%. Cu(InGa)(SeS)2 is now in the early stages of commercialization using a precursor reaction process referred to as a "selenization/sulfization" reaction. The precursor reaction process is promising because it has demonstrated high efficiency along with the large area (approximately 1 m2) uniformity that is required for modules. However, some challenges remain that limit the growth of the chalcopyrite solar cell industry including: slow reactions that limit process throughput, a limited understanding of complex reaction kinetics and transport phenomena that affect the through-film composition, and the use of highly toxic H2Se in the reaction process. In this work, I approach each of these challenges. First, to improve process throughput, I designed and implemented a rapid thermal processing (RTP) reactor, whereby the samples are heated by a 1000 W quartz-halogen lamp that is capable of fast temperature ramps and high temperature dwells. With the reactor in place, however, achieving effective temperature control in the thin film material system is complicated by two intrinsic process characteristics: (i) the temperature of the Cu(InGa)(SeS)2 film cannot be measured directly, which leaves the system without

Chemical, experimental, and morphological evidence for diagenetically altered melanin in exceptionally preserved fossils.

PubMed

Colleary, Caitlin; Dolocan, Andrei; Gardner, James; Singh, Suresh; Wuttke, Michael; Rabenstein, Renate; Habersetzer, Jörg; Schaal, Stephan; Feseha, Mulugeta; Clemens, Matthew; Jacobs, Bonnie F; Currano, Ellen D; Jacobs, Louis L; Sylvestersen, Rene Lyng; Gabbott, Sarah E; Vinther, Jakob

2015-10-13

In living organisms, color patterns, behavior, and ecology are closely linked. Thus, detection of fossil pigments may permit inferences about important aspects of ancient animal ecology and evolution. Melanin-bearing melanosomes were suggested to preserve as organic residues in exceptionally preserved fossils, retaining distinct morphology that is associated with aspects of original color patterns. Nevertheless, these oblong and spherical structures have also been identified as fossilized bacteria. To date, chemical studies have not directly considered the effects of diagenesis on melanin preservation, and how this may influence its identification. Here we use time-of-flight secondary ion mass spectrometry to identify and chemically characterize melanin in a diverse sample of previously unstudied extant and fossil taxa, including fossils with notably different diagenetic histories and geologic ages. We document signatures consistent with melanin preservation in fossils ranging from feathers, to mammals, to amphibians. Using principal component analyses, we characterize putative mixtures of eumelanin and phaeomelanin in both fossil and extant samples. Surprisingly, both extant and fossil amphibians generally exhibit melanosomes with a mixed eumelanin/phaeomelanin composition rather than pure eumelanin, as assumed previously. We argue that experimental maturation of modern melanin samples replicates diagenetic chemical alteration of melanin observed in fossils. This refutes the hypothesis that such fossil microbodies could be bacteria, and demonstrates that melanin is widely responsible for the organic soft tissue outlines in vertebrates found at exceptional fossil localities, thus allowing for the reconstruction of certain aspects of original pigment patterns.

Chemical, experimental, and morphological evidence for diagenetically altered melanin in exceptionally preserved fossils

PubMed Central

Colleary, Caitlin; Dolocan, Andrei; Gardner, James; Singh, Suresh; Wuttke, Michael; Rabenstein, Renate; Habersetzer, Jörg; Schaal, Stephan; Feseha, Mulugeta; Clemens, Matthew; Jacobs, Bonnie F.; Currano, Ellen D.; Jacobs, Louis L.; Sylvestersen, Rene Lyng; Gabbott, Sarah E.; Vinther, Jakob

2015-01-01

In living organisms, color patterns, behavior, and ecology are closely linked. Thus, detection of fossil pigments may permit inferences about important aspects of ancient animal ecology and evolution. Melanin-bearing melanosomes were suggested to preserve as organic residues in exceptionally preserved fossils, retaining distinct morphology that is associated with aspects of original color patterns. Nevertheless, these oblong and spherical structures have also been identified as fossilized bacteria. To date, chemical studies have not directly considered the effects of diagenesis on melanin preservation, and how this may influence its identification. Here we use time-of-flight secondary ion mass spectrometry to identify and chemically characterize melanin in a diverse sample of previously unstudied extant and fossil taxa, including fossils with notably different diagenetic histories and geologic ages. We document signatures consistent with melanin preservation in fossils ranging from feathers, to mammals, to amphibians. Using principal component analyses, we characterize putative mixtures of eumelanin and phaeomelanin in both fossil and extant samples. Surprisingly, both extant and fossil amphibians generally exhibit melanosomes with a mixed eumelanin/phaeomelanin composition rather than pure eumelanin, as assumed previously. We argue that experimental maturation of modern melanin samples replicates diagenetic chemical alteration of melanin observed in fossils. This refutes the hypothesis that such fossil microbodies could be bacteria, and demonstrates that melanin is widely responsible for the organic soft tissue outlines in vertebrates found at exceptional fossil localities, thus allowing for the reconstruction of certain aspects of original pigment patterns. PMID:26417094

A Perspective on Diagenetic Geometries and Patterns of Iron Oxide Cement and Coloration: Understanding Challenges and Complexities

NASA Astrophysics Data System (ADS)

Chan, M. A.; Wang, Y.

2015-12-01

Diagenetic records of fluid flow are underutilized proxies of water and environmental conditions in sedimentary rocks on Earth as well as Mars. The terrestrial iron-oxide records can be highly varied from faint wisps of coloration, to heavily cemented masses and layers. Other than vein cements, concretionary forms are some of the most prominent, yet enigmatic records. Concretions can have various mineral cement compositions with sizes that can span three orders of magnitude from mm, to cm, and m scales, in remarkably consistent, common spheroidal forms. Concretion geometries and banding may indicate directions and timings of fluid flow and precipitation, but deciphering the origins can be difficult with limited analytical tools. Definite complexities are the possibilities of: 1) overprinted events in an open system; 2) the role of organics in the nucleation and precipitation of authigenic minerals; and 3) multiple fluids, pathways, or processes that may produce similar-looking end products. In near-surface environments, likely any water since the Proterozoic has contained microbial life, and thus it seems highly probable that microbes play a significant role in the precipitation of diagenetic minerals due to the interactions of the biosphere and geosphere. However, recognition of ancient biosignatures that may have poor preservation potential remains a challenge. Iron oxides are particularly common, valuable indicators of near-surface iron cycling and are recognizable because the visual coloration. Our recent studies in Jurassic sandstones indicate preserved records of fingering at the interface of two immiscible fluids. The integration of geochemical self-organization models and field data provides new insights to understanding diagenetic fluid compositions, their relative densities, and flow direction flux and movement. These studies can have valuable implications and applications for understanding past fluid flow history, and reservoir characterization for CO2

Assessing the role of hydrogen in Fermi-level pinning in chalcopyrite and kesterite solar absorbers from first-principles calculations

NASA Astrophysics Data System (ADS)

Varley, J. B.; Lordi, V.; Ogitsu, T.; Deangelis, A.; Horsley, K.; Gaillard, N.

2018-04-01

Understanding the impact of impurities in solar absorbers is critical to engineering high-performance in devices, particularly over extended periods of time. Here, we use hybrid functional calculations to explore the role of hydrogen interstitial (Hi) defects in the electronic properties of a number of attractive solar absorbers within the chalcopyrite and kesterite families to identify how this common impurity may influence device performance. Our results identify that Hi can inhibit the highly p-type conditions desirable for several higher-band gap absorbers and that H incorporation could detrimentally affect the open-circuit voltage (Voc) and limit device efficiencies. Additionally, we find that Hi can drive the Fermi level away from the valence band edge enough to lead to n-type conductivity in a number of chalcopyrite and kesterite absorbers, particularly those containing Ag rather than Cu. We find that these effects can lead to interfacial Fermi-level pinning that can qualitatively explain the observed performance in high-Ga content CIGSe solar cells that exhibit saturation in the Voc with increasing band gap. Our results suggest that compositional grading rather than bulk alloying, such as by creating In-rich surfaces, may be a better strategy to favorably engineering improved thin-film photovoltaics with larger-band gap absorbers.

Some chemical aspects of diagenetic carbonates from the Miocene of Sitakund, Bangladesh

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akhter, S.H.; Chowdhury, S.Q.; Kandaker, N.I.

1990-05-01

A preliminary chemical and petrological study was done of the Miocene limestone and its comparison with surrounding and overlying marine shales. The material for these studies was obtained from the Miocene Surma sediments exposed in Sitakund region, Cluttagong, Bangladesh. These limestones occur in a predominantly marine shale sequence and show an apparent angular structural relationship with respect to the host marine shales. Three types of carbonates are recognized: banded limestone, dark laminated limestone, and argillaceous limestone. These are devoid of any skeletal remains and often show recrystallization phenomena. Carbonate mineral phases included calcite, aragonite, dolomite, and more rarely magnesite andmore » ankerite. Noncarbonate fraction shows quartz, although very fine grained, is intricately intergrown, indicating that it is at least recrystallized, if not authigenic. Petrographic study of these carbonates show a great variability in terms of texture and composition and suggest a complex multistep and presumably continuous diagenesis. Relatively high REE (rare earth elements) abundances in these carbonates are most likely due to diagenesis and incorporation of mobile REE from local detrital phases into diagenetic carbonates. The anomalously low abundances of cerium in all the carbonates indicates a predominantly marine source for the REE. Recrystallization of carbonate resulted in the extensive exchange of Sr and O between carbonate and diagenetic fluid, the latter being low in REE/Ca ratios. Associated marine shales have quite dissimilar trace-element signatures. This may reflect uncommon crustal sources of REE for the carbonates and clastics. The enrichment of Ni and Zn in marine shales are related to the proximality of local bedrock source areas and clay minerals in the marine sediments.« less

Assessment of diagenetic alteration of dinosaur eggshells through petrography and geochemical analysis

NASA Astrophysics Data System (ADS)

Enriquez, M. V.; Eagle, R.; Eiler, J. M.; Tripati, A. K.; Ramirez, P. C.; Loyd, S. J.; Chiappe, L.; Montanari, S.; Norell, M.; Tuetken, T.

2012-12-01

Carbonate clumped isotope analysis of fossil eggshells has the potential to constrain both the physiology of extinct animals and, potentially, paleoenvironmental conditions, especially when coupled with isotopic measurements of co-occurring soil carbonates. Eggshell samples from both modern vertebrates and Cretaceous Hadrosaurid, Oviraptorid, Titanosaur, Hypselosaurus, Faveoolithus, dinosaur fossils have been collected from Auca Mahuevo, Argentina and Rousett, France, amongst other locations, for geochemical analysis to determine if isotopic signatures could be used to indicate warm- or cold-bloodedness. In some locations soil carbonates were also analyzed to constrain environmental temperatures. In order to test the validity of the geochemical results, an extensive study was undertaken to establish degree of diagenetic alteration. Petrographic and cathodoluminescence characterization of the eggshells were used to assess diagenetic alteration. An empirical 1-5 point scale was used to assign each sample an alteration level, and the observations were then compared with the geochemical results. Specimens displayed a wide range of alteration states. Some of which were well preserved and others highly altered. Another group seemed to be structural intact and only under cathodoluminescence was alteration clearly observed. In the majority of samples, alteration level was found to be predictably related to geochemical results. From specimens with little evidence for diagenesis, carbonate clumped isotope signatures support high (37-40°C) body temperature for Titanosaurid dinosaurs, but potentially lower body temperatures for other taxa. If these data do, in fact, represent original eggshell growth temperatures, these results support variability in body temperature amongst Cretaceous dinosaurs and potentially are consistent with variations between adult body temperature and size — a characteristic of 'gigantothermy'.

Saline-water bioleaching of chalcopyrite with thermophilic, iron(II)- and sulfur-oxidizing microorganisms.

PubMed

Watling, Helen R; Collinson, David M; Corbett, Melissa K; Shiers, Denis W; Kaksonen, Anna H; Watkin, Elizabeth L J

2016-09-01

The application of thermoacidophiles for chalcopyrite (CuFeS2) bioleaching in hot, acidic, saline solution was investigated as a possible process route for rapid Cu extraction. The study comprised a discussion of protective mechanisms employed for the survival and/or adaptation of thermoacidophiles to osmotic stress, a compilation of chloride tolerances for three genera of thermoacidophiles applied in bioleaching and an experimental study of the activities of three species in a saline bioleaching system. The data showed that the oxidation rates of iron(II) and reduced inorganic sulfur compounds (tetrathionate) were reduced in the presence of chloride levels well below chloride concentrations in seawater, limiting the applicability of these microorganisms in the bioleaching of CuFeS2 in saline water. Copyright © 2016. Published by Elsevier Masson SAS.

Design of Multifunctional Materials: Chalcogenides and Chalcopyrites

NASA Technical Reports Server (NTRS)

Singh, N. B.; Su, Ching Hua; Arnold, Brad; Choa, Fow-Sen

2017-01-01

There is a strong need for developing multifunctional materials to reduce the cost of applied material without compromising the performance of the detectors, devices and sensors. The materials design, processing, growth and fabrication of bulk and nanocrystals and fabrication into devices and sensors involve huge cost and resources including a multidisciplinary team of experts. Because of this reason, prediction of multifunctionality of materials before design and development should be evaluated. Chalcogenides and chalcopyrites are a very exciting class of materials for developing multifunctionality. Materials such as Gallium selenide GaSe and zinc selenide ZnSe have been proven to be excellent examples. GaSe is a layered material and very difficult to grow in large crystal. However, it's ternary and quaternary analogs such as thallium gallium selenide TlGaSe2, thallium gallium selenide sulfide TlGaSe2-xSs, thallium arsenic selenide Tl3AsSe3, silver gallium selenide AgGaGe3Se8, AgGaGe5Se12 and several others have shown great promise for multifunctionality. Several of these materials have shown good efficiency for frequency conversion (nonlinear optical NLO), electro-optic modulation, and acousto-optic tunable filters and imagers suitable for the visible, near-infrared wavelength, mid wave infrared (MWIR), long wave infrared (LWIR) and even up to Tera hertz wavelength (THW) regions. In addition, this class of materials have demonstrated low absorption coefficients and power handling capability in the systems. Also, these crystals do not require post growth annealing, show very large transparency range and fabricability.

Development and Application of a Paleomagnetic/Geochemical Method for Constraining the Timing of Burial Diagenetic Events

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elmore, Richard D.; Engel, Michael H.

2006-01-05

Studies of diagenesis caused by fluid migration or other events are commonly hindered by a lack of temporal control. Our results to date demonstrate that a paleomagnetic/geochemical approach can be used to date fluid migration as well as burial diagenetic events. Our principal working hypothesis is that burial diagenetic processes (e.g., maturation of organic-rich sediments and clay diagenesis) and the migration of fluids can trigger the authigenesis of magnetic mineral phases. The ages of these events can be constrained by comparing chemical remanent magnetizations (CRMs) to independently established Apparent Polar Wander Paths. Whilst geochemical (e.g. stable isotope and organic analyses)more » and petrographic studies provide important clues for establishing these relationships, the ultimate test of this hypothesis requires the application of independent dating methods to verify the paleomagnetic ages. Towards this end, we have used K-Ar dating of illitization as an alternative method for constraining the ages of magnetic mineral phases in our field areas. We have made significant progress toward understanding the origin and timing of chemical remagnetization related to burial diagenetic processes. For example, a recently completed field study documents a relationship between remagnetization and the maturation of organic matter (Blumstein et al., 2004). We have tested the hypothesized connection between clay diagenesis and remagnetization by conducting K-Ar dating of authigenic illites in units in Scotland and Montana with CRMs (e.g., Elliott et al., 2006a; Elliott et al., 2006b). We have also developed a fluid related model for alteration and remagnetization of Appalachian red beds that involves reduction and mobilization of iron phases by hydrocarbons and precipitation of authigenic hematite as a result of the introduction of meteoric fluid recharge (Cox et al., 2005). In addition, our recent studies of fluid-related CRMs along faults in Scotland provide

Bacterial consortium for copper extraction from sulphide ore consisting mainly of chalcopyrite

PubMed Central

Romo, E.; Weinacker, D.F.; Zepeda, A.B.; Figueroa, C.A.; Chavez-Crooker, P.; Farias, J.G.

2013-01-01

The mining industry is looking forward for bacterial consortia for economic extraction of copper from low-grade ores. The main objective was to determine an optimal bacterial consortium from several bacterial strains to obtain copper from the leach of chalcopyrite. The major native bacterial species involved in the bioleaching of sulphide ore (Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans, Leptospirillum ferrooxidans and Leptospirillum ferriphilum) were isolated and the assays were performed with individual bacteria and in combination with At. thiooxidans. In conclusion, it was found that the consortium integrated by At. ferrooxidans and At. thiooxidans removed 70% of copper in 35 days from the selected ore, showing significant differences with the other consortia, which removed only 35% of copper in 35 days. To validate the assays was done an escalation in columns, where the bacterial consortium achieved a higher percentage of copper extraction regarding to control. PMID:24294251

Diagenetically altered fossil micrometeorites suggest cosmic dust is common in the geological record

NASA Astrophysics Data System (ADS)

Suttle, Martin D.; Genge, Matthew J.

2017-10-01

We report the discovery of fossil micrometeorites from Late Cretaceous chalk. Seventy-six cosmic spherules were recovered from Coniacian (87 ± 1 Ma) sediments of the White Chalk Supergroup. Particles vary from pristine silicate and iron-type spherules to pseudomorphic spherules consisting of either single-phase recrystallized magnetite or Fe-silicide. Pristine spherules are readily identified as micrometeorites on the basis of their characteristic mineralogies, textures and compositions. Both magnetite and silicide spherules contain dendritic crystals and spherical morphologies, testifying to rapid crystallisation of high temperature iron-rich metallic and oxide liquids. These particles also contain spherical cavities, representing weathering and removal of metal beads and irregular cavities, representing vesicles formed by trapped gas during crystallization; both features commonly found among modern Antarctic Iron-type (I-type) cosmic spherules. On the basis of textural analysis, the magnetite and Fe-silicide spherules are shown to be I-type cosmic spherules that have experienced complete secondary replacement during diagenesis (fossilization). Our results demonstrate that micrometeorites, preserved in sedimentary rocks, are affected by a suite of complex diagenetic processes, which can result in disparate replacement minerals, even within the same sequence of sedimentary beds. As a result, the identification of fossil micrometeorites requires careful observation of particle textures and comparisons with modern Antarctic collections. Replaced micrometeorites imply that geochemical signatures the extraterrestrial dust are subject to diagenetic remobilisation that limits their stratigraphic resolution. However, this study demonstrates that fossil, pseudomorphic micrometeorites can be recognised and are likely common within the geological record.

Origin and diagenetic evolution of gypsum and microbialitic carbonates in the Late Sag of the Namibe Basin (SW Angola)

NASA Astrophysics Data System (ADS)

Laurent, Gindre-Chanu; Edoardo, Perri; Ian, Sharp R.; Peacock, D. C. P.; Roger, Swart; Ragnar, Poulsen; Hercinda, Ferreira; Vladimir, Machado

2016-08-01

Ephemeral evaporitic conditions developed within the uppermost part of the transgressive Late Sag sequence in the Namibe Basin (SW Angola), leading to the formation of extensive centimetre- to metre-thick sulphate-bearing deposits and correlative microbialitic carbonates rich in pseudomorphs after evaporite crystals. The onshore pre-salt beds examined in this study are located up to 25 m underneath the major mid-Aptian evaporitic succession, which is typified at the outcrop by gypsiferous Bambata Formation and in the subsurface by the halite-dominated Loeme Formation. Carbonate-evaporite cycles mostly occur at the top of metre-thick regressive parasequences, which progressively onlap and overstep landward the former faulted (rift) topography, or fill major pre-salt palaeo-valleys. The sulphate beds are made up of alabastrine gypsum associated with embedded botryoidal nodules, dissolution-related gypsum breccia, and are cross-cut by thin satin-spar gypsum veins. Nodular and fine-grained fabrics are interpreted as being diagenetic gypsum deposits resulting from the dissolution and recrystallisation of former depositional subaqueous sulphates, whereas gypsum veins and breccia result from telogenetic processes. The carbonates display a broader diversity of facies, characterised by rapid lateral variations along strike. Thin dolomitic and calcitic bacterial-mediated filamentous microbialitic boundstones enclose a broad variety of evaporite pseudomorphs and can pass laterally over a few metres into sulphate beds. Dissolution-related depositional breccias are also common and indicate early dissolution of former evaporite layers embedded within the microbialites. Sulphate and carbonate units are interpreted as being concomitantly deposited along a tide-dominated coastal supra- to intertidal- sabkha and constitute high-frequency hypersaline precursor events, prior to the accumulation of the giant saline mid-Aptian Bambata and Loeme Formations. Petrographic and geochemical

Expression of Critical Sulfur- and Iron-Oxidation Genes and the Community Dynamics During Bioleaching of Chalcopyrite Concentrate by Moderate Thermophiles.

PubMed

Zhou, Dan; Peng, Tangjian; Zhou, Hongbo; Liu, Xueduan; Gu, Guohua; Chen, Miao; Qiu, Guanzhou; Zeng, Weimin

2015-07-01

Sulfate adenylyltransferase gene and 4Fe-4S ferredoxin gene are the key genes related to sulfur and iron oxidations during bioleaching system, respectively. In order to better understand the bioleaching and microorganism synergistic mechanism in chalcopyrite bioleaching by mixed culture of moderate thermophiles, expressions of the two energy metabolism genes and community dynamics of free and attached microorganisms were investigated. Specific primers were designed for real-time quantitative PCR to study the expression of these genes. Real-time PCR results showed that sulfate adenylyltransferase gene was more highly expressed in Sulfobacillus thermosulfidooxidans than that in Acidithiobacillus caldus, and expression of 4Fe-4S ferredoxin gene was higher in Ferroplasma thermophilum than that in S. thermosulfidooxidans and Leptospirillum ferriphilum. The results indicated that in the bioleaching system of chalcopyrite concentrate, sulfur and iron oxidations were mainly performed by S. thermosulfidooxidans and F. thermophilum, respectively. The community dynamics results revealed that S. thermosulfidooxidans took up the largest proportion during the whole period, followed by F. thermophilum, A. caldus, and L. ferriphilum. The CCA analysis showed that 4Fe-4S ferredoxin gene expression was mainly affected (positively correlated) by high pH and elevated concentration of ferrous ion, while no factor was observed to prominently influence the expression of sulfate adenylyltransferase gene.

Making a black shale shine: the interaction of hydrothermal fluids and diagenetic processes

NASA Astrophysics Data System (ADS)

Gleeson, Sarah; Magnall, Joe; Reynolds, Merilie

2016-04-01

Hydrothermal fluids are important agents of mass and thermal transfer in the upper crust. This is exemplified by shale-hosted massive sulphide deposits (SHMS), which are anomalous accumulations of Zn and Pb sulphides (± barite) in sedimentary basins created by hydrothermal fluids. These deposits occur in passive margin settings and, typically, there is no direct evidence of magmatic input. Recent studies of Paleozoic deposits in the North American Cordillera (MacMillan Pass and Red Dog Districts) have shown that the deposits are formed in a sub-seafloor setting, where the potential for thermal and chemical gradients is high. Mineralization is characterized by the replacement and displacement of unconsolidated, partially lithified and lithified biosiliceous mudstones (± carbonates), and commonly the sulphide mineralization post-dates, and replaces, bedded barite units in the sediments. The Red Dog District (Alaska, USA) contain some of the largest Zn-Pb deposits ever discovered. The host-rocks are dominantly carbonaceous mudstones, with carbonate units and some radiolarites. The ore forms massive sulphide bodies that replace pyritized mudstones, barite and carbonate units. Lithological and textural relationships provide evidence that much of the ore formed in bioturbated, biosiliceous zones that may have had high primary porosity and/or permeability. Sediment permeability may have been further modified by aging of the silica rich sediments and the dissolution/replacement of carbonate and barite beds. At the Tom and Jason deposits (MacMillan Pass, Yukon) the fault-controlled hydrothermal upflow zone is uniquely preserved as an unequivocal vent complex. Here, the metal bearing fluids are hot (300°C), low salinity (6 wt% NaCl equiv.) and acidic (pH < 4.5). These fluids were initially in thermal and chemical disequilibrium with a partially lithified organic rich host-rock but cooled rapidly during fluid rock interaction and the input of diagenetic pore fluids

Complete genome sequence of Acidihalobacter prosperus strain F5, an extremely acidophilic, iron- and sulfur-oxidizing halophile with potential industrial applicability in saline water bioleaching of chalcopyrite.

PubMed

Khaleque, Himel N; Corbett, Melissa K; Ramsay, Joshua P; Kaksonen, Anna H; Boxall, Naomi J; Watkin, Elizabeth L J

2017-11-20

Successful process development for the bioleaching of mineral ores, particularly the refractory copper sulfide ore chalcopyrite, remains a challenge in regions where freshwater is scarce and source water contains high concentrations of chloride ion. In this study, a pure isolate of Acidihalobacter prosperus strain F5 was characterized for its ability to leach base metals from sulfide ores (pyrite, chalcopyrite and pentlandite) at increasing chloride ion concentrations. F5 successfully released base metals from ores including pyrite and pentlandite at up to 30gL -1 chloride ion and chalcopyrite up to 18gL -1 chloride ion. In order to understand the genetic mechanisms of tolerance to high acid, saline and heavy metal stress the genome of F5 was sequenced and analysed. As well as being the first strain of Ac. prosperus to be isolated from Australia it is also the first complete genome of the Ac. prosperus species to be sequenced. The F5 genome contains genes involved in the biosynthesis of compatible solutes and genes encoding monovalent cation/proton antiporters and heavy metal transporters which could explain its abilities to tolerate high salinity, acidity and heavy metal stress. Genome analysis also confirmed the presence of genes involved in copper tolerance. The study demonstrates the potential biotechnological applicability of Ac. prosperus strain F5 for saline water bioleaching of mineral ores. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface modifications of chalcopyrite CuInS2 thin films for photochatodes in photoelectrochemical water splitting under sunlight irradiation

NASA Astrophysics Data System (ADS)

Gunawan; Haris, A.; Widiyandari, H.; Septina, W.; Ikeda, S.

2017-02-01

Copper chalcopyrite semiconductors include a wide range of compounds that are of interest for photoelectrochemical water splitting which enables them to be used as photochatodes for H2 generation. Among them, CuInS2 is one of the most important materials due to its optimum band gap energy for sunlight absorption. In the present study, we investigated the application of CuInS2 fabricated by electrodeposition as photochatodes for water splitting. Thin film of CuInS2 chalcopyrite was formed on Mo-coated glass substrate by stacked electrodeposition of copper and indium followed by sulfurization under H2S flow. The films worked as a H2 liberation electrode under cathodic polarization from a solution containing Na2SO4 after loading Pt deposits on the film. Introduction of an n-type CdS layer by chemical bath deposition on the CuInS2 surface before the Pt loading resulted appreciable improvements of H2 liberation efficiency and a higher photocurrent onset potential. Moreover, the use of In2S3 layer as an alternative n-type layer to the CdS significantly improved the H2 liberation performance: the CuInS2 film modified with In2S3 and Pt deposits worked as an efficient photocathode for photoelectrochemical water splitting.

Mineralogy, early marine diagenesis, and the chemistry of shallow-water carbonate sediments

NASA Astrophysics Data System (ADS)

Higgins, J. A.; Blättler, C. L.; Lundstrom, E. A.; Santiago-Ramos, D. P.; Akhtar, A. A.; Crüger Ahm, A.-S.; Bialik, O.; Holmden, C.; Bradbury, H.; Murray, S. T.; Swart, P. K.

2018-01-01

Shallow-water carbonate sediments constitute the bulk of sedimentary carbonates in the geologic record and are widely used archives of Earth's chemical and climatic history. One of the main limitations in interpreting the geochemistry of ancient carbonate sediments is the potential for post-depositional diagenetic alteration. In this study, we use paired measurements of calcium (44Ca/40Ca or δ44Ca) and magnesium (26Mg/24Mg or δ26Mg) isotope ratios in sedimentary carbonates and associated pore-fluids as a tool to understand the mineralogical and diagenetic history of Neogene shallow-water carbonate sediments from the Bahamas and southwest Australia. We find that the Ca and Mg isotopic composition of bulk carbonate sediments at these sites exhibits systematic stratigraphic variability that is related to both mineralogy and early marine diagenesis. The observed variability in bulk sediment Ca isotopes is best explained by changes in the extent and style of early marine diagenesis from one where the composition of the diagenetic carbonate mineral is determined by the chemistry of the fluid (fluid-buffered) to one where the composition of the diagenetic carbonate mineral is determined by the chemistry of the precursor sediment (sediment-buffered). Our results indicate that this process, together with variations in carbonate mineralogy (aragonite, calcite, and dolomite), plays a fundamental and underappreciated role in determining the regional and global stratigraphic expressions of geochemical tracers (δ13C, δ18O, major, minor, and trace elements) in shallow-water carbonate sediments in the geologic record. Our results also provide evidence that a large shallow-water carbonate sink that is enriched in 44Ca can explain the mismatch between the δ44/40Ca value of rivers and deep-sea carbonate sediments and call into question the hypothesis that the δ44/40Ca value of seawater depends on the mineralogy of primary carbonate precipitations (e.g. 'aragonite seas' and

Influences of Sedimentary Environments and Volcanic Sources on Diagenetic Alteration of Volcanic Tuffs in South China.

PubMed

Gong, Nina; Hong, Hanlie; Huff, Warren D; Fang, Qian; Bae, Christopher J; Wang, Chaowen; Yin, Ke; Chen, Shuling

2018-05-16

Permian-Triassic (P-Tr) altered volcanic ashes (tuffs) are widely distributed within the P-Tr boundary successions in South China. Volcanic altered ashes from terrestrial section-Chahe (CH) and marine section-Shangsi (SS) are selected to further understand the influence of sedimentary environments and volcanic sources on diagenetic alterarion on volcanic tuffs. The zircon 206 Pb/ 238 U ages of the corresponding beds between two sections are almost synchronous. Sedimentary environment of the altered tuffs was characterized by a low pH and did not experience a hydrothermal process. The dominant clay minerals of all the tuff beds are illite-smectite (I-S) minerals, with minor chlorite and kaolinite. I-S minerals of CH (R3) are more ordered than SS (R1), suggesting that CH also shows a higher diagenetic grade and more intensive chemical weathering. Besides, the nature of the volcanism of the tuff beds studied is derived from different magma sources. The clay mineral compositions of tuffs have little relation with the types of source volcanism and the depositional environments. Instead, the degree of the mixed-layer clay minerals and the REE distribution are mainly dependent upon the sedimentary environments. Thus, the mixed-layer clay minerals ratio and their geochemical index can be used as the paleoenvironmental indicator.

(S, C, O, Sr) isotopic constraints on the diagenetic evolution of the COX clay formations at the Bure URL site, Paris Basin)

NASA Astrophysics Data System (ADS)

Lerouge, C.; Gaucher, E. C.; Tournassat, C.; Agrinier, P.; Widory, D.; Guerrot, C.; Buschaert, S.

2009-04-01

The Underground Research Laboratory of Bure, located in the Eastern part of the Paris Basin, was selected by ANDRA (French Agency for Nuclear Management) in order to study the feasibility of a nuclear waste disposal in the Callovian-Oxfordian thick clayey formation at 400 meters depth. Since 1994's, numerous investigations have been initiated to understand and predict the behaviour of the clay formation in time and in space, by constraining its stability, the chemical evolution of the porewaters, and solution transfers between the clayey formation and its adjacent limestone sequences during geological times (ANDRA, 2005). In that way, this study presents combined new mineralogical and isotopic data of the diagenetic mineral sequence to constrain the porewater chemistry of the rock at different stages of the sedimentary then burial history of the clayey formation. The petrological study of Callovian-Oxfordian claystones provided evidence of the following diagenetic mineral sequence: 1) Framboïdal pyrite ± micritic calcite in replacement of carbonate bioclasts and in bioturbations, 2) Iron-rich euhedral carbonates (ankerite, sideroplesite), Glauconite, 3) Sparry dolomite, celestite in residual porosity, 4) Chalcedony 5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ34S (-38 to +74 permil/CDT), providing evidence of bacterial sulphate reduction processes. The lowest negative values (-38 to -22 permil) indicate precipitation of pyrite in a marine environment with a permanent recharge in sulphate, whereas the higher pyrite δ34S values (-14 up to +74 permil) show that pyrite precipitated in a system that closed for sulphate. Consequently the variations of pyrite δ34S in bioturbations along the lithostratigraphic profil indicate a change of sedimentation conditions from a deep marine environment to an environment with alternative recharge of marine sulphates; that is consistent with the transgression/regression cycle observed in the middle sequence

Diagenetic evidence for an epigenetic origin of the Courtbrown Zn-Pb deposit, Ireland

NASA Astrophysics Data System (ADS)

Reed, Christopher P.; Wallace, Malcolm W.

2001-08-01

Mineralisation at the Courtbrown deposit in south-western Ireland is concentrated in the basal section of the Chadian Waulsortian Limestone, immediately above the Courceyan Ballysteen Limestone. Two episodes of sulphide deposition have been identified: an early stage of minor pyrite precipitation, and a later base-metal-rich mineralisation event. Sphalerite, galena and pyrite of the later mineralisation event occur predominantly as replacement phases along stylolites, dissolution seams, and within the micritic matrix of the host limestone. These sulphide minerals also occur as cements within late stage fractures. The following diagenetic phases are present in the Waulsortian and Ballysteen Limestones in the Courtbrown area (from oldest to youngest): non-luminescent synsedimentary calcite cements, non-luminescent equant calcite cements, bright luminescent calcite cement, dull luminescent calcite cement, planar dolomite cement and replacement dolomite (regional dolomite), saddle dolomite cement, and fibrous dull luminescent calcite cement filling pressure-shadows around the sulphide minerals. Homogenisation temperatures for primary fluid inclusions within dull luminescent calcite cements (precipitated penecontemporaneously with base-metal mineralisation) range from 160 to 200 °C, with a mode at 170-180 °C. These values are unlikely to be representative of mineralisation temperatures as the fluid inclusions may have been significantly affected by heating and/or deformation during late burial (maximum paleotemperatures from Ro and CAI data around 310 °C). The observed paragenetic sequence indicates that mineralisation is completely epigenetic. As the earliest mineralisation is hosted by macro-stylolites, the sequence must have obtained a minimum burial depth of around 800 m prior to the onset of mineralisation. A burial depth of 800 m would correspond to an approximate early Chadian age for the Courtbrown area. Pressure-shadows around sphalerite further indicate

LASER APPLICATIONS AND OTHER ASPECTS OF QUANTUM ELECTRONICS Nonlinearity, optoelectronic properties, and their correlations for some mixed ternary defect chalcopyrites

NASA Astrophysics Data System (ADS)

Dutta Roy, S.

2010-12-01

The refractive index, optical nonlinearity, lowest energy band gap, and other related parameters of some mixed defect ternary chalcopyrites are calculated using Levine's bond charge model and its modification developed by Samanta et al. for multinary and mixed compounds. The dependence of the band gap energy on the average quantum number, molecular weight, and anion displacement parameter is shown for the first time, which will be very useful for designing various optoelectronic and nonlinear laser devices.

Recent Compositional Trends within the Murray Formation, Gale Crater, Mars, as seen by APXS: Implications for Sedimentary, Diagenetic and Alteration History.

NASA Astrophysics Data System (ADS)

Thompson, L. M.; Yen, A.; Spray, J. G.; Johnson, J. R.; Fraeman, A. A.; Berger, J. A.; Gellert, R.; Boyd, N.; Desouza, E.; O'Connell-Cooper, C.; VanBommel, S.

2017-12-01

The >230 m thick Murray Formation is the lower-most unit of the Mount Sharp Group, and interpreted as primarily lacustrine. Representative mudstone, siltstone and fine sandstone targets, encountered above -4330 m elevation, trend to lower Si, Al, Ti, Cr and Ca, and higher Fe, Mn, Zn, P and Mg than the Murray below. Less common, distinctive, coarser grained sandstone lenses tend to exhibit slightly different compositions to the more typical Murray but, overall, show similar elemental trends with elevation, albeit exaggerated. This suggests that the variations observed with elevation in Al, Ti, Cr, K, Fe, Mn, Zn and P within both the coarser sandstones and finer grained Murray are the result of diagenetic and/or alteration processes rather than provenance or physical sedimentary processes such as sorting. This is supported by the chemistry of obvious diagenetic, dark grey nodules, and other potential diagenetic/alteration features within this section, which show variations in the same element concentrations (i.e., P, Mn, Fe, Zn, Mg, Ca and S), distinct from diagenetic features lower down in the stratigraphy, indicating mobility of these elements within this section and changing fluid chemistry. Trends in FeO/MnO generally mimic the presence of ferric absorption features observed in visible/near infrared passive spectra from the ChemCam instrument and from CRISM orbital data, which may be consistent with changes in redox conditions as we climb up section towards Vera Rubin Ridge (Hematite Ridge). Layer-parallel CaSO4 is also common, and not observed below -4330 m. This may represent syndepositional evaporite layers, or late bedding/laminae parallel veins emplaced after lithification, in conjunction with cross-cutting veins. The overall differences in composition between the sandstone targets and finer grained Murray are attributed to distinct provenances and/or sorting during transport. We will discuss the implications of the trends and composition of the Murray above

Low-temperature heat capacity and entropy of chalcopyrite (CuFeS2): estimates of the standard molar enthalpy and Gibbs free energy of formation of chalcopyrite and bornite (Cu5FeS4)

USGS Publications Warehouse

Robie, R.A.; Wiggins, L.B.; Barton, P.B.; Hemingway, B.S.

1985-01-01

The heat capacity of CuFeS2 (chalcopyrite) was measured between 6.3 and 303.5 K. At 298.15 K, Cp,mo and Smo(T) are (95.67??0.14) J??K-1??mol-1 and (124.9??0.2) J??K-1??mol-1, respectively. From a consideration of the results of two sets of equilibrium measurements we conclude that ??fHmo(CuFeS2, cr, 298.15 K) = -(193.6??1.6) kJ??mol-1 and that the recent bomb-calorimetric determination by Johnson and Steele (J. Chem. Thermodynamics 1981, 13, 991) is in error. The standard molar Gibbs free energy of formation of bornite (Cu5FeS4) is -(444.9??2.1) kJ??mol-1 at 748 K. ?? 1985.

Bacterial and Thermochemical Sulfate Reduction in Diagenetic Settings - Old and New Insights

NASA Astrophysics Data System (ADS)

Machel, H.

2006-12-01

The association of dissolved sulfate and hydrocarbons is thermodynamically unstable in virtually all diagenetic environments. Hence, redox-reactions occur, whereby sulfate is reduced by hydrocarbons either bacterially (bacterial sulfate reduction = BSR) or inorganically (thermochemical sulfate reduction = TSR). Based on empirical evidence, BSR and TSR occur in two mutually exclusive thermal regimes, i.e., low-T and high-T diagenetic environments, respectively. BSR is common in diagenetic settings at T = 0 - 80 ° C. Above this T range, almost all sulfate reducers cease to metabolize. Those few types of hyperthermophiles that can form H2S at higher T appear to be very rare and do not normally occur and/or metabolize in geologic settings that are otherwise conducive to BSR. TSR appears to be common in geologic settings at T = 100 - 140 ° C, but in some settings T up to 180 ° C appears to be necessary. TSR does not have a sharply defined, generally valid minimum T because the onset and rate of TSR are governed by several factors that vary from place to place, i.e., the composition of the available organic reactants, kinetic inhibitors and/or catalysts, anhydrite dissolution rates, wettability, as well as migration and diffusion rates of the major reactants. A well- defined, specific minimum T for TSR can be expected only where the reservoir conditions are fairly homogeneous on the scale of a field or a play. BSR is geologically instantaneous in most geologic settings. Rates of TSR are much lower, but still geologically significant. TSR may form sour gas reservoirs and/or MVT deposits in several tens of thousands to a few million years at T = 100 - 140 ° C. BSR and TSR may be exothermic or endothermic, depending mainly on the presence or absence of specific organic reactants. The main organic reactants for BSR are organic acids and other products of aerobic or fermentative biodegradation, and those for TSR are branched and n-alkanes, followed by cyclic and mono

Tunable optical properties of ZnCdTe2-xSex(x =0.625) chalcopyrite for photovoltaics; a mBJLDA approach

NASA Astrophysics Data System (ADS)

Kashyap, Manish K.; Paudyal, D.; Harmon, B. N.

In the present study, we have performed ab-initio simulations of sp-element defect in ZnCdTe2-xSex (x =0.625) chalcopyrite to check the tuning of band gap as compared to the pristine case. The exchange and correlation (XC) effects are taken into account by an orbital independent modified Becke-Johnson (mBJ) potential as coupled with Local Density Approximation (LDA) for these calculations. The calculated energy band structures show a direct band gap at the point in the brillouin zone for the pristine as well as the defected case and the band gap decreases with inclusion of sp-disorder. The imaginary dielectric function predicts the optical band gap of pristine ZnCdTe2 very close to the experimental value and the results are in reasonable agreement without applying any scissor operator. With inclusion of sp-element defect, the optical spectra is tuned to optimal region, suitable for photovoltaics. It is apparent that mBJ functional is well suited for calculating electronic structure of pristine as well as defected ZnCdTe2chalcopyrite. MKK acknowledges financial support from UGC, India in the form of RAMAN Post-doctoral fellowship. This work at Ames Laboratory was supported by the DOE, Office of Basic Energy Sciences, Materials Sciences Division under contract No. DE-AC02-07CH11358.

Phosphorus retention and internal loading in the Bay of Quinte, Lake Ontario, using diagenetic modelling.

PubMed

Doan, Phuong T K; Watson, Sue B; Markovic, Stefan; Liang, Anqi; Guo, Jay; Mugalingam, Shan; Stokes, Jonathan; Morley, Andrew; Zhang, Weitao; Arhonditsis, George B; Dittrich, Maria

2018-04-24

Internal phosphorus (P) loading significantly contributes to hysteresis in ecosystem response to nutrient remediation, but the dynamics of sediment P transformations are often poorly characterized. Here, we applied a reaction-transport diagenetic model to investigate sediment P dynamics in the Bay of Quinte, a polymictic, spatially complex embayment of Lake Ontario, (Canada). We quantified spatial and temporal variability of sediment P binding forms and estimated P diffusive fluxes and sediment P retention in different parts of the bay. Our model supports the notion that diagenetic recycling of redox sensitive and organic bound P forms drive sediment P release. In the recent years, summer sediment P diffusive fluxes varied in the range of 3.2-3.6 mg P m -2  d -1 in the upper bay compared to 1.5 mg P m -2  d -1 in the middle-lower bay. Meanwhile sediment P retention ranged between 71% and 75% in the upper and middle-lower bay, respectively. The reconstruction of temporal trends of internal P loading in the past century, suggests that against the backdrop of reduced external P inputs, sediment P exerts growing control over the lake nutrient budget. Higher sediment P diffusive fluxes since mid-20th century with particular increase in the past 20 years in the shallower upper basins, emphasize limited sediment P retention potential and suggest prolonged ecosystem recovery, highlighting the importance of ongoing P control measures. Copyright © 2018 Elsevier B.V. All rights reserved.

Repeated occurrences of methanogenic zones, diagenetic dolomite formation and linked silicate alteration in southern Bering Sea sediments (Bowers Ridge, IODP Exp. 323 Site U1341)

NASA Astrophysics Data System (ADS)

Wehrmann, L. M.; Ockert, C.; Mix, A. C.; Gussone, N.; Teichert, B. M. A.; Meister, P.

2016-03-01

Diagenetic precipitates, such as dolomite, and the chemistry of residual deeply buried porewater often represent the only traces of past biogeochemical activity in marine sediments. A 600 m thick sedimentary section, recently drilled at Integrated Ocean Drilling Program (IODP) Site U1341 on Bowers Ridge (southern Bering Sea), provides insight into such a 4.3 Ma old paleo-diagenetic archive. Hard-lithified calcite-dolomite layers, and laminae of disseminated carbonate, were recovered in diatom-rich sediments over a depth range of 400 m. Carbon isotope values of the diagenetic carbonates between -16.6 and -14.4‰ (VPDB) and strontium isotope ratios of dolomites close to past seawater values suggest carbonate precipitation induced by the production of dissolved inorganic carbon (DIC) during elevated rates of organic carbon mineralization, primarily via sulfate reduction, at shallow sediment depth below the paleo-seafloor. Diagenetic carbonates at 280-440 m below seafloor were likely also produced by the intermittent onset of sulfate reduction coupled to the anaerobic oxidation of methane (AOM) at sulfate-methane transition zones (SMTZ). These microbially mediated processes do not occur in the sediment at this site at present but were likely connected to the presence of a methanogenic zone at 2.58-2.51 Ma. A minimum in sulfate concentrations in modern porewaters and low sedimentary Ba/Al ratios resulting from former sulfate depletion are reminiscent of the presence of this large methanogenic zone. The minimum in sulfate concentrations is reflected in a minimum in magnesium concentrations, less radiogenic strontium and isotopically light calcium in the porewater. It is proposed that magnesium was removed from the porewater during carbonate precipitation and volcanic ash alteration which occurred in the former methanogenic zone and also released strontium with a less radiogenic isotope ratio and isotopically light calcium into the porewater. The isotopic composition of

Optimization of staged bioleaching of low-grade chalcopyrite ore in the presence and absence of chloride in the irrigating lixiviant: ANFIS simulation.

PubMed

Vakylabad, Ali Behrad; Schaffie, Mahin; Naseri, Ali; Ranjbar, Mohammad; Manafi, Zahra

2016-07-01

In this investigation, copper was bioleached from a low-grade chalcopyrite ore using a chloride-containing lixiviant. In this regard, firstly, the composition of the bacterial culture media was designed to control the cost in commercial application. The bacterial culture used in this process was acclimated to the presence of chloride in the lixiviant. Practically speaking, the modified culture helped the bio-heap-leaching system operate in the chloridic media. Compared to the copper recovery from the low-grade chalcopyrite by bioleaching in the absence of chloride, bioleaching in the presence of chloride resulted in improved copper recovery. The composition of the lixiviant used in this study was a modification with respect to the basal salts in 9 K medium to optimize the leaching process. When leaching the ore in columns, 76.81 % Cu (based on solid residues of bioleaching operation) was recovered by staged leaching with lixiviant containing 34.22 mM NaCl. The quantitative findings were supported by SEM/EDS observations, X-ray elemental mapping, and mineralogical analysis of the ore before and after leaching. Finally, Adaptive neuro-fuzzy inference system (ANFIS) was used to simulate the operational parameters affecting the bioleaching operation in chloride-sulfate system.

Early diagenetic high-magnesium calcite and dolomite indicate that coal balls formed in marine or brackish water: Stratigraphic and paleoclimatic implications

NASA Astrophysics Data System (ADS)

Raymond, Anne

2016-04-01

Coal balls are carbonate and pyrite permineralizations of peat that contain three-dimensional plant fossils preserved at the cellular level. Coal balls, which occur in Pennsylvanian and earliest Permian equatorial coals, provide a detailed record of terrestrial ecology and tropical climate during the Late Paleozoic Ice Age; yet their depositional environment remains controversial. The exquisite preservation of some coal-ball fossils, e.g. pollen with pollen tubes and leaves with mesophyll, indicates rapid formation. The presence of abundant, cement-filled, void spaces within and between the plant debris in most coal balls indicates that they formed in uncompacted peat, near the surface of the mire. Botanical, taphonomic and isotopic evidence point to a freshwater origin for coal balls. The nearest living relatives of coal ball plants (modern lycopsids, sphenopsids, marratialean ferns and conifers) grow in fresh water. Coal-ball peat contains a high percentage of aerial debris, similar to modern freshwater peat. The stable oxygen isotopes of coal-ball carbonate (δ18O = 16 to 3 per mil) suggest a freshwater origin. However, the widespread occurrence of marine invertebrates and early diagenetic framboidal pyrite in coal balls suggests that many formed in close proximity to marine water. Indeed, carbonate petrology points to a marine or brackish water origin for the first-formed carbonate cements in coal balls. Petrographic and geochemical (microprobe) analysis of coal-ball carbonates in Pennsylvanian coals from the midcontinent of North America (Western Interior Basin, West Pangaea) and the Ruhr and Donets Basins (East Pangaea) indicate that the first formed carbonate is either radaxial, nonstochiometric dolomite or high magnesium calcite (9 - 17 mol % MgCO3, indicating precipitation in marine or brackish water. Although both primary dolomite and high magnesium calcite can form in lacustrine settings, the lakes in which these minerals form occur in carbonate terranes

Paleo-fluid flow in folded, poorly lithified Quaternary sediments revealed by diagenetic concretions developed during the growth of Quattro Castella Anticline (Northern Apennines, Italy)

NASA Astrophysics Data System (ADS)

Pizzati, Mattia; Balsamo, Fabrizio; Iacumin, Paola; Swennen, Rudy; Storti, Fabrizio

2017-04-01

Diagenetic concretions and mineral masses may provide a useful tool to better understand paleo-fluid flows in transforming porous media. Moreover, the selective cementation responsible of diagenetic alterations formation, plays a key role in diminishing sediments porosity and permeability and hence reservoir quality. In compressive settings of a fold-and-thrust-belt, the presence of deep or blind thrusts could lead to the generation of folds which may influence syn-kinematic sedimentation, deep fluids migration and shallow fluid flow pattern. In this contribution we present a multidisciplinary field and laboratory study on carbonate concretions developed in Quaternary poorly lithified, shallow marine syn-kinematic sediments of the Quattro Castella Anticline in Northern Apennines (Italy). The study site is located along the Enza River, where shallow marine to continental sediments are exposed along the forelimb of the fold nucleated during Late Miocene and still active today. Field mapping was aimed to link bedding attitude of syn-kinematic sediments with the geometry, arrangement, shape and size of concretionary bodies. The studied concretions are both tabular (i.e. parallel to sediment bedding) and elongate single or coalescent concretionary bodies (i.e. plunging at different angle to bedding dip throughout the stratigraphic section). Concretions dimensions range from a few centimeters in single elongate concretions, up to a few meters in tabular and coalescent ones. In situ permeability measurements and laboratory grain size analyses were performed along the studied section to constrain the petrophysical properties of sediments hosting carbonate concretions. Carbon and oxygen stable isotopes analyses on carbonate concretions (performed both on hand specimens and also on thin sections), together with petrographic and cathodoluminescence observations, were used to better constrain the diagenetic environment in which calcite precipitation occurred. Our results

Simulation of Bioleaching Heat Effects for Enhancement of Copper Recovery from Sarcheshmeh Chalcopyrite

NASA Astrophysics Data System (ADS)

Mahmoudian, Ali Reza; Sadrnezhaad, S. K.; Manafi, Zahra

2014-08-01

A heat-transfer model was formulated to determine the distribution of temperature within a bioheap of chalcopyrite of Sarcheshmeh copper mine. Bioleaching employs mixed mesophilic and thermophilic microbes for Cu extraction. Thermophiles are better than mesophiles to dissolve CuFeS2. The solution irrigation and aeration rates were taken into account as the main operational factors. The model was validated by comparing the temperature profiles of test columns with those of bioheap. The model was used to find the optimal ratio of irrigation to aeration. It was found that when the solution was fed at a flow rate of 5 kg/m2 h and air was blown at a flow rate of 7.5 kg/m2 h, the transition from a mesophilic to thermophilic state inside the heap was possible. In this situation, the maximum temperature rise inside the heap was about 332 K (59 °C) after 60 days.

An AEM-TEM study of weathering and diagenesis, Abert Lake, Oregon: II. Diagenetic modification of the sedimentary assemblage

USGS Publications Warehouse

Banfield, J.F.; Jones, B.F.; Veblen, D.R.

1991-01-01

This paper compares the mineralogy and chemistry of clay minerals in sediments from various depths and positions in Abert Lake and surrounding playa with those of the weathered materials entering the lake in order to reveal the nature and extent of post-depositional mineralogical modification. Analytical electron microscope (AEM) data from individual clay particles reveal that each sample is comprised of a highly inhomogeneous smectite assemblage. The thin clay flakes (commonly less than 10 nm wide) display a complete range in octahedral sheet compositions from nearly dioctahedral to nearly trioctahedral. The very abundant Mg-rich lake smectites with an estimated composition K0.29(Al0.23-Mg2.16Fe0.30)Si3.80Al0.20O10(OH)2 are not formed by weathering. This confirms the importance of diagenetic Mg uptake. Lattice-fringe imaging failed to reveal distinct brucite-like or vermiculite-like layers, suggesting that interstratifications of this type are rare or absent. Siliceous coatings on clay particles (identified by silica excess in smectite analyses) seem to favor topotactic overgrowth of stevensite rather than addition of brucite-like layers to the dioctahedral nuclei. The growth of K-stevensite dilutes the Al content of the crystal, and thus the increasing diagenetic modification reduces rather than supplements its illite component. Smectite compositions within individual samples were highly variable, yet source-related characteristics such as the abundance of Fe-rich smectite were apparent. Little evidence for systematic K or Mg enrichment with depth was identified in samples from depths of down to 16 feet below the sediment-water interface. The most magnesian assemblages are associated both with weathering sources of Mg-rich smectite and playa environments subjected to repeated wetting and drying cycles. Thus, the observations suggest that clay compositions primarily reflect changes in lake levels, brine composition, and source characteristics, rather than time and

Mineralogy of Nicobar Fan turbidites (IODP Leg 362): Himalayan provenance and diagenetic control.

NASA Astrophysics Data System (ADS)

Limonta, M.; Garzanti, E.; Ando, S.; Carter, A.; Milliken, K. L.; Pickering, K. T.

2017-12-01

In this study we use quantitative petrographic and heavy-mineral data on silt-sized and sand-sized sediments from the Nicobar Fan turbiditic depositional system to unravel their provenance and discriminate between pre-depositional and post-depositional processes controlling sediment mineralogy. Eighteen samples from the two drill sites U1480 e U1481, collected down to a depth of 1400 m during International Ocean Discovery Expedition 362, were selected for analysis. A complete section of the sedimentary section overlying oceanic basaltic basement was recovered at the U1480 drill site, whereas the U1481 drill site, located 35 km to the southeast, focused on the deeper interval of the sedimentary section overlying oceanic basement. Here we illustrate the compositional trends observed throughout the recovered succession, and compare heavy-mineral suites characterizing sediments drilled at the two U1480 and U1481 sites to check for potential differences in sediment provenance over a relatively short distance in trench settings. Diagenetic control with increasing burial depth was also specifically investigated. In Pleistocene sediments at depths of a few tens of meters only, rich heavy-mineral assemblages include mainly hornblende, epidote, and garnet, associated with apatite, clinopyroxene, tourmaline, sillimanite, kyanite, zircon, titanite, and rare staurolite and rutile, testifying to long-distance provenance from the Himalayan range via the Ganga-Brahmaputra fluvio-deltaic-turbiditic system. Heavy-mineral concentration shows a progressive decrease with burial depth, pointing to selective diagenetic dissolution of less durable detrital minerals. Clinopyroxene becomes rare below 400 m depth and was not recorded below 500 m depth, where amphibole decreases notably in relative abundance. More durable heavy minerals, including zircon, tourmaline, apatite, garnet and epidote, consequently tend to be relatively enriched with increasing age and burial depth. Petrographic and

Investigation on microwave heating for direct leaching of chalcopyrite ores and concentrates

NASA Astrophysics Data System (ADS)

Onol, Kubra; Saridede, Muhlis Nezihi

2013-03-01

The use of microwave energy in materials processing is a relatively new development presenting numerous advantages because of the rapid heating feature. Microwave technology has great potential to improve the extraction efficiency of metals in terms of both a reduction in required leaching time and an increase in the recovery of valuable metals. This method is especially pertinent in view of the increased demand for environment-friendly processes. In the present study, the influence of microwave heating on the direct leaching of chalcopyrite ores and concentrates were investigated. The results of microwave leaching experiments were compared with those obtained under conventional conditions. During these processes, parameters such as leaching media, temperature, and time have been worked to determine the optimum conditions for proper copper dissolution. Experimental results show that microwave leaching is more efficient than conventional leaching. The optimum leaching conditions for microwave leaching are the solid-to-liquid ratio of 1:100 g/mL, the temperature of 140°C, the solution of 0.5 M H2SO4 + 0.05 M Fe2(SO4)3, and the time of 1 h.

Dissolution characteristics of sericite in chalcopyrite bioleaching and its effect on copper extraction

NASA Astrophysics Data System (ADS)

Dong, Ying-bo; Li, Hao; Lin, Hai; Zhang, Yuan

2017-04-01

The effects of sericite particle size, rotation speed, and leaching temperature on sericite dissolution and copper extraction in a chalcopyrite bioleaching system were examined. Finer particles, appropriate temperature and rotation speed for Acidithiobacillus ferrooxidans resulted in a higher Al3+ dissolution concentration. The Al3+ dissolution concentration reached its highest concentration of 38.66 mg/L after 48-d leaching when the sericite particle size, temperature, and rotation speed were -43 μm, 30°C, and 160 r/min, respectively. Meanwhile, the sericite particle size, rotation speed, and temperature can affect copper extraction. The copper extraction rate is higher when the sericite particle size is finer. An appropriately high temperature is favorable for copper leaching. The dissolution of sericite fitted the shrinking core model, 1-(2/3) α-(1- α)2/3 = k 1 t, which indicates that internal diffusion is the decision step controlling the overall reaction rate in the leaching process. Scanning electron microscopy analysis showed small precipitates covered on the surface of sericite after leaching, which increased the diffusion resistance of the leaching solution and dissolved ions.

Thallium isotope variations in seawater and hydrogenetic, diagenetic, and hydrothermal ferromanganese deposits

USGS Publications Warehouse

Rehkamper, M.; Frank, M.; Hein, J.R.; Porcelli, D.; Halliday, A.; Ingri, J.; Liebetrau, V.

2002-01-01

Results are presented for the first in-depth investigation of TI isotope variations in marine materials. The TI isotopic measurements were conducted by multiple collector-inductively coupled plasma mass spectrometry for a comprehensive suite of hydrogenetic ferromanganese crusts, diagenetic Fe-Mn nodules, hydrothermal manganese deposits and seawater samples. The natural variability of TI isotope compositions in these samples exceeds the analytical reproducibility (?? 0.05???) by more than a factor of 40. Hydrogenetic Fe-Mn crusts have ??205TI of + 10 to + 14, whereas seawater is characterized by values as low as -8 (??205TI represents the deviation of the 205TI/203TI ratio of a sample from the NIST SRM 997 TI isotope standard in parts per 104). This ~ 2??? difference in isotope composition is thought to result from the isotope fractionation that accompanies the adsorption of TI onto ferromanganese particles. An equilibrium fractionation factor of ?? ~ 1.0021 is calculated for this process. Ferromanganese nodules and hydrothermal manganese deposits have variable TI isotope compositions that range between the values obtained for seawater and hydrogenetic Fe-Mn crusts. The variability in ??205TI in diagenetic nodules appears to be caused by the adsorption of TI from pore fluids, which act as a closed-system reservoir with a TI isotope composition that is inferred to be similar to seawater. Nodules with ??205TI values similar to seawater are found if the scavenging of TI is nearly quantitative. Hydrothermal manganese deposits display a positive correlation between ??205TI and Mn/Fe. This trend is thought to be due to the derivation of TI from distinct hydrothermal sources. Deposits with low Mn/Fe ratios and low ??205TI are produced by the adsorption of TI from fluids that are sampled close to hydrothermal sources. Such fluids have low Mn/Fe ratios and relatively high temperatures, such that only minor isotope fractionation occurs during adsorption. Hydrothermal

Geochemical gradients within modern and fossil shells of Concholepas concholepas from northern Chile: an insight into U-Th systematics and diagenetic/authigenic isotopic imprints in mollusk shells

NASA Astrophysics Data System (ADS)

Labonne, Maylis; Hillaire-Marcel, Claude

2000-05-01

Seriate geochemical measurements through shells of one modern, one Holocene, and two Sangamonian Concholepas concholepas, from marine terraces of Northern Chile, were performed to document diagenetic vs. authigenic geochemical signatures, and to better interpret U-series ages on such material. Subsamples were recovered by drilling from the outer calcitic layer to the inner aragonitic layer of each of the studied shells. Unfortunately, this sampling procedure induces artifacts, notably the convertion of up to ˜20% of calcite into aragonite, and of up to ˜6% of aragonite into calcite, as well as in the epimerization of a few percent of isoleucine into D-alloisoleucine/ L-isoleucine. Negligible sampling artifacts were noticed for stable isotope and total amino acid contents. Diagenetic effects on the geochemical properties of the shells are particularly pronounced in the inner aragonitic layer and more discrete in the outer calcitic layer. The time-dependent decay of the organic matrix of the shell is illustrated by a one order of magnitude lower total amino acid content in the Sangamonian specimens by comparison with the modern shell. Conversely, the Sangamonian shells U contents increase by a similar factor and 13C- 18O enrichments as high as 2 to 3‰ seem also to occur through the same time interval possibly due to partial replacement of aragonite by gypsum. The decay of the organic matrix of the aragonitic layer of the shell is thought to play a major role with respect to U-uptake processes and stable isotope shifts. Nevertheless, asymptotic 230Th-ages (˜100 ka) in the inner U-rich layers of the Sangamonian shells, and 234U/ 238U ratios compatible with a marine origin for U, suggest U-uptake within a short diagenetic interval, when marine waters were still bathing the embedding sediment. Thus, U-series ages on fossil mollusks from such a hyper-arid environment should not differ much from the age of the corresponding marine unit deposition. However, the

(012)-cut chalcopyrite ZnGeP2 as a high-bandwidth terahertz electro-optic detection crystal

NASA Astrophysics Data System (ADS)

Carnio, B. N.; Greig, S. R.; Firby, C. J.; Zawilski, K. T.; Schunemann, P. G.; Elezzabi, A. Y.

2017-02-01

The detection properties of a chalcopyrite zinc germanium diphosphide (ZnGeP2, ZGP) electro-optic (EO) crystal, having thickness of 1080 μm and cut along the <012> plane, is studied in the terahertz (THz) frequency range. Outstanding phase matching is achieved between the optical probe pulse and the THz frequency components, leading to a large EO detection bandwidth. ZGP has the ability to measure frequencies that are 1.3 and 1.2 times greater than that of ZnTe for crystal thicknesses of 1080 and 500 μm, respectively. Furthermore, the ZGP crystal is able to detect frequency components that are >=4.6 times larger than both ZnSe and GaP (for crystal thicknesses of 1080 μm) and >=2.2 times larger than ZnSe and GaP (for crystal thicknesses of 500 μm).

Microwave heating synthesis and formation mechanism of chalcopyrite structured CuInS{sub 2} nanorods in deep eutectic solvent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jianjun, E-mail: zhangjianjun7110@163.com; Chen, Jun; Li, Qiang

2015-03-15

Graphical abstract: Chalcopyrite structured CuInS{sub 2} nanorods were synthesized by an environmentally friendly microwave heating method in deep eutectic solvent. Results show that microwave heating time plays an important role in the formation of CuInS{sub 2} nanostructure phase. The SEM results indicated that the obtained CuInS{sub 2} nanostructures display rod-like morphology with diameters of about 40 nm and lengths of about 400 nm. The UV–vis spectrum results indicated that the CuInS{sub 2} nanorods exhibit strong absorption from the entire visible light region to the near-infrared region beyond 1100 nm. The possible growth mechanism of CuInS{sub 2} nanorods was discussed. -more » Abstract: Chalcopyrite structured CuInS{sub 2} nanorods were synthesized by an environmentally friendly microwave heating method in deep eutectic solvent. The as-synthesized CuInS{sub 2} nanorods were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), respectively. The results indicated that the obtained CuInS{sub 2} nanostructures display rod-like morphology with diameters of about 40 nm and lengths of about 400 nm. The influences of microwave heating time on the formation of CuInS{sub 2} phase were discussed. Ultraviolet–visible (UV–vis) and photoluminescence (PL) spectra were utilized to investigate the optical properties of CuInS{sub 2} nanorods. The results showed that the as-synthesized CuInS{sub 2} nanorods exhibit strong absorption from the entire visible light region to the near-infrared region beyond 1100 nm. PL spectrum of the as-synthesized CuInS{sub 2} nanorods displays an emission peak centered at 580 nm under excitation wavelength of 366 nm at room temperature. The possible growth mechanism of CuInS{sub 2} nanorods was discussed.« less

Cryogenic brines as diagenetic fluids: Reconstructing the diagenetic history of the Victoria Land Basin using clumped isotopes

NASA Astrophysics Data System (ADS)

Staudigel, Philip T.; Murray, Sean; Dunham, Daniel P.; Frank, Tracy D.; Fielding, Christopher R.; Swart, Peter K.

2018-03-01

The isotopic analyses (δ13C, δ18O, and Δ47) of carbonate phases recovered from a core in McMurdo Sound by ANtarctic geologic DRILLing (ANDRILL-2A) indicate that the majority of secondary carbonate mineral formation occurred at cooler temperatures than the modern burial temperature, and in the presence of fluids with δ18Owater values ranging between -11 and -6‰ VSMOW. These fluids are interpreted as being derived from a cryogenic brine formed during the freezing of seawater. The Δ47 values were converted to temperature using an in-house calibration presented in this paper. Measurements of the Δ47 values in the cements indicate increasingly warmer crystallization temperatures with depth and, while roughly parallel to the observed geothermal gradient, consistently translate to temperatures that are cooler than the current burial temperature. The difference in temperature suggests that cements formed when they were ∼260 ± 100 m shallower than at the present day. This depth range corresponds to a period of minimal sediment accumulation from 3 to 11 Myr; it is therefore interpreted that the majority of cements formed during this time. This behavior is also predicted by time-integrated modeling of cementation at this site. If this cementation had occurred in the presence of these fluids, then the cryogenic brines have been a longstanding feature in the Victoria Land Basin. Brines such as those found at this site have been described in numerous modern high-latitude settings, and analogous fluids could have played a role in the diagenetic history of other ice-proximal sediments and basins during glacial intervals throughout geologic history. The agreement between the calculated δ18Owater value and the measured values in the pore fluids shows how the Δ47 proxy can be used to identify the origin of negative δ18O values in carbonate rocks and that extremely negative values do not necessarily need to be a result of the influence of meteoric fluids or reaction at

A stochastic model of solid state thin film deposition: Application to chalcopyrite growth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lovelett, Robert J.; Pang, Xueqi; Roberts, Tyler M.

Developing high fidelity quantitative models of solid state reaction systems can be challenging, especially in deposition systems where, in addition to the multiple competing processes occurring simultaneously, the solid interacts with its atmosphere. In this work, we develop a model for the growth of a thin solid film where species from the atmosphere adsorb, diffuse, and react with the film. The model is mesoscale and describes an entire film with thickness on the order of microns. Because it is stochastic, the model allows us to examine inhomogeneities and agglomerations that would be impossible to characterize with deterministic methods. We demonstratemore » the modeling approach with the example of chalcopyrite Cu(InGa)(SeS){sub 2} thin film growth via precursor reaction, which is a common industrial method for fabricating thin film photovoltaic modules. The model is used to understand how and why through-film variation in the composition of Cu(InGa)(SeS){sub 2} thin films arises and persists. We believe that the model will be valuable as an effective quantitative description of many other materials systems used in semiconductors, energy storage, and other fast-growing industries.« less

A stochastic model of solid state thin film deposition: Application to chalcopyrite growth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lovelett, Robert J.; Pang, Xueqi; Roberts, Tyler M.

Developing high fidelity quantitative models of solid state reaction systems can be challenging, especially in deposition systems where, in addition to the multiple competing processes occurring simultaneously, the solid interacts with its atmosphere. Here, we develop a model for the growth of a thin solid film where species from the atmosphere adsorb, diffuse, and react with the film. The model is mesoscale and describes an entire film with thickness on the order of microns. Because it is stochastic, the model allows us to examine inhomogeneities and agglomerations that would be impossible to characterize with deterministic methods. We also demonstrate themore » modeling approach with the example of chalcopyrite Cu(InGa)(SeS) 2 thin film growth via precursor reaction, which is a common industrial method for fabricating thin film photovoltaic modules. The model is used to understand how and why through-film variation in the composition of Cu(InGa)(SeS) 2 thin films arises and persists. Finally, we believe that the model will be valuable as an effective quantitative description of many other materials systems used in semiconductors, energy storage, and other fast-growing industries.« less

A stochastic model of solid state thin film deposition: Application to chalcopyrite growth

DOE PAGES

Lovelett, Robert J.; Pang, Xueqi; Roberts, Tyler M.; ...

2016-04-01

Developing high fidelity quantitative models of solid state reaction systems can be challenging, especially in deposition systems where, in addition to the multiple competing processes occurring simultaneously, the solid interacts with its atmosphere. Here, we develop a model for the growth of a thin solid film where species from the atmosphere adsorb, diffuse, and react with the film. The model is mesoscale and describes an entire film with thickness on the order of microns. Because it is stochastic, the model allows us to examine inhomogeneities and agglomerations that would be impossible to characterize with deterministic methods. We also demonstrate themore » modeling approach with the example of chalcopyrite Cu(InGa)(SeS) 2 thin film growth via precursor reaction, which is a common industrial method for fabricating thin film photovoltaic modules. The model is used to understand how and why through-film variation in the composition of Cu(InGa)(SeS) 2 thin films arises and persists. Finally, we believe that the model will be valuable as an effective quantitative description of many other materials systems used in semiconductors, energy storage, and other fast-growing industries.« less

Early diagenetic partial oxidation of organic matter and sulfides in the Middle Pennsylvanian (Desmoinesian) Excello Shale Member of the Fort Scott Limestone and equivalents, northern Midcontinent region, USA

USGS Publications Warehouse

Hatch, J.R.; Leventhal, M.S.

1997-01-01

A process of early diagenetic partial oxidation of organic matter and sulfides has altered the chemical composition of the Middle Pennsylvanian Excello Shale Member of the Fort Scott Limestone and equivalents in the northern Midcontinent region. This process was identified by comparison of organic carbon contents, Rock-Eval hydrogen indices, organic carbon ??13C and element compositions of core and surface mine samples of the Excello Shale Member with analyses of three other underlying and overlying organic-matter-rich marine shales (offshore shale lithofacies) from southern Iowa, northern Missouri, eastern Kansas and northeastern Oklahoma. The end product of the partial oxidation process is shale with relatively low contents of hydrogen-poor, C13-enriched organic matter, lower contents of sulfur and sulfide-forming elements, and relatively unchanged contents of phosphorus and many trace elements (e.g. Cr, Ni, and V). However, because of lower organic carbon contents, element/organic carbon ratios are greatly increased. The partial oxidation process apparently took place during subaerial exposure of the overlying marine carbonate member (Blackjack Creek Member of the Fort Scott Limestone) following a marine regression when meteoric waters percolated down to the level of the Excello muds allowing oxidation of organic matter and sulfides. This hypothesis is supported by earlier workers, who have identified meteoric carbonate cements within, and soil horizons at the top of the Blackjack Creek Member. The period of oxidation is constrained in that organic matter and sulfides in the Little Osage Shale Member of the Fort Scott Limestone and equivalents (immediately overlying the Blackjack Creek Member) appear unaltered. Similar alteration of other shales in the Middle and Upper Pennsylvanian sections may be local to regional in extent and would depend on the extent and duration of the marine regression and be influenced by local variations in permeability and topography

Sedimentary Carbon, Sulfur, and Iron Relationships in Modern and Ancient Diagenetic Environments of the Eel River Basin (U.S.A.)

USGS Publications Warehouse

Sommerfield, C.K.; Aller, R.C.; Nittrouer, C.A.

2001-01-01

Depositional and diagenetic controls on the distributions of carbon, sulfur, and iron (C-S-Fe) in modern sediments and upper Pleistocene mudrocks of the Eel River Basin (ERB), northern California continental margin, were investigated using a combination of geochemical, radioisotopic, and sedimentological methods. A mass balance based on down-core profiles of porewater and solid-phase constituents and diagenetic modeling suggests that only 12-30% of the pyrite-S produced via SO4-2 reduction during burial is retained in modern shelf and upper slope deposits of the ERB. Bioturbational reoxidation of initially reduced S is inferred to be the major control on S preservation, on the basis of an observed inverse relationship between pyrite-S retention and biological mixing intensity, estimated from profiles of excess 234Th. Importantly, these findings argue that massive depositional episodes on the shelf following floods of the Eel River have a negligible long-term impact on bioturbating macrofauna and the potential to affect geochemical properties of the sediments. Down-core profiles of reactive Fe3+and Py-Fe(II) for the modern deposits suggest that highly reactive Fe phases are sulfidized well within ∼ 500-2000 years of burial, thereby limiting later pyritization, which could occur through sulfidation of less reactive phases. This result explains the low (≤ 0.4) degree of pyritization (DOP) values exhibited by both modern and ancient deposits of the ERB and lends support to the notion that pyritization in aerobic continental-margin sediments is largely associated with highly reactive detrital Fe oxides. Comparable mean C/S weight ratios for modern sediments (5.4 ± 3.3, 1σ) and mudrocks (6.9 ± 4.5) of the ERB suggest that the upper Pleistocene strata reflect a geochemical environment analogous to that of the modern margin. Specifically, the C-S-Fe signatures shared by the modern and ancient deposits are a consequence of similar detrital Fe mineralogies, initial

Synthesis and Characterization of the First Liquid Single Source Precursors for the Deposition of Ternary Chalcopyrite (CuInS2) Thin Film Materials

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K.; Cowen, Jonathan; Hepp, Aloysius

2002-01-01

Molecular engineering of ternary single source precursors based on the [{PBu3}2Cu(SR')2In(SR')2] architecture have afforded the first liquid CIS ternary single source precursors (when R = Et, n-Pr), which are suitable for low temperature deposition (< 350 C). Thermogravimetric analyses (TGA) and modulated-differential scanning calorimetry (DSC) confirm their liquid phase and reduced stability. X-ray diffraction studies, energy dispersive analyzer (EDS), and scanning electron microscopy (SEM) support the formation of the single-phase chalcopyrite CuInS2 at low temperatures.

Positive temperature variation of the bandgap energy in the single-crystalline chalcopyrite semiconductor AgInS{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ozaki, Shunji, E-mail: ozaki@el.gunma-u.ac.jp; Horikoshi, Yoshimichi

2014-02-07

Optical absorption spectra have been measured on the single-crystalline chalcopyrite semiconductor AgInS{sub 2} using polarized light at T = 10–300 K. The bandgap energy E{sub g} of AgInS{sub 2} shows unusual temperature dependence at low temperatures. The resultant temperature coefficient ∂E{sub g}/∂T is found to be positive at T < 130 K and negative above 130 K. This result has been successfully explained by considering the effects of thermal expansion and electron–phonon interaction. The free-exciton emission of photoluminescence spectra also indicates positive temperature dependence of the peak energies at low temperatures. The exciton binding energy of AgInS{sub 2} is determined to be 26.4 meV.

Prediction of electronic and optical properties of ZnAl2Te4 defect chalcopyrite semiconductor: an ab-initio study

NASA Astrophysics Data System (ADS)

Mayengbam, Rishikanta; Tripathy, S. K.; Pandey, B. P.

2018-03-01

In this paper, we have investigated the structural, electronic and optical properties of ZnAl2Te4 defect chalcopyrite semiconductor using generalized gradient approximation (GGA) within density functional theory (DFT). We have calculated the optimized lattice constants (a and c) and compared with the available experimental values. The optimized lattice constants have been used to calculate the energy band gap and found to be 1.57 eV. The partial density of states and total density of states have been discussed in detail. The frequency dependent dielectric constant and refractive index have been calculated and plotted in the energy range 0-13 eV. All the above parameters have been compared with the available experimental and theoretical values and found good agreement between them.

The community dynamics of major bioleaching microorganisms during chalcopyrite leaching under the effect of organics.

PubMed

Li, Qihou; Tian, Ye; Fu, Xian; Yin, Huaqun; Zhou, Zhijun; Liang, Yiting; Qiu, Guanzhou; Liu, Jie; Liu, Hongwei; Liang, Yili; Shen, Li; Cong, Jing; Liu, Xueduan

2011-08-01

To determine the effect of organics (yeast extract) on microbial community during chalcopyrite bioleaching at different temperature, real-time polymerase chain reaction (PCR) was employed to analyze community dynamics of major bacteria applied in bioleaching. The results showed that yeast extract exerted great impact on microbial community, and therefore influencing bioleaching rate. To be specific, yeast extract was adverse to this bioleaching process at 30°C due to decreased proportion of important chemolithotrophs such as Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. However, yeast extract could promote bioleaching rate at 40°C on account of the increased number and enhanced work of Ferroplasma thermophilum, a kind of facultative bacteria. Similarly, bioleaching rate was enhanced under the effect of yeast extract at 50°C owing to the work of Acidianus brierleyi. At 60°C, bioleaching rate was close to 100% and temperature was the dominant factor determining bioleaching rate. Interestingly, the existence of yeast extract greatly enhanced the relative competitiveness of Ferroplasma thermophilum in this complex bioleaching microbial community.

Thermoelectricity Generation and Electron-Magnon Scattering in a Natural Chalcopyrite Mineral from a Deep-Sea Hydrothermal Vent.

PubMed

Ang, Ran; Khan, Atta Ullah; Tsujii, Naohito; Takai, Ken; Nakamura, Ryuhei; Mori, Takao

2015-10-26

Current high-performance thermoelectric materials require elaborate doping and synthesis procedures, particularly in regard to the artificial structure, and the underlying thermoelectric mechanisms are still poorly understood. Here, we report that a natural chalcopyrite mineral, Cu1+x Fe1-x S2 , obtained from a deep-sea hydrothermal vent can directly generate thermoelectricity. The resistivity displayed an excellent semiconducting character, and a large thermoelectric power and high power factor were found in the low x region. Notably, electron-magnon scattering and a large effective mass was detected in this region, thus suggesting that the strong coupling of doped carriers and antiferromagnetic spins resulted in the natural enhancement of thermoelectric properties during mineralization reactions. The present findings demonstrate the feasibility of thermoelectric energy generation and electron/hole carrier modulation with natural materials that are abundant in the Earth's crust. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Review of Single Source Precursors for the Deposition of Ternary Chalcopyrite Materials

NASA Technical Reports Server (NTRS)

Banger, K. K.; Cowen, J.; Harris, J.; McClarnon, R.; Hehemann, D. G.; Duraj, S. A.; Scheiman, D.; Hepp, A. F.

2002-01-01

The development of thin-film solar cells on flexible, lightweight, space-qualified durable substrates (i.e. Kapton) provides an attractive solution to fabricating solar arrays with high specific power, (W/kg). The syntheses and thermal modulation of ternary single source precursors, based on the [{LR}2Cu(SR')2In(SR')2] architecture in good yields are described. Thermogravimetric analyses (TGA) and Low temperature Differential Scanning Caloriometry, (DSC) demonstrate that controlled manipulation of the steric and electronic properties of either the group five-donor and/or chalcogenide moiety permits directed adjustment of the thermal stability and physical properties of the precursors. TGA-Evolved Gas Analysis, confirms that single precursors decompose by the initial extrusion of the sulphide moiety, followed by the loss of the neutral donor group, (L) to release the ternary chalcopyrite matrix. X-ray diffraction studies, EDS and SEM on the non-volatile pyrolized material demonstrate that these derivatives afford single-phase CuInS2/CuInSe2 materials at low temperature. Thin-film fabrication studies demonstrate that these single source precursors can be used in a spray chemical vapor deposition process, for depositing CuInS2 onto flexible polymer substrates at temperatures less than 400 C.

Diagenetic fate of organic contaminants on the Palos Verdes Shelf, California

USGS Publications Warehouse

Eganhouse, R.P.; Pontolillo, J.; Leiker, T.J.

2000-01-01

Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6-8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT + metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p,p'-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60-70% of ??DDT. The p,p-DDE/p,p'-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p,p'-DDE is occurring. Approximately 9-23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p,p'-DDE inventory that has been observed at the study site for the period 1981-1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 102-103 times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., Mueller, S.A., Jain, M.K., Tiedje, J.M., 1998. Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280, 722-724.). This explains why the DDT composition (i.e. o,p'-, p,p'-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB

Texture-specific Si isotope variations in Barberton Greenstone Belt cherts record low temperature fractionations in early Archean seawater

NASA Astrophysics Data System (ADS)

Stefurak, Elizabeth J. T.; Fischer, Woodward W.; Lowe, Donald R.

2015-02-01

Sedimentary cherts are unusually abundant in early Archean (pre-3.0 Ga) sequences, suggesting a silica cycle that was profoundly different than the modern system. Previously applied for the purpose of paleothermometry, Si isotopes in ancient cherts can offer broader insight into mass fluxes and mechanisms associated with silica concentration, precipitation, diagenesis, and metamorphism. Early Archean cherts contain a rich suite of sedimentological and petrographic textures that document a history of silica deposition, cementation, silicification, and recrystallization. To add a new layer of insight into the chemistry of early cherts, we have used wavelength-dispersive spectroscopy and then secondary ion mass spectrometry (SIMS) to produce elemental and Si and O isotope ratio data from banded black-and-white cherts from the Onverwacht Group of the Barberton Greenstone Belt, South Africa. This geochemical data is then interpreted in the framework of depositional and diagenetic timing of silica precipitation provided by geological observations. SIMS allows the comparison of Si and O isotope ratios of distinct silica phases, including black carbonaceous chert beds and bands (many including well-defined sedimentary grains), white relatively pure chert bands including primary silica granules, early cavity-filling cements, and later quartz-filled veins. Including all chert types and textures analyzed, the δ30Si dataset spans a range from -4.78‰ to +3.74‰, with overall mean 0.20‰, median 0.51‰, and standard deviation 1.30‰ (n = 1087). Most samples have broadly similar δ30Si distributions, but systematic texture-specific δ30Si differences are observed between white chert bands (mean +0.60‰, n = 750), which contain textures that represent primary and earliest diagenetic silica phases, and later cavity-filling cements (mean -1.41‰, n = 198). We observed variations at a ∼100 μm scale indicating a lack of Si isotope homogenization at this scale during

First-principles study of structural, electronic, linear and nonlinear optical properties of Ga{2}PSb ternary chalcopyrite

NASA Astrophysics Data System (ADS)

Ouahrani, T.; Reshak, A. H.; de La Roza, A. Otero; Mebrouki, M.; Luaña, V.; Khenata, R.; Amrani, B.

2009-12-01

We report results from first-principles density functional calculations using the full-potential linear augmented plane wave (FP-LAPW) method. The generalized gradient approximation (GGA) and the Engel-Vosko-generalized gradient approximation (EV-GGA) were used for the exchange-correlation energy of the structural, electronic, linear and nonlinear optical properties of the chalcopyrite Ga2PSb compound. The valence band maximum (VBM) is located at the Γv point, and the conduction band minimum (CBM) is located at the Γc point, resulting in a direct band gap of about 0.365 eV for GGA and 0.83 eV for EV-GGA. In comparison with the experimental one (1.2 eV) we found that EV-GGA calculation gives energy gap in reasonable agreement with the experiment. The spin orbit coupling has marginal influence on the optical properties. The ground state quantities such as lattice parameters (a, c and u), bulk modules B and its pressure derivative B^primeare evaluated.

Acidithiobacillus thiooxidans secretome containing a newly described lipoprotein Licanantase enhances chalcopyrite bioleaching rate

PubMed Central

Bobadilla Fazzini, Roberto A.; Levican, Gloria

2010-01-01

The nature of the mineral–bacteria interphase where electron and mass transfer processes occur is a key element of the bioleaching processes of sulfide minerals. This interphase is composed of proteins, metabolites, and other compounds embedded in extracellular polymeric substances mainly consisting of sugars and lipids (Gehrke et al., Appl Environ Microbiol 64(7):2743–2747, 1998). On this respect, despite Acidithiobacilli—a ubiquitous bacterial genera in bioleaching processes (Rawlings, Microb Cell Fact 4(1):13, 2005)—has long been recognized as secreting bacteria (Jones and Starkey, J Bacteriol 82:788–789, 1961; Schaeffer and Umbreit, J Bacteriol 85:492–493, 1963), few studies have been carried out in order to clarify the nature and the role of the secreted protein component: the secretome. This work characterizes for the first time the sulfur (meta)secretome of Acidithiobacillus thiooxidans strain DSM 17318 in pure and mixed cultures with Acidithiobacillus ferrooxidans DSM 16786, identifying the major component of these secreted fractions as a single lipoprotein named here as Licanantase. Bioleaching assays with the addition of Licanantase-enriched concentrated secretome fractions show that this newly found lipoprotein as an active protein additive exerts an increasing effect on chalcopyrite bioleaching rate. Electronic supplementary material The online version of this article (doi:10.1007/s00253-010-3063-8) contains supplementary material, which is available to authorized users. PMID:21191788

Characterization of porosity in sulfide ore minerals: A USANS/SANS study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, F.; Zhao, J.; Etschmann, B. E.

Porosity plays a key role in the formation and alteration of sulfide ore minerals, yet our knowledge of the nature and formation of the residual pores is very limited. Herein, we report the application of ultra-small-angle neutron scattering and small-angle neutron scattering (USANS/SANS) to assess the porosity in five natural sulfide minerals (violarite, marcasite, pyrite, chalcopyrite, and bornite) possibly formed by hydrothermal mineral replacement reactions and two synthetic sulfide minerals (violarite and marcasite) prepared experimentally by mimicking natural hydrothermal conditions. USANS/SANS data showed very different pore size distributions for these minerals. Natural violarite and marcasite tend to possess less poresmore » in the small size range (<100 nm) compared with their synthetic counterparts. This phenomenon is consistent with a higher degree of pore healing or diagenetic compaction experienced by the natural violarite and marcasite. Surprisingly, nanometer-sized (<20 nm) pores were revealed for a natural pyrite cube from La Rioga, Spain, and the sample has a pore volume fraction of ~7.7%. Both chalcopyrite and bornite from the massive sulfide assemblage of the Olympic Dam deposit in Roxby Downs, South Australia, were found to be porous with a similar pore volume fraction (~15%), but chalcopyrite tends to have a higher proportion of nanometer-size pores centered at ~4 nm while bornite tends to have a broader pore size distribution. The specific surface area is generally low for these minerals ranging from 0.94 to 6.28 m2/g, and the surfaces are generally rough as surface fractal behavior was observed for all these minerals. This investigation has demonstrated that USANS/SANS is a very useful tool for analyzing porosity in ore minerals. We believe that with this quantified porosity information a deeper understanding of the complex fluid flow behavior within the porous minerals can be expected.« less

Experimental indication for band gap widening of chalcopyrite solar cell absorbers after potassium fluoride treatment

NASA Astrophysics Data System (ADS)

Pistor, P.; Greiner, D.; Kaufmann, C. A.; Brunken, S.; Gorgoi, M.; Steigert, A.; Calvet, W.; Lauermann, I.; Klenk, R.; Unold, T.; Lux-Steiner, M.-C.

2014-08-01

The implementation of potassium fluoride treatments as a doping and surface modification procedure in chalcopyrite absorber preparation has recently gained much interest since it led to new record efficiencies for this kind of solar cells. In the present work, Cu(In,Ga)Se2 absorbers have been evaporated on alkali containing Mo/soda-lime glass substrates. We report on compositional and electronic changes of the Cu(In,Ga)Se2 absorber surface as a result of a post deposition treatment with KF (KF PDT). In particular, by comparing standard X-ray photoelectron spectroscopy and synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES), we are able to confirm a strong Cu depletion in the absorbers after the KF PDT which is limited to the very near surface region. As a result of the Cu depletion, we find a change of the valence band structure and a shift of the valence band onset by approximately 0.4 eV to lower binding energies which is tentatively explained by a band gap widening as expected for Cu deficient compounds. The KF PDT increased the open circuit voltage by 60-70 mV compared to the untreated absorbers, while the fill factor deteriorated.

Lipidic biosignatures in diagenetically stabilized ironstones terraces of Rio Tinto, an acidic environment with analogies to Mars

NASA Astrophysics Data System (ADS)

Sánchez-García, L.; Carrizo, D.; Fernández-Remolar, D.; Parro, V.

2017-09-01

The characterization of extreme environments with analogies to Mars is important for understanding if/how life may have thrived in the Red Planet. Río Tinto in SW Spain is an extreme environment with constant acidic waters (mean pH of 2.3) and high concentration of heavy metals, which are direct consequence of the active metabolism of chemolithotrophic microorganisms thriving in the rich polymetallic sulfides present in the massive Iberian Pyritic Belt. Abundant minerals rich in ferric iron and sulfates, which result from the pyrite metabolism (e.g. jarosite, goethite, hematites, etc.) are of special interest for their potential for organics preservation [1]. Here, we investigate the occurrence and preservation of biological signatures in diagenetically stabilized ironstone deposits in Río Tinto, by using geolipidic markers.

Thermally Altered Silurian Cyanobacterial Mats: A Key to Earth's Oldest Fossils

NASA Astrophysics Data System (ADS)

Kazmierczak, Józef; Kremer, Barbara

2009-10-01

Diagenetic changes in thermally altered cyanobacterial mats from early Silurian black radiolarian cherts of southwestern Poland (Bardzkie Montains, Sudetes) have been studied. These early diagenetically silicified mats are composed of variously degraded remains of benthic microbes that resemble some modern chroococcalean and pleurocapsalean cyanobacteria. Two modes of degradational processes have been recognized in the studied mats: (i) early postmortem biodegradation and (ii) late diagenetic thermal or thermobaric degradation. The latter led to partial transformation of the fossilized organic remnants of cyanobacterial sheaths and capsules, which resulted in the formation of objects morphologically distant from the original microbiota but preserved features that allow for their identification as bona fide biogenic structures. Some of these thermally generated Silurian fossils are highly similar to the controversial microfossil-like carbonaceous structures described from the Early Archean Apex Chert of Australia. This similarity opens a promising way for credible recognition of remnants of cyanobacteria and similar microbiota in other thermally metamorphosed Archean sedimentary rocks

Diagenetic Microcrystalline Opal Varieties from the Monterey Formation, CA: HRTEM Study of Structures and Phase Transformation Mechanisms

NASA Technical Reports Server (NTRS)

Cady, Sherry L.; Wenk, H.-R.; DeVincenzi, Don (Technical Monitor)

1994-01-01

Microcrystalline opal varieties form as intermediary precipitates during the diagenetic transformation of biogenically precipitated non-crystalline opal (opal-A) to microquartz. With regard to the Monterey Formation of California, X-ray powder diffraction studies have shown that a decrease in the primary d-spacing of opal-CT toward that of cristobalite occurs with increasing diagenesis. The initial timing of opal-CT/quartz formation and the value of the primary opal-CT d-spacing, are influenced by the sediment. lithology. Transmission electron microscopy methods (CTEM/HRTEM) were used to investigate the structure of the diagenetic phases and establish transformation mechanisms between the varieties of microcrystalline opals in charts and porcelanites from the Monterey Formation. HRTEM images revealed that the most common fibrous varieties of microcrystalline opals contain varying amounts of structural disorder. Finite lamellar units of cristobalite-and tridymite-type. layer sequences were found to be randomly stacked in a direction perpendicular to the fiber axis. Disordered and ordered fibers were found to have coprecipitated within the same radial fiber bundles that formed within the matrix of the Most siliceous samples. HRTEM images, which reveal that the fibers within radial and lepispheric fiber bundles branch non-crystallographically, support an earlier proposal that microspheres in chert grow via a spherulitic growth mechanism. A less common variety of opal-CT was found to be characterized by non-parallel (low-angle) stacking sequences that often contain twinned lamellae. Tabular-shaped crystals of orthorhombic tridymite (PO-2) were also identified in the porcelanite samples. A shift in the primary d-spacing of opal-CT has been interpreted as an indication of solid-state ordering g toward a predominantly cristobalite structure, (opal-C). Domains of opal-C were identified as topotactically-oriented overgrowths on discrete Sections of opal-CT fibers and as

The diagenetic behavior of cutin acids in buried conifer needles and sediments from a coastal marine environment

NASA Astrophysics Data System (ADS)

Goñi, Miguel A.; Hedges, John I.

1990-11-01

Whole green, litter, and sedimentary fir, hemlock, and cedar needles and bulk sediments collected from the Dabob Bay region in Washington state were analyzed for their cutin-derived CuO reaction products. All samples yielded dihydroxyhexadecanoic acid isomers (x,ω-C 16), 16-hydroxyhexa-decanoic acid (ω-C 16), 14-hydroxytetradecanoic acid (ω-C 14), and 18-hydroxyoctadec-9-enoic acid (ω-C 18: 1) as the major cutin acids. Fir/hemlock needle mixtures were characterized by a high abundance of the 9,16-dihydroxyhexadecanoic acid positional isomer, while cedar needles produced primarily the 10,16-dihydroxy counterpart. Cutin acids accounted for ~3% of tissue C in green needles, ~4% in needle litter, 0.5-1.5% in sedimentary needles, and about 0.1% of the organic carbon (OC) in bulk sediments. Approximately 80% of the original cutin acids in fresh green needles were lost from the deepest (~100 years old) sedimentary tissues. Cutin was more reactive than lignin and polysaccharides, but more stable than the cyclitol components of the same needles. Comparative diagenetic losses of the individual cutin acids were not uniform and suggest that additional hydroxy groups and the presence of C double bonds both increase overall reactivity. The relative stability series derived for all the molecular constituents measured is: total vanillyl phenols > total P- hydroxy phenols, ferulic acid, most aldoses, bulk organic matter > mannose, ω-C 14, ω-C 16 ⩾ ω-C 18:1 > glucose, p- coumaric acid, x, ω-C 16 > all cyclitols. Diagenetically induced changes in the various cutin parameters used to characterize nonwoody vascular plant tissues were not large enough to confuse degraded conifer tissues with other cutin sources. Based on these trends, the finely disseminated cutin-bearing tissues in Dabob Bay sediments appear to be comprised approximately of equal amounts of highly degraded fir/hemlock and cedar needle fragments. According to this estimate, nonwoody vascular plant debris

Diagenetic Carbonates Related to Hydrocarbon-rich Fluid Seepage in the Nile Deep Sea Fan (East Mediterranean Sea)

NASA Astrophysics Data System (ADS)

Pierre, C.; Gontharet, S.; Blanc-Valleron, M. M.; Bayon, G.; Dupré, S.; Mascle, J.

2017-12-01

During the NAUTINIL (September-October 2003), MIMES (July 2004), BIONIL (October 2006) and MEDECO2 (November 2007) cruises, coring and submersible dives were realized in the Nile Deep Sea Fan (NDSF) area. Active fluid venting sites were identified by the presence of living benthic organisms and by methane plumes in the bottom waters above the seeping structures. At all sites, hard carbonate crusts cover irregularly the sea floor. The sediments from the venting areas are organic-rich, contain sometimes carbonate concretions and have a strong H2S smell indicative of active sulfate reduction. The mineralogy of carbonate crusts is dominated by aragonite and Mg-calcite; the mineralogy of concretions is more complex, with mixtures of Mg-calcite, dolomite and ankerite. The oxygen and carbon isotopic compositions of the carbonate from crusts and concretions exhibit large variations (-2.8< δ18O ‰ VPDB <+9.5; -42.6< δ13C ‰ VPDB <+22.4). The wide range of δ18O values reflects variable sources of fluids. Most of the authigenic carbonates from the NDSF were precipitated in isotopic equilibrium with the Mediterranean bottom water. The carbonate crusts and concretions from the brine seeps of the north-western NDSF are enriched in 18O indicating that a source of 18O-rich fluids originated from depth. Differently, a few crusts and concretions from the eastern NDSF exhibit relatively low δ18O values, which are due to precipitation at warm temperatures. The very low δ13C values of the diagenetic carbonates indicate that methane and possibly other heavier hydrocarbons were the major source of carbon that was oxidized as bicarbonate mostly through bacterial sulfate reduction coupled with anaerobic methane oxidation within the anoxic sediment. The very positive δ13C values of the diagenetic carbonates from many carbonate concretions are related to the production of 13C-rich CO2 during methanogenesis within the sub-seafloor sediments.

Fine-grained rutile in the Gulf of Maine: Diagenetic origin, source rocks, and sedimentary environment of deposition

USGS Publications Warehouse

Valentine, P.C.; Commeau, J.A.

1990-01-01

The Gulf of Maine, an embayment of the New England margin, is floored by shallow, glacially scoured basins that are partly filled with late Pleistocene and Holocene silt and clay containing 0.7 to 1.0 wt percent TiO2 chiefly in the form of silt-size rutile. Much of the rutile in the Gulf of Maine mud probably formed diagenetically in poorly cemented Carboniferous and Triassic coarse-grained sedimentary rocks of Nova Scotia and New Brunswick after the dissolution of titanium-rich detrital minerals (ilmenite, ilmenomagnetite). The diagenesis of rutile in coarse sedimentary rocks (especially arkose and graywacke) followed by erosion, segregation, and deposition (and including recycling of fine-grained rutile from shales) can serve as a model for predicting and prospecting for unconsolidated deposits of fine-grained TiO2. -from Authors

Detection of microstructural defects in chalcopyrite Cu(In,Ga)Se2 solar cells by spectrally-filtered electroluminescence

NASA Astrophysics Data System (ADS)

Skvarenina, L.; Gajdos, A.; Macku, R.; Skarvada, P.

2017-12-01

The aim of this research is to detect and localize microstructural defects by using an electrically excited light emission from a forward/reverse-bias stressed pn-junction in thin-film Cu(In; Ga)Se2 solar cells with metal wrap through architecture. A different origin of the local light emission from intrinsic/extrinsic imperfections in these chalcopyrite-based solar cells can be distinguished by a spectrally-filtered electroluminescence mapping. After a light emission mapping and localization of the defects in a macro scale is performed a micro scale exploration of the solar cell surface by a scanning electron microscope which follows the particular defects obtained by an electroluminescence. In particular, these macroscopic/microscopic examinations are performed independently, then the searching of the corresponding defects in the micro scale is rather difficult due to a diffused light emission obtained from the macro scale localization. Some of the defects accompanied by a highly intense light emission very often lead to a strong local overheating. Therefore, the lock-in infrared thermography is also performed along with an electroluminescence mapping.

Synthesis and structures of metal chalcogenide precursors

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Duraj, Stan A.; Eckles, William E.; Andras, Maria T.

1990-01-01

The reactivity of early transition metal sandwich complexes with sulfur-rich molecules such as dithiocarboxylic acids was studied. Researchers recently initiated work on precursors to CuInSe2 and related chalcopyrite semiconductors. Th every high radiation tolerance and the high absorption coefficient of CuInSe2 makes this material extremely attractive for lightweight space solar cells. Their general approach in early transition metal chemistry, the reaction of low-valent metal complexes or metal powders with sulfur and selenium rich compounds, was extended to the synthesis of chalcopyrite precursors. Here, the researchers describe synthesis, structures, and and routes to single molecule precursors to metal chalcogenides.

Experimental indication for band gap widening of chalcopyrite solar cell absorbers after potassium fluoride treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pistor, P., E-mail: paul.pistor@physik.uni-halle.de; Greiner, D.; Kaufmann, C. A.

2014-08-11

The implementation of potassium fluoride treatments as a doping and surface modification procedure in chalcopyrite absorber preparation has recently gained much interest since it led to new record efficiencies for this kind of solar cells. In the present work, Cu(In,Ga)Se{sub 2} absorbers have been evaporated on alkali containing Mo/soda-lime glass substrates. We report on compositional and electronic changes of the Cu(In,Ga)Se{sub 2} absorber surface as a result of a post deposition treatment with KF (KF PDT). In particular, by comparing standard X-ray photoelectron spectroscopy and synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES), we are able to confirm a strong Cu depletionmore » in the absorbers after the KF PDT which is limited to the very near surface region. As a result of the Cu depletion, we find a change of the valence band structure and a shift of the valence band onset by approximately 0.4 eV to lower binding energies which is tentatively explained by a band gap widening as expected for Cu deficient compounds. The KF PDT increased the open circuit voltage by 60–70 mV compared to the untreated absorbers, while the fill factor deteriorated.« less

Characterization of diagenetic siderites formed in recent and ancient ferruginous sediments of Lake Towuti, Indonesia.

NASA Astrophysics Data System (ADS)

Vuillemin, Aurele; Kallmeyer, Jens; Wagner, Dirk; Kemnitz, Helga; Wirth, Richard; Luecke, Andreas; Mayr, Christoph

2016-04-01

Authigenic minerals in lacustrine settings can be formed in the water column and within the sediment, abiotically and/or triggered by biological activity. Such minerals have been used as paleosalinity and paleoproductivity proxies, reflecting trophic state, and/or early diagenetic conditions. They have also been considered as potential biosignatures of past and present microbial activity. Here we present a study from Lake Towuti, a deep tectonic basin in Sulawesi, Indonesia. Its geographic position makes it a prime location to record paleoclimatic changes in the tropical Western Pacific warm pool in its sedimentary sequence. The ultramafic rocks and surrounding lateritic soils in the catchment area supply considerable amounts of iron and other metals to the lake. These elements further restrain primary productivity along with the development of specific microbial metabolic pathways involved in early diagenesis. Lake Towuti is stratified with anoxic conditions below 130 m, allowing metal reduction processes to take place in the hypolimnion. The extreme scarcity of sulphate and nitrate/nitrite make Lake Towuti's bottom waters a modern analogue for the Archaean Ocean. It was therefore chosen as a drilling target by the International Continental Drilling Program (ICDP). In May to July 2015, the Towuti Drilling Project recovered a total >1000 m of sediment core from three drilling sites, including a 114 m long core drilled with a contamination tracer dedicated to geomicrobiological studies. Heavy mineral fractions were extracted from core catcher samples and siderite crystals (FeCO3) were selected from different depths. Characterization of their habitus was achieved via SEM and TEM imaging. Preliminary results show that siderites grow from amorphous into nanocrystalline phases and form twinned aggregates developing into mosaic monocrystals with depth. Gradual filling of vugs and microporosity were observed along with inclusions of magnetite nanocrystals. Work in

Analysis of the structural, electronic and optic properties of Ni doped MgSiP{sub 2} semiconductor chalcopyrite compound

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kocak, Belgin, E-mail: koakbelgin@gmail.com; Ciftci, Yasemin Oztekin, E-mail: yasemin@gazi.edu.tr

2016-03-25

The structural, electronic band structure and optic properties of the Ni doped MgSiP{sub 2} chalcopyrite compound have been performed by using first-principles method in the density functional theory (DFT) as implemented in Vienna Ab-initio Simulation Package (VASP). The generalized gradient approximation (GGA) in the scheme of Perdew, Burke and Ernzerhof (PBE) is used for the exchange and correlation functional. The present lattice constant (a) follows generally the Vegard’s law. The electronic band structure, total and partial density of states (DOS and PDOS) are calculated. We present data for the frequency dependence of imaginary and real parts of dielectric functions ofmore » Ni doped MgSiP{sub 2}. For further investigation of the optical properties the reflectivity, refractive index, extinction coefficient and electron energy loss function are also predicted. Our obtained results indicate that the lattice constants, electronic band structure and optical properties of this compound are dependent on the substitution concentration of Ni.« less

Structural-Diagenetic Controls on Fracture Opening in Tight Gas Sandstone Reservoirs, Alberta Foothills

NASA Astrophysics Data System (ADS)

Ukar, Estibalitz; Eichhubl, Peter; Fall, Andras; Hooker, John

2013-04-01

In tight gas reservoirs, understanding the characteristics, orientation and distribution of natural open fractures, and how these relate to the structural and stratigraphic setting are important for exploration and production. Outcrops provide the opportunity to sample fracture characteristics that would otherwise be unknown due to the limitations of sampling by cores and well logs. However, fractures in exhumed outcrops may not be representative of fractures in the reservoir because of differences in burial and exhumation history. Appropriate outcrop analogs of producing reservoirs with comparable geologic history, structural setting, fracture networks, and diagenetic attributes are desirable but rare. The Jurassic to Lower Cretaceous Nikanassin Formation from the Alberta Foothills produces gas at commercial rates where it contains a network of open fractures. Fractures from outcrops have the same diagenetic attributes as those observed in cores <100 km away, thus offering an ideal opportunity to 1) evaluate the distribution and characteristics of opening mode fractures relative to fold cores, hinges and limbs, 2) compare the distribution and attributes of fractures in outcrop vs. core samples, 3) estimate the timing of fracture formation relative to the evolution of the fold-and-thrust belt, and 4) estimate the degradation of fracture porosity due to postkinematic cementation. Cathodoluminescence images of cemented fractures in both outcrop and core samples reveal several generations of quartz and ankerite cement that is synkinematic and postkinematic relative to fracture opening. Crack-seal textures in synkinematic quartz are ubiquitous, and well-developed cement bridges abundant. Fracture porosity may be preserved in fractures wider than ~100 microns. 1-D scanlines in outcrop and core samples indicate fractures are most abundant within small parasitic folds within larger, tight, mesoscopic folds. Fracture intensity is lower away from parasitic folds; intensity

Structural-Diagenetic Controls on Fracture Opening in Tight Gas Sandstone Reservoirs, Alberta Foothills

NASA Astrophysics Data System (ADS)

Ukar, E.; Eichhubl, P.; Fall, A.; Hooker, J. N.

2012-12-01

In tight gas reservoirs, understanding the characteristics, orientation and distribution of natural open fractures, and how these relate to the structural and stratigraphic setting are important for exploration and production. Outcrops provide the opportunity to sample fracture characteristics that would otherwise be unknown due to the limitations of sampling by cores and well logs. However, fractures in exhumed outcrops may not be representative of fractures in the reservoir because of differences in burial and exhumation history. Appropriate outcrop analogs of producing reservoirs with comparable geologic history, structural setting, fracture networks, and diagenetic attributes are desirable but rare. The Jurassic to Lower Cretaceous Nikanassin Formation from the Alberta Foothills produces gas at commercial rates where it contains a network of open fractures. Fractures from outcrops have the same diagenetic attributes as those observed in cores <100 km away, thus offering an ideal opportunity to 1) evaluate the distribution and characteristics of opening mode fractures relative to fold cores, hinges and limbs, 2) compare the distribution and attributes of fractures in outcrop vs. core samples, 3) estimate the timing of fracture formation relative to the evolution of the fold-and-thrust belt, and 4) estimate the degradation of fracture porosity due to postkinematic cementation. Cathodoluminescence images of cemented fractures in both outcrop and core samples reveal several generations of quartz and ankerite cement that is synkinematic and postkinematic relative to fracture opening. Crack-seal textures in synkinematic quartz are ubiquitous, and well-developed cement bridges abundant. Fracture porosity may be preserved in fractures wider than ~100 microns. 1-D scanlines in outcrop and core samples indicate fractures are most abundant within small parasitic folds within larger, tight, mesoscopic folds. Fracture intensity is lower away from parasitic folds; intensity

Reactive transport and mass balance modeling of the Stimson sedimentary formation and altered fracture zones constrain diagenetic conditions at Gale crater, Mars

NASA Astrophysics Data System (ADS)

Hausrath, E. M.; Ming, D. W.; Peretyazhko, T. S.; Rampe, E. B.

2018-06-01

On a planet as cold and dry as present-day Mars, evidence of multiple aqueous episodes offers an intriguing view into very different past environments. Fluvial, lacustrine, and eolian depositional environments are being investigated by the Mars Science Laboratory Curiosity in Gale crater, Mars. Geochemical and mineralogical observations of these sedimentary rocks suggest diagenetic processes affected the sediments. Here, we analyze diagenesis of the Stimson formation eolian parent material, which caused loss of olivine and formation of magnetite. Additional, later alteration in fracture zones resulted in preferential dissolution of pyroxene and precipitation of secondary amorphous silica and Ca sulfate. The ability to compare the unaltered parent material with the reacted material allows constraints to be placed on the characteristics of the altering solutions. In this work we use a combination of a mass balance approach calculating the fraction of a mobile element lost or gained, τ, with fundamental geochemical kinetics and thermodynamics in the reactive transport code CrunchFlow to examine the characteristics of multiple stages of aqueous alteration at Gale crater, Mars. Our model results indicate that early diagenesis of the Stimson sedimentary formation is consistent with leaching of an eolian deposit by a near-neutral solution, and that formation of the altered fracture zones is consistent with a very acidic, high sulfate solution containing Ca, P and Si. These results indicate a range of past aqueous conditions occurring at Gale crater, Mars, with important implications for past martian climate and environments.

The use of strontium and barium analyses for the reconstruction of the diet of the early medieval coastal population of Gdańsk (Poland): A preliminary study.

PubMed

Szostek, Krzysztof; Głab, Henryk; Pudło, Aleksandra

2009-01-01

Barium and strontium analyses yield an important perspective on temporal shifts in diet in relation to social and environmental circumstances. This research focuses on reconstructing dietary strategies of individuals in the early medieval (12-13th century) population of Gdańsk on the coast of the Baltic Sea. To describe these strategies where seafood rich in minerals was included in the diet, levels of strontium, barium, calcium and phosphorus were measured in first permanent molars of adult men and women whose remains were excavated from the churchyard in the city centre. Faunal remains from the excavation were analysed as an environmental background with respect to the content of the above-mentioned elements. The impact of diagenesis on the odontological material under study was also determined by an analysis of the soil derived from the grave and non-grave surroundings. For verification of diagenetic processes, the calcium/phosphorus index was used. Strontium, calcium, phosphorus and barium levels were determined with the spectrophotometric method using the latest generation plasma spectrophotometer Elan 6100 ICP-MS. From the results of the analysis of taphonomic parameters such as the soil pH, potential ion exchange in the grave surroundings and the Ca/P ratio, it can be inferred that diagenetic factors had little impact on the studied material. From this pilot study we can conclude that in the early Middle Ages in the Baltic Sea basin, seafood was included in the diet from early childhood and at the same time the diet contained calcium-rich milk products (also rich in minerals). The lack of sex differences may indicate the absence of a sex-specific nutritional strategy in childhood and early adolescence.

dSED: A database tool for modeling sediment early diagenesis

NASA Astrophysics Data System (ADS)

Katsev, S.; Rancourt, D. G.; L'Heureux, I.

2003-04-01

Sediment early diagenesis reaction transport models (RTMs) are becoming powerful tools in providing kinetic descriptions of the metal and nutrient diagenetic cycling in marine, lacustrine, estuarine, and other aquatic sediments, as well as of exchanges with the water column. Whereas there exist several good database/program combinations for thermodynamic equilibrium calculations in aqueous systems, at present there exist no database tools for classification and analysis of the kinetic data essential to RTM development. We present a database tool that is intended to serve as an online resource for information about chemical reactions, solid phase and solute reactants, sorption reactions, transport mechanisms, and kinetic and equilibrium parameters that are relevant to sediment diagenesis processes. The list of reactive substances includes but is not limited to organic matter, Fe and Mn oxides and oxyhydroxides, sulfides and sulfates, calcium, iron, and manganese carbonates, phosphorus-bearing minerals, and silicates. Aqueous phases include dissolved carbon dioxide, oxygen, methane, hydrogen sulfide, sulfate, nitrate, phosphate, some organic compounds, and dissolved metal species. A number of filters allow extracting information according to user-specified criteria, e.g., about a class of substances contributing to the cycling of iron. The database also includes bibliographic information about published diagenetic models and the reactions and processes that they consider. At the time of preparing this abstract, dSED contained 128 reactions and 12 pre-defined filters. dSED is maintained by the Lake Sediment Structure and Evolution (LSSE) group at the University of Ottawa (www.science.uottawa.ca/LSSE/dSED) and we invite input from the geochemical community.

Diagenesis in coastal carbonates related to Pleistocene sea level, Bermuda Platform

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vollbrecht, R.; Meischner, D.

1996-01-01

Pleistocene glacioeustatic sea-level oscillation on the stable Bermuda Platform is expressed in a succession of shallow-water carbonates interrupted by lowstand unconformities. In Bermuda, the maximum highstands of the last 400,000 yr ranged within 10 m around the present level. Coastal carbonates of various highstands are exposed along the present shoreline. These carbonates were penetrated by meteoric and marine pore waters during lowstands and highstands following on deposition. Two representative Pleistocene shoreline sections were studied to see whether early diagenesis has recorded these pore-water changes. The sediments of both sections show multiple generations of cement. Optical and scanning electron microscopy, cathodoluminescencemore » microscopy, X-ray diffraction, microprobe studies and stable-isotope analyses were used to determine the diagenetic environments involved. Regardless of the degree of substrate cementation, freshwater alteration was mainly vadose whereas marine cementation was either phreatic or vadose or both. Early diagenetic oscillation is easier recorded in coastal successions than in lagoonal sediments, mainly because marine cementation is more active nearshore.Because the coastal environment is prone to wave destruction, the potential for preserving these diagenetic features is usually low. Data published on tectonically unstable areas suggest that early diagenetic oscillation may characterize stable coastlines.« less

Gold paragenesis and chemistry at Batu Hijau, Indoneisa: implications for gold-rich porphyry copper deposits

NASA Astrophysics Data System (ADS)

Arif, J.; Baker, T.

2004-10-01

Gold is an important by-product in many porphyry-type deposits but the distribution and chemistry of gold in such systems remains poorly understood. Here we report the results of petrographic, electron microprobe, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and flotation test studies of gold and associated copper sulfides within a paragenetic framework from the world-class Batu Hijau (914 mt @ 0.53% Cu, 0.40 g/t Au) porphyry copper gold deposit, Indonesia. Unlike many other porphyry copper gold deposits, early copper minerals (bornite digenite chalcocite) are well preserved at Batu Hijau and the chalcopyrite pyrite overprint is less developed. Hence, it provides an excellent opportunity to study the entire gold paragenesis of the porphyry system. In 105 polished thin sections, 699 native gold grains were identified. Almost all of the native gold grains occurred either within quartz veins, attached to sulfide, or as free gold along quartz or silicate grain boundaries. The native gold grains are dominantly round in shape and mostly 1 12 μm in size. The majority of gold was deposited during the formation of early ‘A’ veins and is dominantly associated with bornite rather than chalcopyrite. The petrographic and LA-ICP-MS study results indicate that in bornite-rich ores gold mostly occurs within copper sulfide grains as invisible gold (i.e., within the sulfide structure) or as native gold grains. In chalcopyrite-rich ores gold mostly occurs as native gold grains with lesser invisible gold. Petrographic observations also indicate a higher proportion of free gold (native gold not attached to any sulfide) in chalcopyrite-rich ores compared to bornite rich ores. The pattern of free gold distribution appears to correlate with the flotation test data, where the average gold recovery value from chalcopyrite-rich ores is consistently lower than bornite-rich ores. Our data suggest that porphyry copper-gold deposits with chalcopyrite-rich ores

Detection of diagenetic processes in bones: the case of Arkoudospilia cave, N. Greece

NASA Astrophysics Data System (ADS)

Zisi, Nikoleta; Dotsika, Elissavet; Tsoukala, Evangelia; Psomiadis, David

2010-05-01

Diagenesis of bone material over geological time is a highly complex phenomenon involving the physical, chemical, histological and mechanical alterations that occur at different time scales from the time of death to present and depend on the local geochemical conditions. The significance of diagenesis and the information that can provide its decoding, led to its study by a variety of physicochemical techniques. Despite serious research efforts, a detailed scenario of bone diagenesis remains elusive. The δ18O of the carbonate material of hydroxyapatite of the bones is though to be a good indicator of the δ18O of the local water precipitation and therefore can be used for palaeoclimatic reconstraction, while δ13C is used for definition of palaeodiet habits. The study of isotopic composition requires the detection of the diagenetic degree, because both δ18O and δ13C can be contaminated by these processes. Stable carbon and oxygen isotope values (δ13C, δ18O) were obtained for structural carbonate in the hydroxy-apatite of bear bones from Arkoudospilia Cave, Pella, N. Greece. The age range of the fossil layers is from 32ka BP to a maximum of 38ka BP (radiocarbon dating). The findings belong to Ursus ingressus, an extinct cave bear. The difficulty in studying an extinct species lies to the fact that it cannot be easily correlated with a present one, so it is impossible to determine the diagenesis by the analytical deviation. However, in order to include the environmental and climatic differences of the past and modern bear habitats, the isotopic composition of the water should be also included in the study. Cave bears are considered to be endemic in Europe. The shortage of data in literature concerning cave bears isotopic analyses in combination with the burden of the difficulties in spotting and sampling such rare materials makes difficult to compare the results of a study. The diet and the physiology of this species are not well known. However the morphology of

Recognition of primary and diagenetic magnetizations to determine the magnetic polarity record and timing of deposition of the moat-fill rocks of the Oligocene Creede Caldera, Colorado

USGS Publications Warehouse

Reynolds, Richard L.; Rosenbaum, Joseph G.; Sweetkind, Donald S.; Lanphere, Marvin A.; Robert, Andrew P.; Verosub, Kenneth L.

2000-01-01

postdepositional magnetite and maghemite that formed in rocks in which most or all detrital megnetic iron oxide was destroyed. Incipient oxidation of early diagenetic pyrite may have normal polarity Snowshoe Mountain Tuff (26.89 ± 0.0 Ma, 1 δ) and on the normal polarity postcaldera Fisher lava flows (as young as 26.23 ± 0.05 Ma, 1 δ) indicate that deposition of the Creede Formation spanned about 340-660 k.y. The intermittently defined normal polarity magnetization for the caldera-fill sequence, compared with different versions of the geomagnetic polarity time scale, is consistent with the shorter time span.

Relationship between karstification and burial dolomitization in Permian platform carbonates (Lower Khuff - Oman)

NASA Astrophysics Data System (ADS)

Beckert, Julia; Vandeginste, Veerle; John, Cédric M.

2016-08-01

Large breccia fabrics associated with karst constitute an important structure in massive limestone successions. The dimensions and shapes of breccia structures are controlled by the initial fracture pattern of the limestone and preferential pathways of the karstifying fluids, but subsequently breccia fabrics can also govern the migration of later fluids. Therefore, breccias are highly relevant features to capture for reservoir characterisation. Outcrop analogues for Lower Khuff units in the Middle East present in the Central Oman Mountains reveal brecciated fabrics up to 10s of metres in diameter. These brecciated units are closely associated with dolomite bodies of late diagenetic origin. Based on an integrated set of data, the breccias are interpreted as collapsed karst cavities either formed by meteoric or hypogenic fluids. The exact origin of the fluids could not be constrained due to an overprint by later dolomitizing fluids. Based on the composition of the clasts and matrix in the breccias, two dolomitization events are interpreted to have affected the succession, one prior to (early diagenetic [ED] dolomite) and one after brecciation (late diagenetic [DT2] dolomite). Dolomite of shallow burial origin (ED dolomite) was only observed as clasts within breccia and is much more frequent than late diagenetic (medium to deep burial) dolomite clasts. Thus, the timing of the brecciation and collapse is assumed to postdate shallow burial early diagenetic dolomitization. Late diagenetic replacive dolomite (DT2 dolomite) forms 90% of the matrix in the breccia fabrics with the exception of a small area that was not affected by dolomitization, but is rarely present as clasts. Stable isotope measurements [δ18O: - 2.5‰ to - 6‰ VPDB and δ13C: 2.9‰ to 4.8‰ VPDB] suggest a burial origin for the late diagenetic dolomite potentially with the participation of hydrothermal fluids. The dolomitized matrix indicates a migration of late dolomitizing fluids subsequent to or

Active hematite concretion formation in modern acid saline lake sediments, Lake Brown, Western Australia

NASA Astrophysics Data System (ADS)

Bowen, Brenda Beitler; Benison, K. C.; Oboh-Ikuenobe, F. E.; Story, S.; Mormile, M. R.

2008-04-01

Concretions can provide valuable records of diagenesis and fluid-sediment interactions, however, reconstruction of ancient concretion-forming conditions can be difficult. Observation of modern hematite concretion growth in a natural sedimentary setting provides a rare glimpse of conditions at the time of formation. Spheroidal hematite-cemented concretions are actively precipitating in shallow subsurface sediments at Lake Brown in Western Australia. Lake Brown is a hypersaline (total dissolved solids up to 23%) and acidic (pH ˜ 4) ephemeral lake. The concretion host sediments were deposited between ˜ 1 and 3 ka, based on dating of stratigraphically higher and lower beds. These age constraints indicate that the diagenetic concretions formed < 3 ka, and field observations suggest that some are currently forming. These modern concretions from Lake Brown provide an example of very early diagenetic formation in acid and saline conditions that may be analogous to past conditions on Mars. Previously, the hematite concretions in the Burns formation on Mars have been interpreted as late stage diagenetic products, requiring long geologic time scales and multiple fluid flow events to form. In contrast, the Lake Brown concretions support the possibility of similar syndepositional to very early diagenetic concretion precipitation on Mars.

Origin and timing of Dauphiné twins in quartz cement in fractured sandstones from diagenetic environments: Insight from fluid inclusions

NASA Astrophysics Data System (ADS)

Fall, András; Ukar, Estibalitz; Laubach, Stephen E.

2016-09-01

Electron backscattered diffraction techniques (EBSD) show that Dauphiné twins in quartz are widespread in many tectonometamorphic environments. Our study documents that under diagenetic temperatures (< 200 °C) and burial depths < 5 km Dauphiné twins are common in isolated fracture quartz deposits spanning between fracture walls (i.e., quartz bridges) in low-porosity quartz-cemented sandstones. Using examples from East Texas and Colorado cores, we show that twins are associated with crack-seal microstructure and fluid inclusions. Fracture wall-parallel and wall-normal inclusion trails contain coexisting aqueous and hydrocarbon gas inclusions, so homogenization temperatures of aqueous inclusions record true trapping temperatures. Inclusions in alignments normal to fracture walls are large and irregularly shaped compared to those aligned parallel to walls, but both show similar liquid-to-vapor ratios. Stacking transmitted light images with scanning electron microscope cathodoluminescence (SEM-CL) and EBSD images demonstrates that Dauphiné twin boundaries are localized along wall-normal inclusion trails. Trapping temperatures for wall-normal inclusion trails are usually higher than those aligned parallel to the fracture wall. Wall-normal fluid inclusion assemblage temperatures typically match the highest temperatures of wall-parallel assemblages trapped during sequential widening, but not necessarily the most recent. In context of burial histories for these samples, this temperature pattern implies that wall-normal assemblages form at discrete times during or after crack-seal fracture widening. Localization in isolated, potentially high-stress quartz deposits in fractures is compatible with a mechanical origin for these Dauphiné twins. Punctuated temperature values and discrepant sizes and shapes of inclusions in wall-normal trails implies that twinning is a by-product of the formation of the wall-normal inclusion assemblages. The association of Dauphiné twins

Identification of novel sulfur-containing steroids in sediments and petroleum: probable incorporation of sulfur into δ 5,7-sterols during early diagenesis

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Schouten, Stefan; de Leeuw, Jan W.; van Duin, Adri C. T.; Geenevasen, Jan A. J.

1999-01-01

A novel sulfur-containing sterane, 4α,7α-epithio-5β-cholestane, has been identified in a sediment extract from the Miocene Northern Apennines marl (Italy) after its isolation by column chromatography and high pressure liquid chromatography. The compound has been characterised by GC-MS and mild Nickel boride desulfurisation and one and two-dimensional 1H NMR techniques. C 27-C 29 homologs have been detected in sediment extracts of three different formations and in one petroleum sample. These sulfur-containing steroids are probably formed by an intramolecular reaction of inorganic sulfides with early diagenetic products of Δ 5,7-sterols.

Temperature and composition of carbonate cements record early structural control on cementation in a nascent deformation band fault zone: Moab Fault, Utah, USA

NASA Astrophysics Data System (ADS)

Hodson, Keith R.; Crider, Juliet G.; Huntington, Katharine W.

2016-10-01

Fluid-driven cementation and diagenesis within fault zones can influence host rock permeability and rheology, affecting subsequent fluid migration and rock strength. However, there are few constraints on the feedbacks between diagenetic conditions and structural deformation. We investigate the cementation history of a fault-intersection zone on the Moab Fault, a well-studied fault system within the exhumed reservoir rocks of the Paradox Basin, Utah, USA. The fault zone hosts brittle structures recording different stages of deformation, including joints and two types of deformation bands. Using stable isotopes of carbon and oxygen, clumped isotope thermometry, and cathodoluminescence, we identify distinct source fluid compositions for the carbonate cements within the fault damage zone. Each source fluid is associated with different carbonate precipitation temperatures, luminescence characteristics, and styles of structural deformation. Luminescent carbonates appear to be derived from meteoric waters mixing with an organic-rich or magmatic carbon source. These cements have warm precipitation temperatures and are closely associated with jointing, capitalizing on increases in permeability associated with fracturing during faulting and subsequent exhumation. Earlier-formed non-luminescent carbonates have source fluid compositions similar to marine waters, low precipitation temperatures, and are closely associated with deformation bands. The deformation bands formed at shallow depths very early in the burial history, preconditioning the rock for fracturing and associated increases in permeability. Carbonate clumped isotope temperatures allow us to associate structural and diagenetic features with burial history, revealing that structural controls on fluid distribution are established early in the evolution of the host rock and fault zone, before the onset of major displacement.

Early Triassic fluctuations of the global carbon cycle: New evidence from paired carbon isotopes in the western USA basin

NASA Astrophysics Data System (ADS)

Caravaca, Gwénaël; Thomazo, Christophe; Vennin, Emmanuelle; Olivier, Nicolas; Cocquerez, Théophile; Escarguel, Gilles; Fara, Emmanuel; Jenks, James F.; Bylund, Kevin G.; Stephen, Daniel A.; Brayard, Arnaud

2017-07-01

In the aftermath of the catastrophic end-Permian mass extinction, the Early Triassic records recurrent perturbations in the carbon isotope signal, most notably during the Smithian and through the Smithian/Spathian Boundary (SSB; 1.5 myr after the Permian/Triassic boundary), which show some of the largest excursions of the Phanerozoic. The late Smithian also corresponds to major biotic turnovers and environmental changes, such as temperature fluctuations, that deeply impacted the recovery after the end-Permian mass extinction. Here we document the paired carbon isotope signal along with an analysis of the trace and major elements at the long-known Hot Springs section (southeastern Idaho, USA). This section records Early Triassic sediments from the Griesbachian-Dienerian up to the lower Spathian. We show that the organic and carbonate δ13C variations mirror the signals identified at a global scale. Particularly, the middle Smithian-SSB event represented by a negative-positive isotopic couplet is well identified and is not of diagenetic origin. We also document a positive excursion potentially corresponding to the Dienerian/Smithian Boundary. Observed Smithian-Spathian excursions are recorded similarly in both the organic and carbonate reservoirs, but the organic matter signal systematically shows unexpectedly dampened variations compared to its carbonate counterpart. Additionally, we show that variations in the net isotopic effect (i.e., Δ13C) probably resulted from a complex set of forcing parameters including either a mixing between terrestrial and marine organic matter depending on the evolution of the depositional setting, or variations in the biological fractionation. We establish that the Δ13C signal cannot be directly related to CO2-driven temperature variations at Hot Springs. Even though the carbon isotope signal mirrors the Early Triassic variations known at the global scale, the Hot Springs signal probably also reflects local influences on the carbon

Origin and Timing of Dauphiné Twins Using Fluid Inclusions in Quartz-Cement Fractures in Sandstones from Diagenetic Environments

NASA Astrophysics Data System (ADS)

Fall, A.; Ukar, E.; Laubach, S.

2016-12-01

Dauphiné twins in quartz are widespread in many tectonometamorphic environments. Under diagenetic temperatures (<200°C) and burial depths less than 5 km Dauphiné twins are also common in isolated fracture quartz deposits spanning between fracture walls in low-porosity quartz-cemented sandstones. The twin boundaries coincide with fracture wall-normal fluid inclusion trails. The association of Dauphiné twins and fluid inclusion trails from which temperature and possibly timing can be inferred provides a way to research mechanism and timing of twinning, and potentially the magnitude of paleostrain and stress in some diagenetic settings. Using examples from East Texas and Colorado cores, we show that twins are associated with crack-seal microstructure and fluid inclusions. Fracture wall-parallel and wall-normal inclusion trails contain coexisting aqueous and hydrocarbon gas inclusions, so homogenization temperatures of aqueous inclusions, ranging from 130°C to 159°C in the East Texas Basin, and from 162°C to 176°C in the Piceance Basin, record true trapping temperatures. Inclusions in wall-normal trails are large and irregularly shaped compared to those in wall-parallel trails, but both show similar liquid-to-vapor ratios. Trapping temperatures for wall-normal inclusion trails are usually higher than those in the wall-parallel trails. Wall-normal fluid inclusion assemblage temperatures typically match the highest temperatures of wall-parallel assemblages trapped during sequential widening, but not necessarily the most recent. In context of burial histories for these samples, this temperature pattern implies that wall-normal assemblages form at discrete times during or after crack-seal fracture widening. Stacking transmitted light images with scanning electron microscope cathodoluminescence (SEM-CL) and electron backscattered diffraction (EBSD) images demonstrates that the twin boundaries are localized along wall-normal inclusion trails. Localization in isolated

Natural flows of H2-rich fluids in the ophiolites of Oman and the Philippines: Tectonic control of migration pathways and associated diagenetic processes

NASA Astrophysics Data System (ADS)

Deville, E. P.; Prinzhofer, A.; Vacquand, C.; Chavagnac, V.; Monnin, C.; Ceuleneer, G.; Arcilla, C. A.

2009-12-01

We compare the geological environments of sites of emission of natural hydrogen in the Oman ophiolite and the Zambales ophiolite (Luzon, Philippines). The genesis of natural H2 results from the interaction between ultrabasic rocks and aqueous solutions circulating in deep fracture networks, by oxidation of metals (Fe2+, Mn2+) and reduction of water, probably under high temperature conditions. This process generates very reducing conditions capable of destabilizing other molecules (notably reduction of deep CO2 being transformed into CH4 by Fisher-Tropsch type reactions). Nitrogen is also commonly associated to the H2-rich fluids. H2 flows are associated with the expulsion of hyperalkaline waters rich in ions OH- and Ca2+ and characterized by high pH (between 11 and 12). Most alkaline springs are found in the vicinity of major faults and/or lithological discontinuities like the basal thrust plane of the ophiolites and the peridotite-gabbro contact (Moho). Within the fracture networks, gas and water separate probably at shallow depth, i.e. close to the top of the upper aquifer level. Locally high flows of gas migrate vertically through fracture pathways and they are able to inflame spontaneously on the surface. Aqueous fluids tends to migrate laterally in the fracture network toward the creeks where most of the hyperalkaline springs are found. This water circulation induces a chain of diagenetic reactions starting in the fracture systems and continuing at the surface where it leads to the precipitation of calcite, aragonite, brucite and more rarely portlandite. This chain of diagenetic reactions is associated with the capture of the atmospheric CO2 during the precipitation of carbonates.

Unravelling the Paleoenvironmental and Diagenetic History of Fluviolacustrine Sediments from a Northern Kenya Rift Basin Through Analysis of HSPDP West Turkana-Kaitio Core Material

NASA Astrophysics Data System (ADS)

Rabideaux, N. M.; Chaudhary, M. S.; Deocampo, D.; Feibel, C. S.; Cohen, A. S.

2016-12-01

The Hominin Sites and Paleolakes Drilling Project (HSPDP) collected sediment cores from six rift basins in Ethiopia and Kenya. The goal of HSPDP is to construct high-resolution records of environmental change, and to understand how those changes relate to early human evolution and cultural adaptations. The West Turkana-Kaitio (WTK) site was targeted due to the abundant archeological and paleontological artifacts and fossils discovered around the basin. We conducted XRD and XRF analyses on HSPDP-WTK core material to construct a high-resolution record of paleoenvironmental conditions in the Kenya Rift during the Early Pleistocene ( 1.9-1.35 Ma). Mineralogical and geochemical trends were also used to identify the diagenetic history of fluviolacustrine sediments in the basin. The bulk mineralogy is comprised of mostly detrital feldspars, muscovite, α-quartz, and carbonates. Zeolites are present in intervals throughout the core, possibly suggesting pulses of increased salinity. Oxides and S-bearing minerals are abundant from 100-170 mbs, which may be indicative of redox and or hydrothermal processes in that interval. The lowermost portion of the core contains α- and β-quartz, pyrite and zeolites, suggesting either low-oxygen saline conditions or hydrothermal activity. Oriented clay analysis indicated multiple intervals of diagenesis, with the illitization of smectite related to hydrothermal and or microbial activity. Clay analysis provided evidence for a low degree of illitization in the upper portion of the core, whereas mixed-layered illite-smectite (I/S) contained 30-50% illite proximal to fault breccia and up to 70% illite below the faulted section, indicative of significant alteration in the lowermost portion of the core. Coupled mineralogical and geochemical analysis revealed a complex alteration history in the basin indicated by: 1) the presence of mixed-layer I/S throughout the 216 m core; 2) pronounced alteration proximal to faulting; and 3) authigenic

Characterization of Primary Carrier Transport Properties of the Light-Harvesting Chalcopyrite Semiconductors CuIn(S 1–xSe x) 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frick, Jessica J.; Kushwaha, Satya K.; Cava, Robert J.

We report the carrier transport properties of CuIn(S 1-xSe x) 2 (0 ≤ x ≤ 1), a promising chalcopyrite semiconductor series for solar water splitting. A low concentration Mg dopant is used to decrease the carrier resistivity through facilitating bulk p-type transport at ambient temperature. Temperature-dependent resistivity measurements reveal a four-order magnitude decrease in bulk electrical resistivity (from 10 3 to 10 –1 Ohm cm) for 1% Mg-doped CuIn(S 1–xSe x) 2 as x increases from 0 to 1. Hall effect measurements at room temperature reveal p-type majority carrier concentrations that vary from 10 15 to 10 18 cm –3more » and mobilities of approximately 1–10 cm 2 V –1 s –1. These results provide insights into the fundamental carrier transport properties of CuIn(S 1–xSe x) 2 and will be of value in optimizing these materials further for photoelectrochemistry applications.« less

Characterization of Primary Carrier Transport Properties of the Light-Harvesting Chalcopyrite Semiconductors CuIn(S 1–xSe x) 2

DOE PAGES

Frick, Jessica J.; Kushwaha, Satya K.; Cava, Robert J.; ...

2017-07-27

We report the carrier transport properties of CuIn(S 1-xSe x) 2 (0 ≤ x ≤ 1), a promising chalcopyrite semiconductor series for solar water splitting. A low concentration Mg dopant is used to decrease the carrier resistivity through facilitating bulk p-type transport at ambient temperature. Temperature-dependent resistivity measurements reveal a four-order magnitude decrease in bulk electrical resistivity (from 10 3 to 10 –1 Ohm cm) for 1% Mg-doped CuIn(S 1–xSe x) 2 as x increases from 0 to 1. Hall effect measurements at room temperature reveal p-type majority carrier concentrations that vary from 10 15 to 10 18 cm –3more » and mobilities of approximately 1–10 cm 2 V –1 s –1. These results provide insights into the fundamental carrier transport properties of CuIn(S 1–xSe x) 2 and will be of value in optimizing these materials further for photoelectrochemistry applications.« less

Quantifying the impact of early calcite cementation on the reservoir quality of carbonate rocks: A 3D process-based model

NASA Astrophysics Data System (ADS)

Hosa, Aleksandra; Wood, Rachel

2017-06-01

The reservoir properties of carbonate rocks are controlled by both deposition and diagenesis. The latter includes the early precipitation of calcite cements, which can exert a strong control on the evolution of subsequent diagenetic pathways. We quantify the impact of early marine cement growth in grainstones on evolving pore space by examining trends in the relationship between cementation and permeability using a 3D process-based model (Calcite3D). The model assumes varying proportions of polycrystalline and monocrystalline grain types, upon which we grow isopachous and syntaxial calcite cement types, respectively. We model two syntaxial cement shapes, compact and elongated, that approximate the geometries of typical rhombohedral calcite forms. Results demonstrate the effect of cement competition: an increasing proportion of monocrystalline grains creates stronger competition and a reduction in the impact of individual grains on final calcite cement volume and porosity. Isopachous cement is effective in closing pore throats and limiting permeability. We also show that the impact of syntaxial cement on porosity occlusion and therefore flow is highly dependent on monocrystalline grain location and the orientation of crystal axes. This demonstrates the importance of diagenetic overprint in controlling the evolution of rock properties, but also that this process can be essentially random. We also show that diagenesis alone can create notable heterogeneity in the permeability of carbonates. While Calcite3D is successful in modelling realistic changes in cement volumes and pore space morphology, modelled permeabilities (0.01 -30D) are above the range reported in reservoir grainstones due to the very high permeability of the initial synthetic sediment deposit (58.9D). Poroperm data generated by Calcite3D, however, exhibits a linear relationship between the logarithms of porosity and permeability with a high coefficient of determination, as observed in natural media.

Diagenetic changes in Concholepas concholepas shells (Gastropoda, Muricidae) in the hyper-arid conditions of Northern Chile - implications for palaeoenvironmental reconstructions

NASA Astrophysics Data System (ADS)

Guzmán, N.; Dauphin, Y.; Cuif, J. P.; Denis, A.; Ortlieb, L.

2009-02-01

Variations in the chemical composition of fossil biogenic carbonates, and in particular of mollusc shells, have been used in a range of palaeoenvironmental reconstructions. It is of primary importance, therefore, to detect and understand the diagenetic processes that may modify the original chemical signature. This microstructural and biogeochemical study focuses on modern and fossil (Holocene and Pleistocene) shells of a littoral gastropod of Northern Chile, and on the characterization of mineral component transformations at the nanometric scale and concomitant intracrystalline organic compound modifications. The inner aragonite layer of the shell exhibits more complex deteriorations than the calcite layer. This preliminary study confirms that physical and chemical alterations of various components of mollusc shell biocrystals are complex and might manifest in different ways even within a single individual. The single criterion of determining the mineralogical composition to verify the conservation state of shell samples is insufficient.

Diagenetic changes in Concholepas concholepas shells (Gastropoda, Muricidae) in the hyper-arid conditions of Northern Chile - implications for palaeoenvironmental reconstructions

NASA Astrophysics Data System (ADS)

Guzman, N.; Dauphin, Y.; Cuif, J. P.; Denis, A.; Ortlieb, L.

2008-02-01

Variations on chemical composition in fossil biogenic carbonates, and in particular of mollusk shells, have been used in a range of palaeoenvironmental reconstructions. Therefore, it is of primary importance to detect and understand the diagenetic processes that may modify the original chemical signature. This microstructural and biogeochemical study focuses on modern and fossil (Pleistocene and Holocene) shells of a littoral gastropod of Northern Chile, and on the characterization of mineral component transformations at the nanometric scale and concomitant intracrystalline organic compound modifications. The inner aragonite layer of the shell exhibits more complex deteriorations than the calcite layer. This preliminary study confirms that physical and chemical alterations of various components of mollusk shell biocrystals are complex and might manifest in different ways even within a single individual. The single criterion of determining the mineralogical composition to attest shell sample conservation state should not be considered as sufficient.

Examining the diagenetic alteration of human bone material from a range of archaeological burial sites using nuclear microscopy

NASA Astrophysics Data System (ADS)

Elliott, T. A.; Grime, G. W.

1993-05-01

The inorganic analysis of archaeological bone material can potentially provide a wealth of information about the chronology, diet and palaeoenvironment of past populations: for example, strontium and uranium levels are used in palaeodietary and dating studies, respectively. However, the extent to which the chemical composition of bone is subject to diagenetic change during burial is open to controversy due, in part, to differences in analytical technique, bone types and burial conditions. To investigate this problem, archaeological human bone material from a number of different geological environments including Pompeii and a 12th century British ecclesiastical site, together with material from two seawater burials (The "Mary Rose" and a 6th century Mediterranean wreck) have been studied using the nuclear microprobe facility at the University of Oxford. Results using microbeam PIXE show that bone is subject to contamination from a wide range of trace elements depending on the burial conditions. Elemental maps are presented to demonstrate the distribution of trace element accumulation under different burial conditions, and the significance of this work to future trace element studies is discussed.

High-Temperature Formation Phases and Crystal Structure of Hot-Pressed Thermoelectric CuGaTe2 with Chalcopyrite-Type Structure

NASA Astrophysics Data System (ADS)

Fujii, Yosuke; Kosuga, Atsuko

2017-11-01

Polycrystalline CuGaTe2 with a chalcopyrite-type structure consolidated by hot-pressing is a potential candidate as a medium-temperature thermoelectric (TE) material. However, its high-temperature formation phases have rarely been reported to date. Here, we investigated the temperature-dependent formation phases and crystal structure at 300-800 K of hot-pressed CuGaTe2. From synchrotron x-ray diffraction data and crystal structure analysis of the heating and cooling processes, it was clarified that a certain amount of impurity phases, such as Te and CuTe, precipitated from the CuGaTe2 matrix when the temperature was increased (to 500-650 K). This is the temperature range where CuGaTe2 has been reported to show high TE performance. After CuGaTe2 was heated to 800 K, such impurity phases remained, even when cooled to room temperature. They also affected the tetragonal distortion and the x-coordinate of Te in the CuGaTe2 matrix, probably due to deficiencies of Cu and Te in the matrix. Our results reveal detailed information on the formation phases of CuGaTe2 at high temperature and thus provide insight for evaluation of its high-temperature stability and transport properties.

Radiative transitions in highly doped and compensated chalcopyrites and kesterites: The case of Cu2ZnSnS4

NASA Astrophysics Data System (ADS)

Teixeira, J. P.; Sousa, R. A.; Sousa, M. G.; da Cunha, A. F.; Fernandes, P. A.; Salomé, P. M. P.; Leitão, J. P.

2014-12-01

The theoretical models of radiative recombinations in both CuIn1 -xGaxSe2 chalcopyrite and Cu2ZnSnS4 kesterite, and related compounds, were revised. For heavily doped materials, electrons are free or bound to large donor agglomerates which hinders the involvement of single donors in the radiative recombination channels. In this work, we investigated the temperature and excitation power dependencies of the photoluminescence of Cu2ZnSnS4-based solar cells in which the absorber layer was grown through sulphurization of multiperiod structures of precursor layers. For both samples the luminescence is dominated by an asymmetric band with peak energy at ˜1.22 eV, which is influenced by fluctuating potentials in both conduction and valence bands. A value of ˜60 meV was estimated for the root-mean-square depth of the tails in the conduction band. The radiative transitions involve the recombination of electrons captured by localized states in tails of the conduction band with holes localized in neighboring acceptors that follow the fluctuations in the valence band. The same acceptor level with an ionization energy of ˜280 meV was identified in both absorber layers. The influence of fluctuating potentials in the electrical performance of the solar cells was discussed.

High-Temperature Formation Phases and Crystal Structure of Hot-Pressed Thermoelectric CuGaTe2 with Chalcopyrite-Type Structure

NASA Astrophysics Data System (ADS)

Fujii, Yosuke; Kosuga, Atsuko

2018-06-01

Polycrystalline CuGaTe2 with a chalcopyrite-type structure consolidated by hot-pressing is a potential candidate as a medium-temperature thermoelectric (TE) material. However, its high-temperature formation phases have rarely been reported to date. Here, we investigated the temperature-dependent formation phases and crystal structure at 300-800 K of hot-pressed CuGaTe2. From synchrotron x-ray diffraction data and crystal structure analysis of the heating and cooling processes, it was clarified that a certain amount of impurity phases, such as Te and CuTe, precipitated from the CuGaTe2 matrix when the temperature was increased (to 500-650 K). This is the temperature range where CuGaTe2 has been reported to show high TE performance. After CuGaTe2 was heated to 800 K, such impurity phases remained, even when cooled to room temperature. They also affected the tetragonal distortion and the x-coordinate of Te in the CuGaTe2 matrix, probably due to deficiencies of Cu and Te in the matrix. Our results reveal detailed information on the formation phases of CuGaTe2 at high temperature and thus provide insight for evaluation of its high-temperature stability and transport properties.

Les minéralisations Cu_(Ni_Bi_U_Au_Ag) d'Ifri (district du Haut Seksaoua, Maroc) : apport de l'étude texturale au débat syngenèse versus épigenèseThe Cu_(Ni_Bi_U_Au_Ag) mineralization of Ifri ('Haut Seksaoua' district, Morocco): contribution of a textural study to the discussion syngenetic versus epigenetic

NASA Astrophysics Data System (ADS)

Barbanson, Luc; Chauvet, Alain; Gaouzi, Aziz; Badra, Lakhifi; Mechiche, Mohamed; Touray, Jean Claude; Oukarou, Saı̈d

2003-11-01

The Cu ore of Ifri is a chalcopyrite stockwork hosted by Cambrian formations and was until now interpreted as a syngenetic massive sulphide deposit. Textural studies highlight two generations of pyrite early (Py I) and late (Py II) with respect to the regional deformation. The chalcopyrite stockwork overprinted Py II, outlining the epigenetic nature of the Cu mineralization. Regarding the origin of Cu-depositing fluids, the presence in the stockwork paragenesis of an U, W, Sn association and preliminary Pb/Pb dating of a brannerite belonging to this association suggest a contribution of the Tichka granite. To cite this article: L. Barbanson et al., C. R. Geoscience 335 (2003).

Impact on sediments and water by release of copper from chalcopyrite bearing rock due to acidic mine drainage

NASA Astrophysics Data System (ADS)

Shukla, Anoop Kant; Pradhan, Manoj; Tiwari, Onkar Nath

2018-04-01

Mining activity causes transition of rock-mass from its original position in earth into open environment. The action of environmental elements such air, water, microorganisms leads to oxidation of minerals which constitute the rock. The oxidation of sulphide minerals in presence of moisture releases acidic mine discharge (AMD). The acidic nature of AMD causes leaching of metals from rock minerals. Dissolution of other minerals may occur upon reaction with AMD. Chalcopyrite (CuFeS2) undergoes oxidation in acidic condition releasing copper among other products. This study reveals contamination of copper in sediment samples and seepage water from the tailing dam of a large copper project in located in central India. Elevation was studied using GIS to ascertain to the topographic elevation of tailing dam area. It was located at relatively high altitude causing seepage to flow away from tailing dam. The seepage water from tailing dam was found to be acidic with mean pH value of 4.0 and elevated copper content. Similarly, sediments from seepage water flow displayed elevated copper concentration. The copper concentration in seepage water was found with a mean value of 10.73 mg/l. The sediments from seepage water flow also displayed elevated copper concentration with mean value of 26.92 g/kg. This indicates impact on sediments by release of copper due to acidic mine drainage.

Flavins in Coastal Marine Sediments: New Perspectives on Diagenetic Electron Transfer

NASA Astrophysics Data System (ADS)

Monteverde, D.; Berelson, W.; Baronas, J. J.; Sanudo-Wilhelmy, S. A.

2016-02-01

Coastal marine sediments play a critical role in the global cycling of metals and nutrients, many of which undergo diagenetic alteration. Central to these transformations are redox reactions where electron-rich organic matter is oxidized via transfer to terminal electron acceptors (NO3-, MnOx, FeOx, SO42-). The flavins (flavin adenine dinucleotide [FAD], flavin mononucleotide [FMN], and riboflavin [B2]) are microbially synthesized organic coenzymes that perform both single and double electron transfer and are known to mediate reduction of insoluble metal oxides. Culture experiments have found high rates of flavin excretion in metal-reducing Shewanella and Geobacter species, however environmental measurements of these highly labile molecules have not been previously reported. Here we present porewater measurements of FAD, FMN, and B2 from San Pedro Basin. This California Borderland basin is silled, suboxic, 900 m deep, and experiences high sedimentation. Flavin concentrations ranged from pico- (FAD: 0- 60 pM; B2: 40 - 90 pM) to nanomolar (FMN: 0.4 - 1.2 nM). The concentration cascade of FMN>B2>FAD fits well within culture experiments. Interestingly, profiles of all three flavins show a near linear increase with depth from 0-30 cm and a relatively steady concentration from 30-45 cm, supporting likely in situ production. Additionally, the flavins showed a negative correlation with dissolved Fe (R2 = 0.7 for FMN, 0.8 for FAD, and 0.9 for B2), which decreased linearly with depth from 160µM to 65µM. We discuss hypothesized mechanisms controlling flavin concentrations based on a suite of sediment geochemical parameters (dissolved Fe, Mn, TCO2, δ13C, NH3, DOM, and SO42-) as well as implications for microbial redox syntrophy. These data provide a critical link between the extensive culture-based mechanistic understanding of flavin function and the sedimentary environment. Furthermore, these results demonstrate that flavins likely serve as a significant electron transfer

High-pressure study of the structural and elastic properties of defect-chalcopyrite HgGa2Se4

NASA Astrophysics Data System (ADS)

Gomis, O.; Vilaplana, R.; Manjón, F. J.; Santamaría-Pérez, D.; Errandonea, D.; Pérez-González, E.; López-Solano, J.; Rodríguez-Hernández, P.; Muñoz, A.; Tiginyanu, I. M.; Ursaki, V. V.

2013-02-01

In this work, we focus on the study of the structural and elastic properties of mercury digallium selenide (HgGa2Se4) which belongs to the family of AB2X4 ordered-vacancy compounds with tetragonal defect chalcopyrite structure. We have carried out high-pressure x-ray diffraction measurements up to 13.2 GPa. Our measurements have been complemented and compared with total-energy ab initio calculations. The equation of state and the axial compressibilities for the low-pressure phase of HgGa2Se4 have been experimentally and theoretically determined and compared to other related ordered-vacancy compounds. The theoretical cation-anion and vacancy-anion distances in HgGa2Se4 have been determined. The internal distance compressibility in HgGa2Se4 has been compared with those that occur in binary HgSe and ɛ-GaSe compounds. It has been found that the Hg-Se and Ga-Se bonds behave in a similar way in the three compounds. It has also been found that bulk compressibility of the compounds decreases following the sequence "ɛ-GaSe > HgGa2Se4 > HgSe." Finally, we have studied the pressure dependence of the theoretical elastic constants and elastic moduli of HgGa2Se4. Our calculations report that the low-pressure phase of HgGa2Se4 becomes mechanically unstable above 13.3 GPa.

Contrasting diagenetic histories of concretions vs. host rocks, Lion Mountain Member, Riley formation (upper Cambrian), Texas

DOE Office of Scientific and Technical Information (OSTI.GOV)

McBride, E.F.

1988-02-01

White, elliptical, calcite-cemented concretion nuclei up to 1 m long contrast markedly in color, composition, and diagenetic history from more glauconite-rich concretion rinds and from dark-green glaucarenite host rocks. Concretion nuclei are loosely packed deposits of trilobite carapaces and minor quartz and glauconite that have intergranular volumes of 58%. The nuclei are shell-lag deposits that were cemented by calcite at the sea floor or after burial of a few meters. Concretion rinds, composed of subequal amounts of quartz and compactionally deformed glauconite, have an intergranular volume of only 32% and minor quartz overgrowths that preceded pore-occluding calcite cement. The rindsmore » underwent burial for several million years to tens of millions of years to depths of several hundred meters before they were cemented. The host rock is predominately glauconite with very minor quartz and calcite cement. Strontium isotopic ratios of host-rock calcite cement are variable (0.7084 to 0.7093), but the lowest value suggests precipitation during the Middle Ordovician. In the absence of significant amounts of carbonate cement, the host rock underwent complete dissolution of trilobite carapaces and maximum compaction with total loss of porosity through squashing of glauconite grains. Maximum burial during this stage was completed by the end of Ordovician time.« less

Depositional and diagenetic models of some miocene evaporites on the Red Sea coast, Egypt

NASA Astrophysics Data System (ADS)

El Sayed A. A., Youssef

1986-06-01

The Miocene evaporites on the Red Sea coast, Egypt, are interpreted as a sabkha-chenier complex, which includes deposition in shallow water as well as in supratidal environments Costal sabkhas and shallow subaqueous evaporite sequences are recognised. The subaqueous sequence is represented by nodular mosaic and massive crystalline gypsum covered by a surface layer of nodular, white, dense powdery anhydrite. The sabkha sequences are represented by (a) small mounds overlying the older rock unit (Gebel El Rusas Formation) composed of fenestral stromatolitic and nodular dolomites overlain by a dolomitic limestone layer, (b) thin layer overlying the subaqueous evaporite sequence and composed of fenestral stromatolitic dolomite overlain by a nodular anhydrite layer. The nodular structure in the subaqueous as well as the sabkha sequences is formed diagenetically by transformation and recrystallization process. The dolomites in both sabkha sequences (a and b) are characterised by low Na + concentrations (143 to 755 ppm) and low values of δ 18O (- 1.85 to -8.7‰ PDB). This indicates that the dolomites were formed from saline water mixed with fresh water. These dolomites are also characterised by a low δ 13C (-12.95 to -27.1‰ PDB). This shows that the light carbon produced by the degradation of organic matter through the sulphate reduction process has played a significant role in the formation of these dolomites. Both microcrystalline and megacrystalline white dolomites are recognised in sabkha sequences. Relatively high concentrations of lead, zinc and copper are associated with the high percent of megacrystalline white dolomite.

Comparison of the diagenetic and reservoir quality evolution between the anticline crest and flank of an Upper Jurassic carbonate gas reservoir, Abu Dhabi, United Arab Emirates

NASA Astrophysics Data System (ADS)

Morad, Daniel; Nader, Fadi H.; Gasparrini, Marta; Morad, Sadoon; Rossi, Carlos; Marchionda, Elisabetta; Al Darmaki, Fatima; Martines, Marco; Hellevang, Helge

2018-05-01

This petrographic, stable isotopic and fluid inclusion microthermometric study of the Upper Jurassic limestones of an onshore field, Abu Dhabi, United Arab Emirates (UAE) compares diagenesis in flanks and crest of the anticline. The results revealed that the diagenetic and related reservoir quality evolution occurred during three phases, including: (i) eogenesis to mesogenesis 1, during which reservoir quality across the field was either deteriorated or preserved by calcite cementation presumably derived from marine or evolved marine pore waters. Improvement of reservoir quality was due to the formation of micropores by micritization of allochems and creation of moldic/intragranular pores by dissolution of peloids and skeletal fragments. (ii) Obduction of Oman ophiolites and formation of the anticline of the studied field was accompanied by cementation by saddle dolomite and blocky calcite. High homogenization temperatures (125-175 °C) and high salinity (19-26 wt% NaCl eq) of the fluid inclusions, negative δ18OVPDB values (-7.7 to -2.9‰), saddle shape of dolomite, and the presence of exotic cements (i.e. fluorite and sphalerite) suggest that these carbonates were formed by flux of hot basinal brines, probably related to this tectonic compression event. (iii) Mesogenesis 2 during subsidence subsequent to the obduction event, which resulted in extensive stylolitization and cementation by calcite. This calcite cement occluded most of the remaining moldic and inter-/intragranular pores of the flank limestones (water zone) whereas porosity was preserved in the crest. This study contributes to: (1) our understanding of differences in the impact of diagenesis on reservoir quality evolution in flanks and crests of anticlines, i.e. impact of hydrocarbon emplacement on diagenesis, and (2) relating various diagenetic processes to burial history and tectonic events of foreland basins in the Arabian Gulf area and elsewhere.

Clues to early diagenetic sulfurization processes from mild chemical cleavage of labile sulfur-rich geomacromolecules

NASA Astrophysics Data System (ADS)

Adam, P.; Schneckenburger, P.; Schaeffer, P.; Albrecht, P.

2000-10-01

suggests that polysulfide-bound unsaturated thiols are intermediates formed during the first sulfurization steps occurring soon after deposition and that they are rapidly transformed by various processes taking place during early diagenesis, notably to yield their saturated counterparts.

Depositional and diagenetic processes of Qa Khanna playa, North Jordan basaltic plateau, Jordan

NASA Astrophysics Data System (ADS)

Howari, F. M.; Banat, K. M.; Abu-Salha, Y. A.

2010-09-01

The present study explored mineral occurrences and sediment characteristics of playas from northern Jordan and explained depositional and diagenetic processes as reflected from bulk chemistry and sedimentary structures. Mudcracks of different sizes and shape patterns, laminations, intersediment vesicles, and bioturbation pipes are the main sedimentary structures. Plagioclase, olivine, orthopyroxene, nepheline and other opaque minerals are all of detrital origin, and are derived from the basaltic bedrocks surrounding the studied playa. Evaporites are very rare; they are represented only by trace amounts of gypsum. The identified clay minerals in the clay fraction of the studied sediments, arranged according to their decreasing abundances are palygorskite, illite, kaolinite, smectite and chlorite. The elemental abundances were tied to clay, CaCO 3 and nearby igneous rocks. The type of clay minerals, the high pH values of the studied sediments, and the considerable incorporation of Mg and K in palygorskite and illite respectively, may strongly reflect a high evaporative and alkaline environment under arid to semi-arid conditions in an ephemeral lake of the Qa Khanna. Concentrations and distributions of both major and trace elements are essentially controlled by the clay mineralogy and the calcium carbonate content; Ca is mainly incorporated in the CaCO 3, which is either generated authigenically or by aeolian deposition. Fe and K are incorporated and fixed by illite under an evaporative and alkaline environment. Mg is incorporated in palygorskite while Mn is adsorbed on various clay minerals. Sr substitutes for Ca in the aeolian CaCO 3 and its presence in the studied sediments is independent of the prevailing conditions during the playa evolution. Rb substitutes for K in illite under the prevailing chemical conditions in the studied playa.

Marine vs. local control on seawater Nd-isotope ratios at the northwest coast of Africa during the late Cretaceous-early Eocene

NASA Astrophysics Data System (ADS)

Kocsis, L.; Gheerbrant, E.; Mouflih, M.; Cappetta, H.; Ulianov, A.; Chiaradia, M.

2013-12-01

At the northwest corner of Africa excellent conditions existed for phosphate formation (i.e., stable upwelling system) during the late Cretaceous-early Eocene. This is probably in relation to stable tectonic evolution of shallow epicontinental basins at a passive continental margin and to their paleogeographic situation between the Atlantic and Tethys marine realms. To better comprehend paleoceanic conditions in this area, radiogenic isotope ratios (87Sr/86Sr and 143Nd/144Nd) and trace element compositions of fossil biogenic apatite are investigated from Maastrichtian to Ypresian shallow marine phosphorite deposits in Morocco (Ouled Abdoun and Ganntour Basins). Rare earth elements (REE) distributions in the fossils are compatible with early diagenetic marine pore fluid represented by negative Ce-anomaly and heavy REE enrichment. An overall shift in Ce-anomaly is apparent with gradually lower values in younger fossils along three distinct assemblages that correspond to Maastrichtian, Danian-Thanetian and Ypresian periods. The temporal change can be interpreted as presence of gradually more oxygenated seawater in the basins. Strontium isotopic ratios of the fossils follow the global Sr-evolution curve. However, the latest Cretaceous and the oldest Paleocene fossils yielded slightly higher ratios than the global ocean, which could reflect minor diagenetic alteration. Neodymium isotopic ratios are quite even along the phosphate series with ɛNd(t) values ranges from -6.8 to -5.8. These values are higher than those reported for average North Atlantic deep water and Tethyan seawater (e.g., Stille et al., 1996; Thomas et al., 2003). For the origin of the stable, high 143Nd/144Nd we propose three main hypotheses: (1) contribution of continental Nd-source, (2) locally controlled deep water Nd-isotope ratios near the coast from where upwelling originated in the area and (3) possible surface marine water contribution from the Pacific across the Atlantic. Stille, P., Steinmann

Origin of the diagenetic carbonate crusts and concretions from the mud volcanoes of the Nile deep-sea fan

NASA Astrophysics Data System (ADS)

Gontharet, S.; Pierre, C.; Blanc Valleron, M.; Rouchy, J.; Fouquet, Y.; Bayon, G.

2004-12-01

sources of diagenetic fluids. Typically, the very low \\delta13C values of the authigenic carbonates indicate that CH4 was the major source of carbon which was oxidized as CO2, either through bacterial sulfate reduction within the sediment, or via bacterial aerobic oxidation at the sea floor. Similar isotopic values were previously measured in the diagenetic carbonate crusts from the mud volcanoes of the Mediterranean Ridge area (Aloisi et al., 2000) as well as in other areas of cold seeps outside the Mediterranean sea (for instance Gulf of Mexico, Cascadia margin, Barbados prism). References: Aloisi G., Pierre C., Rouchy J.M., Foucher J.P., Woodside J. and the Medinaut Scientific Party, 2000. E.P.S.L., 184, 321-338. Loncke L., Gaullier V., Bellaiche G., and Mascle J., 2004. A.A.P.G. Bull

Geochemistry of Precambrian carbonates. IV - Early Paleoproterozoic (2.25 +/- 0.25 Ga) seawater

NASA Technical Reports Server (NTRS)

Veizer, Jan; Clayton, R. N.; Hinton, R. W.

1992-01-01

The mineralogy, chemistry, and isotopic composition of the Malmani Dolomite, Duck Creek Dolomite, and Bruce 'Limestone' Member of the Espanola Formation are studied in an effort to restrict the first- and second-order variations in isotopic composition of Early Paleoproterozoic seawater. The diagenetic rank is found to increase in the order Duck Creek less than Bruce less than Malmani. The interpolation of alteration trends to 'best' value yields an estimate of 0.70550 for Sr-87/Sr-86. For delta C-13, the measured range of 0 +/- 1.5 percent PDB is similar to that observed for Phanerozoic marine carbonates, while the 'best' delta O-18 value for dolostones is -5 percent PDB, depleted in O-18 relative to Phanerozoic counterparts but comparable to estimates obtained for Archean facies. The isotope geochemistry and mineralogy of Bruce 'Limestone' Member is consistent with the proposition that the sequence was deposited in a lacustrine environment.

Rechargeable solid state neutron detector and visible radiation indicator

DOEpatents

Stowe, Ashley C.; Wiggins, Brenden; Burger, Arnold

2017-05-23

A radiation detection device, including: a support structure; and a chalcopyrite crystal coupled to the support structure; wherein, when the chalcopyrite crystal is exposed to radiation, a visible spectrum of the chalcopyrite crystal changes from an initial color to a modified color. The visible spectrum of the chalcopyrite crystal is changed back from the modified color to the initial color by annealing the chalcopyrite crystal at an elevated temperature below a melting point of the chalcopyrite crystal over time. The chalcopyrite crystal is optionally a .sup.6LiInSe.sub.2 crystal. The radiation is comprised of neutrons that decrease the .sup.6Li concentration of the chalcopyrite crystal via a .sup.6Li(n,.alpha.) reaction. The initial color is yellow and the modified color is one of orange and red. The annealing temperature is between about 450 degrees C. and about 650 degrees C. and the annealing time is between about 12 hrs and about 36 hrs.

Molar tooth structures in calcareous nodules, early Neoproterozoic Burovaya Formation, Turukhansk region, Siberia

NASA Astrophysics Data System (ADS)

Pope, Michael C.; Bartley, Julie K.; Knoll, Andrew H.; Petrov, Peter Yu.

2003-05-01

Molar tooth structures are abundant in large (1-2 m diameter) carbonate nodules within fine-grained, subtidal carbonates of the early Neoproterozoic (lower Upper Riphean) Burovaya Formation along the Sukhaya Tunguska River, Turukhansk Uplift, northwestern Siberia. Although molar tooth structures are regionally abundant in this unit, here they occur only within the nodules. Stable isotopic compositions of molar-tooth-filling dolomicrospar cements and of thinly bedded dolomicrite within and surrounding the nodules are indistinguishable from one another. The carbon isotopic compositions (mean δ13C=+2.8‰ PDB±0.4) reflect mean average oceanic surface water composition during their formation; the light oxygen isotopic compositions (mean δ18O=-6.4‰ PDB±2.2) are generally similar to those of other little-altered Meso- to Neoproterozoic limestones and dolostones. These molar tooth structures have no features that would support a tectonic origin; they more likely formed through bacterial processes. Carbonate cement filling of these voids occurred soon after their formation, but the mechanism responsible for this carbonate precipitation is currently uncertain. Local restriction of molar tooth structures to early diagenetic nodules suggests that penecontemporaneous lithification was required for the formation, or at least preservation, of these widespread Mesoproterozoic to Neoproterozoic features.

X-ray photoelectron spectrum and electronic properties of a noncentrosymmetric chalcopyrite compound HgGa(2)S(4): LDA, GGA, and EV-GGA.

PubMed

Reshak, Ali Hussain; Khenata, R; Kityk, I V; Plucinski, K J; Auluck, S

2009-04-30

An all electron full potential linearized augmented plane wave method has been applied for a theoretical study of the band structure, density of states, and electron charge density of a noncentrosymmetric chalcopyrite compound HgGa(2)S(4) using three different approximations for the exchange correlation potential. Our calculations show that the valence band maximum (VBM) and conduction band minimum (CBM) are located at Gamma resulting in a direct energy gap of about 2.0, 2.2, and 2.8 eV for local density approximation (LDA), generalized gradient approximation (GGA), and Engel-Vosko (EVGGA) compared to the experimental value of 2.84 eV. We notice that EVGGA shows excellent agreement with the experimental data. This agreement is attributed to the fact that the Engel-Vosko GGA formalism optimizes the corresponding potential for band structure calculations. We make a detailed comparison of the density of states deduced from the X-ray photoelectron spectra with our calculations. We find that there is a strong covalent bond between the Hg and S atoms and Ga and S atoms. The Hg-Hg, Ga-Ga, and S-S bonds are found to be weaker than the Hg-S and Ga-S bonds showing that a covalent bond exists between Hg and S atoms and Ga and S atoms.

Diagenetic effects on magnetic minerals in a Holocene lacustrine sediment core from Huguangyan maar lake, southeast China

NASA Astrophysics Data System (ADS)

Wu, Xudong; Wang, Yong; Bian, Liu; Shen, Ji

2016-09-01

strong Asian summer monsoon intensity during the early Holocene are accountable for intensive diagenesis in the lowermost subsection. Complete erasing of detrital magnetic input signal at certain positions of the lowermost subsection, and considerable formation of authigenic siderite indicate that palaeomagnetic records of the studied core have been significantly compromised. The studied core has relatively higher TOC content, lower detrital matter content, calmer sedimentary environments, and less DO available at its water-sediment interface than the cores retrieved at relatively shallower water depths, which all contribute to its relatively stronger diagenesis. Progressive thickening of the upper two subsections with increasing water depth is owing to progressive increase in sedimentation rate with increasing water depth, which is the key factor in determining the thickness of each diagenetic subsection of cores from HGY. It would be better that lake sediments for palaeomagnetic investigations collected at a water depth shallower than the depth of its thermocline.

Prediction for electronic, vibrational and thermoelectric properties of chalcopyrite AgX(X=In,Ga)Te2: PBE + U approach

PubMed Central

Yang, Jianhui; Cheng, Xinlu

2017-01-01

The electronic, vibrational and thermoelectric transport characteristics of AgInTe2 and AgGaTe2 with chalcopyrite structure have been investigated. The electronic structures are calculated using the density-functional theory within the generalized gradient approximation (GGA) of Perdew–Burke–Ernzerhof functional considering the Hubbard-U exchange correlation. The band-gaps of AgInTe2 and AgGaTe2 are much larger than previous standard GGA functional results and agree well with the existing experimental data. The effective mass of the hole and the shape of density of states near the edge of the valence band indicate AgInTe2 and AgGaTe2 are considerable p-type thermoelectric materials. An analysis of lattice dynamics shows the low thermal conductivities of AgInTe2 and AgGaTe2. The thermoelectric transport properties' dependence on carrier concentration for p-type AgInTe2 and AgGaTe2 in a wide range of temperatures has been studied in detail. The results show that p-type AgInTe2 and AgGaTe2 at 800 K can achieve the merit values of 0.91 and 1.38 at about 2.12 × 1020 cm−3 and 1.97 × 1020 cm−3 carrier concentrations, respectively. This indicates p-type AgGaTe2 is a potential thermoelectric material at high temperature. PMID:29134079

Prediction for electronic, vibrational and thermoelectric properties of chalcopyrite AgX(X=In,Ga)Te2: PBE + U approach.

PubMed

Yang, Jianhui; Fan, Qiang; Cheng, Xinlu

2017-10-01

The electronic, vibrational and thermoelectric transport characteristics of AgInTe 2 and AgGaTe 2 with chalcopyrite structure have been investigated. The electronic structures are calculated using the density-functional theory within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof functional considering the Hubbard-U exchange correlation. The band-gaps of AgInTe 2 and AgGaTe 2 are much larger than previous standard GGA functional results and agree well with the existing experimental data. The effective mass of the hole and the shape of density of states near the edge of the valence band indicate AgInTe 2 and AgGaTe 2 are considerable p-type thermoelectric materials. An analysis of lattice dynamics shows the low thermal conductivities of AgInTe 2 and AgGaTe 2 . The thermoelectric transport properties' dependence on carrier concentration for p-type AgInTe 2 and AgGaTe 2 in a wide range of temperatures has been studied in detail. The results show that p-type AgInTe 2 and AgGaTe 2 at 800 K can achieve the merit values of 0.91 and 1.38 at about 2.12 × 10 20  cm -3 and 1.97 × 10 20  cm -3 carrier concentrations, respectively. This indicates p-type AgGaTe 2 is a potential thermoelectric material at high temperature.

Bacterially mediated diagenetic origin for chert-hosted manganese deposits in the Franciscan Complex, California Coast Ranges

NASA Astrophysics Data System (ADS)

Hein, James R.; Koski, Randolph A.

1987-08-01

Numerous manganese deposits in the Franciscan Complex, California, occur as conformable lenses within bedded radiolarian chert-argillite sequences that are, in turn, intercalated within thicker sections of sandstone and shale. The field relations, composition, and petro-graphic and isotopic characteristics indicate that the manganese was concentrated by diagenetic reconstitution of siliceous and hemipelagic sediment during burial. The ore lenses are Mn-rich and Fe-poor assemblages consisting largely of rhodochrosite, manganese silicates, opal-CT (disordered cristobalite-tridymite), and quartz. Highly negative δ13C values for the carbonate carbon in rhodochrosite indicate that CO2 likely originated from oxidation of methane; less negative values result from mixing of methanogenic carbon and CO2 derived from bacterial degradation of organic matter. The δ18O values for the carbonate of rhodochrosite indicate temperatures of formation between 12 and 100 °C. The oxidation of methane prior to carbonate precipitation may have used the minor (0.4% 0.5%) Mn and Fe oxyhydroxides and oxides deposited with the sediment. The mobilization of manganese from biogenic and terrigenous sources in the sediment column into discrete horizons and the fractioriation of manganese from iron reflect the presence of oxidation-reduction boundaries and gradients in the sediment column. Fluids derived from compaction and silica-dehydration reactions in the transformation of opal-A (X-ray amorphous biogenic silica) to quartz were involved in transportation of principal components. Sedimentary and geochemical attributes suggest that the deposits formed in a deep-water environment in a zone of oceanic upwelling near a continental margin.

Hybrid particles and associated methods

DOEpatents

Fox, Robert V; Rodriguez, Rene; Pak, Joshua J; Sun, Chivin

2015-02-10

Hybrid particles that comprise a coating surrounding a chalcopyrite material, the coating comprising a metal, a semiconductive material, or a polymer; a core comprising a chalcopyrite material and a shell comprising a functionalized chalcopyrite material, the shell enveloping the core; or a reaction product of a chalcopyrite material and at least one of a reagent, heat, and radiation. Methods of forming the hybrid particles are also disclosed.

New potassium-argon data on the age of mineralization and metamorphism in the Willow Creek mining district, southern Talkeetna Mountains, Alaska: A section in The United States Geological Survey in Alaska: Accomplishments during 1977

USGS Publications Warehouse

Silberman, Miles L.; Csejtey, Bela; Smith, James G.; Lanphere, Marvin A.; Wilson, Frederic H.

1978-01-01

The now largely abandoned Willow Creek mining district, southern Talkeetna Mountains, Alaska, produced nearly $18,000,000 in gold and minor silver between 1909 and the early 1950's. Mineralized quartz veins, which contain gold and silver along with minor quantities of base metals (in pyrite, galena, chalcopyrite, sphalerite, molybdenite, and arsenopyrite), cut Late Cretaceous and early Tertiary tonalite and quartzmica schist of probable Jurassic age (Ray, 1954; Silberman and others, 1976; Bela Csejtey, Jr., unpub. data, 1978).

Fluid inclusions in calcite filled opening fractures of the Serra Alta Formation reveal paleotemperatures and composition of diagenetic fluids percolating Permian shales of the Paraná Basin

NASA Astrophysics Data System (ADS)

Teixeira, C. A. S.; Sawakuchi, A. O.; Bello, R. M. S.; Nomura, S. F.; Bertassoli, D. J.; Chamani, M. A. C.

2018-07-01

The thermal and diagenetic evolution of shale units has received renewed focus because of their emergence as unconventional hydrocarbon reservoirs. The Serra Alta Formation (SAF) is a Permian shale unit of the Paraná Basin, which is the largest South American cratonic basin. The SAF stands out as a pathway for aqueous fluids and hydrocarbon migration from the Irati organic-rich shales to the Pirambóia fluvial-eolian sandstone reservoirs. Vertical NNW and NNE opening fractures would be the main pathways for the migration of buried pore waters and aqueous fluids, besides the input of meteoric water. These fractures would be associated to the reactivation of basement discontinuities such as the Jacutinga (NE) and Guapiara (NW) faults. Thus, vertical NNE and NNW associated fractures would represent the main pathways for fluid migration in the studied area. The vertical calcite filled opening fractures from SAF record moderately low salinity (0-4.5 wt % of NaCl eq.) aqueous fluids, suggesting the input of meteoric water in the buried fracture system. Eutectic melting temperatures at -52±5 °C indicate an H2O + NaCl + CaCl2 system with CaCl2 or MgCl2 in solution. Homogenization temperatures recorded in fluid inclusion assemblages (FIAs) of calcite filled opening fractures indicate that the SAF in the studied area reached temperatures above 200 °C, suitable for generation of gaseous hydrocarbons. The recorded paleotemperatures point to a thermal peak associated with Serra Geral volcanic event during the Early Cretaceous, with the thermal effect of volcanic rock cap possibly overcoming the effect of intrusive igneous bodies. The detection of methane in SAF shale pores indicates conditions for hydrocarbon generation. However, additionally studies are necessary to confirm the thermogenic and/or biogenic origin of the methane within the SAF.

Microfacies and diagenesis of the Middle Jurassic Dhruma carbonates, southwest Riyadh, Saudi Arabia

NASA Astrophysics Data System (ADS)

El-Sorogy, Abdelbaset S.; Galmed, Mahmoud A.; Al-Kahtany, Khaled; Al-Zahrani, Ali

2017-06-01

In order to document the microfacies analysis and diagenetic alterations of the Middle Jurassic Dhruma Formation at southwest Riyadh City of central Saudi Arabia, a stratigraphic section was studied in detail at Khashm adh Dhi'bi area. Mudstones, wackstones, packstones, grainstones and boundstones are the main microfacies types in the studied area. These microfacies types with field investigations and fossil content indicated an environment ranging from deep shelf to organic buildup on platform margins for the studied carbonates. Cementation and recrystallization, dissolution, fragmentation and compaction, silicification, dolomitization, and bioerosion were the main diagenetic alterations affected the carbonate rocks of the Dhruma Formation. Cementation and recrystallization are represented by equant calcite crystals, Dog-tooth fringes of thin isopachous calcites and blocky low Mg-calcites. Gastrochaenolites, Trypanites and Meandropolydora spp. were the most bioeroders in coral heads and large bivalves and hardgrounds. These bioeroders indicated a long post-mortem period during the early diagenetic stage.

Late Diagenetic Cements in the Murray Formation, Gale Crater, Mars: Implications for Postdepositional Fluid Flow

NASA Astrophysics Data System (ADS)

Kah, L. C.; Kronyak, R. E.; Van Beek, J.; Nachon, M.; Mangold, N.; Thompson, L. M.; Wiens, R. C.; Grotzinger, J. P.; Schieber, J.

2015-12-01

The Murray formation in its type section at Pahrump Hills, consists of approximately 14 meters of recessive-weathering mudstone interbedded with decimeter-scale cross-bedded sandstone in the upper portions of the exposed section. Mudstone textures vary from massive, to poorly laminated, to well laminated. Unusual 3-dimensional crystal clusters and dendrites occur in the lowermost part of the section and are erosionally resistant with respect to the host rock. Crystal clusters consist of elongate lathes that occur within individual blocks of the fractured substrate. Individual lathes show tabular morphologies with a pseudo-rectangular cross-section and the three dimensional morphology of the crystal clusters cross-cut host rock lamination with little or no deformation. Dendritic structures are typically larger and show predominantly planar growth aligned with bedding planes. Individual lathes within the dendrites are elongate and pseudo-rectangular in cross-section. Unlike crystal clusters, dendritic morphologies appear to nucleate at bedrock fractures and near mineralized veins. Here we show evidence that crystal clusters and dendrites are post-depositional, potentially burial diagenetic features. Association of features with through-going fractures suggests that fractures may have been a primary transport pathway for ions responsible for dendrite growth. Even where dendrites do not occur, enhanced cementation suggests that fluids permeated the rock matrix. We suggest that growth of clusters proceeded as inter-particle crystal growth, wherein mineral growth within inter-particle spaces resulted in cementation and porosity loss, with little further effect on the rock matrix. Crystal clusters and dendrites are most likely to form when mineral saturation states are highest, for instance with initial intrusion of fracture-borne fluids and mixing with ambient pore fluids, and thus emphasize the importance of fractures in ion transport during late diagenesis.

Sedimentary sulfur geochemistry of the Paleogene Green River Formation, western USA: Implications for interpreting depositional and diagenetic processes in saline alkaline lakes

USGS Publications Warehouse

Tuttle, M.L.; Goldhaber, M.B.

1993-01-01

The sulfur geochemistry of the lacustrine Paleogene Green River Formation (Colorado, Utah, and Wyoming, USA) is unlike that of most marine and other lacustrine rocks. Distinctive chemical, isotopic, and mineralogical characteristics of the formation are pyrrhotite and marcasite, high contents of iron mineral sulfides strikingly enriched in 34S, cyclical trends in sulfur abundance and ??34S values, and long-term evolutionary trends in ??34S values. Analyses that identified and quantified these characteristics include carbonate-free abundance of organic carbon (0.13-47 wt%), total iron (0.31-13 wt%), reactive iron (>70% of total iron), total sulfur (0.02-16 wt%), acid-volatile monosulfide (SAv), disulfide (SDi > 70% of total sulfur), sulfate (SSO4) and organosulfur (SOrg); isotopic composition of separated sulfur phases (??34SDi,Av up to +49???); and mineralogy, morphology and paragenesis of sulfide minerals. Mineralogy, morphology, ??34SDi,Av, and ??34SOrg have a distinctive relation, reflecting variable and unique depositional and early diagenetic conditions in the Green River lakes. When the lakes were brackish, dissimilatory sulfate-reducing bacteria in the sediment produced H2S, which initially reacted with labile iron to form pyrite framboids and more gradually with organic matter to form organosulfur compounds. During a long-lived stage of saline lake water, the amount of sulfate supplied by inflow decreased and alkalinity and pH of lake waters increased substantially. Extensive bacterial sulfate reduction in the water column kept lake waters undersaturated with sulfate minerals. A very high H2S:SO4 ratio developed in stagnant bottom water aided by the high pH that kinetically inhibited iron sulfidization. Progressive removal of H2S by coeval formation of iron sulfides and organosulfur compounds caused the isotopic composition of the entire dissolved sulfur reservoir to evolve to ??34S values much greater than that of inflow sulfate, which is estimated to have

Comparative study on the passivation layers of copper sulphide minerals during bioleaching

NASA Astrophysics Data System (ADS)

Fu, Kai-bin; Lin, Hai; Mo, Xiao-lan; Wang, Han; Wen, Hong-wei; Wen, Zi-long

2012-10-01

The bioleaching of copper sulphide minerals was investigated by using A. ferrooxidans ATF6. The result shows the preferential order of the minerals bioleaching as djurleite>bornite>pyritic chalcopyrite>covellite>porphyry chalcopyrite. The residues were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It is indicated that jarosite may not be responsible for hindered dissolution. The elemental sulfur layer on the surface of pyritic chalcopyrite residues is cracked. The compact surface layer of porphyry chalcopyrite may strongly hinder copper extraction. X-ray photoelectron spectroscopy (XPS) further confirms that the passivation layers of covellite, pyritic chalcopyrite, and porphyry chalcopyrite are copper-depleted sulphide Cu4S11, S8, and copper-rich iron-deficient polysulphide Cu4Fe2S9, respectively. The ability of these passivation layers was found as Cu4Fe2S9>Cu4S11>S8>jarosite.

Provenance and diagenesis of the evaporite-bearing Burns formation, Meridiani Planum, Mars

USGS Publications Warehouse

McLennan, S.M.; Bell, J.F.; Calvin, W.M.; Christensen, P.R.; Clark, B. C.; de Souza, P.A.; Farmer, J.; Farrand, W. H.; Fike, D.A.; Gellert, Ralf; Ghosh, A.; Glotch, T.D.; Grotzinger, J.P.; Hahn, B.; Herkenhoff, K. E.; Hurowitz, J.A.; Johnson, J. R.; Johnson, S.S.; Jolliff, B.; Klingelhofer, G.; Knoll, A.H.; Learner, Z.; Malin, M.C.; McSween, H.Y.; Pocock, J.; Ruff, S.W.; Soderblom, L.A.; Squyres, S. W.; Tosca, N.J.; Watters, W.A.; Wyatt, M.B.; Yen, A.

2005-01-01

Impure reworked evaporitic sandstones, preserved on Meridiani Planum, Mars, are mixtures of roughly equal amounts of altered siliciclastic debris, of basaltic provenance (40 ?? 10% by mass), and chemical constituents, dominated by evaporitic minerals (jarosite, Mg-, Ca-sulfates ?? chlorides ?? Fe-, Na-sulfates), hematite and possibly secondary silica (60 ?? 10%). These chemical constituents and their relative abundances are not an equilibrium evaporite assemblage and to a substantial degree have been reworked by aeolian and subaqueous transport. Ultimately they formed by evaporation of acidic waters derived from interaction with olivine-bearing basalts and subsequent diagenetic alteration. The rocks experienced an extended diagenetic history, with at least two and up to four distinct episodes of cementation, including stratigraphically restricted zones of recrystallization and secondary porosity, non-randomly distributed, highly spherical millimeter-scale hematitic concretions, millimeter-scale crystal molds, interpreted to have resulted from dissolution of a highly soluble evaporite mineral, elongate to sheet-like vugs and evidence for minor synsedimentary deformation (convolute and contorted bedding, possible teepee structures or salt ridge features). Other features that may be diagenetic, but more likely are associated with relatively recent meteorite impact, are meter-scale fracture patterns, veins and polygonal fractures on rock surfaces that cut across bedding. Crystallization of minerals that originally filled the molds, early cement and sediment deformation occurred syndepositionally or during early diagenesis. All other diagenetic features are consistent with formation during later diagenesis in the phreatic (fluid saturated) zone or capillary fringe of a groundwater table under near isotropic hydrological conditions such as those expected during periodic groundwater recharge. Textural evidence suggests that rapidly formed hematitic concretions post

Provenance and diagenesis of the evaporite-bearing Burns formation, Meridiani Planum, Mars

NASA Astrophysics Data System (ADS)

McLennan, S. M.; Bell, J. F.; Calvin, W. M.; Christensen, P. R.; Clark, B. C.; de Souza, P. A.; Farmer, J.; Farrand, W. H.; Fike, D. A.; Gellert, R.; Ghosh, A.; Glotch, T. D.; Grotzinger, J. P.; Hahn, B.; Herkenhoff, K. E.; Hurowitz, J. A.; Johnson, J. R.; Johnson, S. S.; Jolliff, B.; Klingelhöfer, G.; Knoll, A. H.; Learner, Z.; Malin, M. C.; McSween, H. Y.; Pocock, J.; Ruff, S. W.; Soderblom, L. A.; Squyres, S. W.; Tosca, N. J.; Watters, W. A.; Wyatt, M. B.; Yen, A.

2005-11-01

Impure reworked evaporitic sandstones, preserved on Meridiani Planum, Mars, are mixtures of roughly equal amounts of altered siliciclastic debris, of basaltic provenance (40 ± 10% by mass), and chemical constituents, dominated by evaporitic minerals (jarosite, Mg-, Ca-sulfates ± chlorides ± Fe-, Na-sulfates), hematite and possibly secondary silica (60 ± 10%). These chemical constituents and their relative abundances are not an equilibrium evaporite assemblage and to a substantial degree have been reworked by aeolian and subaqueous transport. Ultimately they formed by evaporation of acidic waters derived from interaction with olivine-bearing basalts and subsequent diagenetic alteration. The rocks experienced an extended diagenetic history, with at least two and up to four distinct episodes of cementation, including stratigraphically restricted zones of recrystallization and secondary porosity, non-randomly distributed, highly spherical millimeter-scale hematitic concretions, millimeter-scale crystal molds, interpreted to have resulted from dissolution of a highly soluble evaporite mineral, elongate to sheet-like vugs and evidence for minor synsedimentary deformation (convolute and contorted bedding, possible teepee structures or salt ridge features). Other features that may be diagenetic, but more likely are associated with relatively recent meteorite impact, are meter-scale fracture patterns, veins and polygonal fractures on rock surfaces that cut across bedding. Crystallization of minerals that originally filled the molds, early cement and sediment deformation occurred syndepositionally or during early diagenesis. All other diagenetic features are consistent with formation during later diagenesis in the phreatic (fluid saturated) zone or capillary fringe of a groundwater table under near isotropic hydrological conditions such as those expected during periodic groundwater recharge. Textural evidence suggests that rapidly formed hematitic concretions post

Early Diagenesis of Trace Elements in Modern Fjord Sediments of the High Arctic

NASA Astrophysics Data System (ADS)

Herbert, L.; Riedinger, N.; Aller, R. C.; Jørgensen, B. B.; Wehrmann, L.

2017-12-01

Marine sediments are critical repositories for elements that are only available at trace concentrations in seawater, such as Fe, Mn, Co, Ni, As, Mo, and U. The behavior of these trace elements in the sediment is governed by a dynamic interplay of diagenetic reactions involving organic carbon, Fe and Mn oxides, and sulfur phases. In the Arctic fjords of Svalbard, glacial meltwater delivers large amounts of reactive Fe and Mn oxides to the sediment, while organic carbon is deposited episodically and diluted by lithogenic material. These conditions result in pronounced Fe and Mn cycling, which in turn drives other diagenetic processes such as rapid sulfide oxidation. These conditions make the Svalbard fjords ideal sites for investigating trace element diagenesis because they allow resolution of the interconnections between Fe and Mn dynamics and trace element cycling. In August 2016, we collected sediment cores from three Svalbard fjords and analyzed trace elements in the pore water and solid sediment over the top meter. Initial results reveal the dynamic nature of these fjords, which are dominated by non-steady state processes and episodic events such as meltwater pulses and phytoplankton blooms. Within this system, the distribution of As appears to be strongly linked to the Fe cycle, while Co and Ni follow Mn; thus, these three elements may be released from the sediment through diffusion and bioturbation along with Fe and Mn. The pore water profiles of U and Mo indicate removal processes that are independent from Fe or Mn, and which are rather unexpected given the apparent diagenetic conditions. Our results will help elucidate the processes controlling trace element cycling in a dynamic, glacially impacted environment and will ultimately contribute to our understanding of the role of fjords in the biogeochemical cycling of trace elements in a rapidly changing Arctic Ocean.

Early diagenesis of bacteriohopanepolyol derivatives: Formation of fossil homohopanoids

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Van Duin, Adri C. T.; Hollander, David; Kohnen, Math E. L.; De Leeuw, Jan W.

1995-12-01

Diagenetic pathways of bacteriohopanepolyol derivatives are proposed based on the concentrations and 13C contents of homohopanes, homohop-17(21)-enes, benzohopanes, hopanoid thiophenes and sulphides, and macromolecularly S-bound homohopanes present in the extracts of twelve composite one metre samples from a 120 m core recovered from the Upper Cretaceous Jurf ed Darawish Oil Shale (Jordan). A large part (>80-95%) of the pentakishomohopane skeleton occurs in a S-bound form. This reveals the selective preservation of the C 35 hopane skeleton by sulphur sequestration and provides a theoretical basis for the homohopane index as an indicator of anoxia in past depositional environments. A smaller part (>50-80%) of the total extended hopane skeletons (C 31-C 35) occurs in a S-bound form. Of the non-sulphur-containing hopanoids the homohop-17(21)-enes dominate. These latter components show a gradual increase of 22S epimers with depth (45-52%) towards the thermodynamic equilibrium (52-53%) as calculated by molecular mechanics. Molecular mechanic calculations indicate that this increase can be explained by either isomerisation of 22R hop-17(21)-enes or by isomerisation of double bonds of homohopenes formed by dehydration of bacteriohopanepolyols "en passant" isomerising the chiral centre at C-22. A combination of these two pathways is also possible and provides an explanation for different δ13C values of pairs of 22R and 22S epimers. Isomerisation of 17β,21β(H)-homohopane to 17α,21,β(H)-homohopane carbon skeletons occurs for all compound classes in a very narrow depth span (ca. 20 m) and is probably induced by small differences in thermal history. Compound-specific carbon isotope analyses indicated that the series of homohop-17(21)-enes have in some cases significant differences in 13C content, indicating that at least two different sources have contributed to this series of components. Differences with macromolecularly S-bound C 35 hopane skeletons and free C 31

Patterns of metal distribution in hypersaline microbialites during early diagenesis: Implications for the fossil record.

PubMed

Sforna, M C; Daye, M; Philippot, P; Somogyi, A; van Zuilen, M A; Medjoubi, K; Gérard, E; Jamme, F; Dupraz, C; Braissant, O; Glunk, C; Visscher, P T

2017-03-01

The use of metals as biosignatures in the fossil stromatolite record requires understanding of the processes controlling the initial metal(loid) incorporation and diagenetic preservation in living microbialites. Here, we report the distribution of metals and the organic fraction within the lithifying microbialite of the hypersaline Big Pond Lake (Bahamas). Using synchrotron-based X-ray microfluorescence, confocal, and biphoton microscopies at different scales (cm-μm) in combination with traditional geochemical analyses, we show that the initial cation sorption at the surface of an active microbialite is governed by passive binding to the organic matrix, resulting in a homogeneous metal distribution. During early diagenesis, the metabolic activity in deeper microbialite layers slows down and the distribution of the metals becomes progressively heterogeneous, resulting from remobilization and concentration as metal(loid)-enriched sulfides, which are aligned with the lamination of the microbialite. In addition, we were able to identify globules containing significant Mn, Cu, Zn, and As enrichments potentially produced through microbial activity. The similarity of the metal(loid) distributions observed in the Big Pond microbialite to those observed in the Archean stromatolites of Tumbiana provides the foundation for a conceptual model of the evolution of the metal distribution through initial growth, early diagenesis, and fossilization of a microbialite, with a potential application to the fossil record. © 2016 John Wiley & Sons Ltd.

Benthic hypoxia and early diagenesis in the Black Sea shelf sediments

NASA Astrophysics Data System (ADS)

Plante, Audrey; Roevros, Nathalie; Capet, Arthur; Grégoire, Marilaure; Fagel, Nathalie; Chou, Lei

2017-04-01

Marine waters of semi-enclosed seas are affected by a major environmental issue which is oxygen depletion in bottom waters. Deoxygenation is one of the most widespread man-induced consequences which can be catastrophic for living species. Between 1970 and 1990, the benthic compartment of the Black Sea underwent modifications due to the occurrence and increase of hypoxia. Indeed, these changes might cause a deterioration of the structure and functioning of the ecosystems. Nowadays, some regions, such as the north-western shelf, are still affected seasonally by this phenomenon. Within the framework of the BENTHOX project, a biogeochemical study focusing on the early diagenesis is conducted in the Black Sea. It aims (1) to obtain a better understanding of the impact of benthic hypoxia on the diagenetic pathways, (2) to contribute to a new dataset of biogeochemical measurements in the sediments including porewaters. During a cruise (Emblas II - May 2016), on board the RV Mare Nigrum, sediment cores were taken at 4 stations on the Ukrainian shelf. Porewaters were extracted on board the ship using Rhizon technique under N2 atmosphere and will be analyzed for dissolved nutrients and major ions. In addition, sediments were sliced and will be determined for major solid phases and trace element contents. A multi-proxies (biological, sedimentological, mineralogical and geochemical) approach will be used to identify the hypoxic events and to reconstruct the history of bottom hypoxia. The results obtained will be presented and discussed with emphasis on the first outcomes and the major biogeochemical processes involved in the early diagenesis.

Apparatus for forming thin-film heterojunction solar cells employing materials selected from the class of I-III-VI.sub.2 chalcopyrite compounds

DOEpatents

Mickelsen, Reid A.; Chen, Wen S.

1983-01-01

Apparatus for forming thin-film, large area solar cells having a relatively high light-to-electrical energy conversion efficiency and characterized in that the cell comprises a p-n-type heterojunction formed of: (i) a first semiconductor layer comprising a photovoltaic active material selected from the class of I-III-VI.sub.2 chalcopyrite ternary materials which is vacuum deposited in a thin "composition-graded" layer ranging from on the order of about 2.5 microns to about 5.0 microns (.congruent.2.5 .mu.m to .congruent.5.0 .mu.m) and wherein the lower region of the photovoltaic active material preferably comprises a low resistivity region of p-type semiconductor material having a superimposed region of relatively high resistivity, transient n-type semiconductor material defining a transient p-n homojunction; and (ii), a second semiconductor layer comprising a low resistivity n-type semiconductor material wherein interdiffusion (a) between the elemental constituents of the two discrete juxtaposed regions of the first semiconductor layer defining a transient p-n homojunction layer, and (b) between the transient n-type material in the first semiconductor layer and the second n-type semiconductor layer, causes the transient n-type material in the first semiconductor layer to evolve into p-type material, thereby defining a thin layer heterojunction device characterized by the absence of voids, vacancies and nodules which tend to reduce the energy conversion efficiency of the system.

Isotope and elemental geochemistry of Cretaceous fossiliferous concretions (Santana Formation, Brazil)

NASA Astrophysics Data System (ADS)

Heimhofer, Ulrich; Meister, Patrick; Bernasconi, Stefano M.; Ariztegui, Daniel; Martill, David M.; Schwark, Lorenz

2014-05-01

Exceptional three-dimensional fossil preservation (incl. phosphatization of soft-tissues) within organic carbon-rich mudstones is often associated with the formation of a protective carbonate shell surrounding the fossil specimen. Examples for this type of preservation are the Early Cretaceous fishes, turtles and pterosaurs from the Brazilian Santana Formation. Numerous studies proposed different conceptual models for concretion formation. Having new state-of-the-art geochemical tools at hand we revisited these models for the Santana Formation as an exemplary case. Differential compaction clearly indicates early precipitation of micritic calcite surrounding a central cavity containing the still decomposing fossil. The presence of pyrite forming a circular rim around the fossil and carbonate with negative carbon isotope compositions suggest intense sulphate reduction whereby the production of ammonium from the decay of proteins led to an increased alkalinity, which induced early carbonate precipitation. By means of micro-XRF scanning we found that pyrite is absent from the interior part of the concretions and that total iron content is very low, which indicate absence of sulphate reduction at the center of the concretions and possibly local onset of methanogenesis. We postulate that the central cavity may even have been filled with methane gas that evolved from the decaying animal. Methane diffusing outward was anaerobically oxidized in the surrounding sulphate reduction zone. Carbonate clumped isotopes revealed that micritic calcite formed early, but that these early precipitates are overprinted by two different late diagenetic cements precipitated at elevated temperatures. The occurrence of an outermost "cone-in-cone" calcite rim can be associated with burial showing temperatures of up to 60°C. Strontium-isotope ratios of matrix calcite and cement phases show radiogenic values (0.710416 to 0.712465), which are significantly higher than typical marine Cretaceous

Phosphate Stability in Diagenetic Fluids Constrains the Acidic Alteration Model for Lower Mt. Sharp Sedimentary Rocks in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Berger, J. A.; Schmidt, M. E.; Izawa, M. R. M.; Gellert, R.; Ming, D. W.; Rampe, E. B.; VanBommel, S. J.; McAdam, A. C.

2016-01-01

The Mars rover Curiosity has encountered silica-enriched bedrock (as strata and as veins and associated halos of alteration) in the largely basaltic Murray Fm. of Mt. Sharp in Gale Crater. Alpha Particle X-ray Spectrometer (APXS) investigations of the Murray Fm. revealed decreasing Mg, Ca, Mn, Fe, and Al, and higher S, as silica increased (Fig. 1). A positive correlation between SiO2 and TiO2 (up to 74.4 and 1.7 wt %, respectively) suggests that these two insoluble elements were retained while acidic fluids leached more soluble elements. Other evidence also supports a silica-retaining, acidic alteration model for the Murray Fm., including low trace element abundances consistent with leaching, and the presence of opaline silica and jarosite determined by CheMin. Phosphate stability is a key component of this model because PO4 3- is typically soluble in acidic water and is likely a mobile ion in diagenetic fluids (pH less than 5). However, the Murray rocks are not leached of P; they have variable P2O5 (Fig. 1) ranging from average Mars (0.9 wt%) up to the highest values in Gale Crater (2.5 wt%). Here we evaluate APXS measurements of Murray Fm. bedrock and veins with respect to phosphate stability in acidic fluids as a test of the acidic alteration model for the Lower Mt. Sharp rocks.

Linking Home Plate and Algonquin Class Rocks through Microtextural Analysis: Evidence for Hydrovolcanism in the Inner Basin of Columbia Hills, Gusev Crater

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Yingst, R. Aileen; Schmidt, Mariek E.; Herkenhoff, Ken E.

2007-01-01

Examining the his-tory of a rock as the summed history of its constituent grains is a proven and powerful strategy that has been used on Earth to maximize the information that can be gleaned from limited samples. Grain size, sorting, roundness, and texture can be observed at the handlens scale, and may reveal clues to transport regime (e.g. fluvial, glacial, eolian) and transport distance. Diagenetic minerals may be of a form and textural context to allow identification, and to point to dominant diagenetic processes (e.g. evaporitic concentration, intermittent dissolution, early vs. late diagenetic emplacement). Handlens scale features of volcaniclastic particles may be diagnostic of primary vs recycled (by surface processes) grains and may provide information about eruptive patterns and processes. When the study site is truly remote, such as Mars, and when there are severe limitations on sample return or sample analysis with other methods, examination at the hand lens scale becomes critical both for extracting a maximum of information, and for best utilizing finite analytical capabilities.

Polygenetic Karsted Hardground Omission Surfaces in Lower Silurian Neritic Limestones: a Signature of Early Paleozoic Calcite Seas

NASA Astrophysics Data System (ADS)

James, Noel P.; Desrochers, André; Kyser, Kurt T.

2015-04-01

Exquisitely preserved and well-exposed rocky paleoshoreline omission surfaces in Lower Silurian Chicotte Formation limestones on Anticosti Island, Quebec, are interpreted to be the product of combined marine and meteoric diagenesis. The different omission features include; 1) planar erosional bedding tops, 2) scalloped erosional surfaces, 3) knobs, ridges, and swales at bedding contacts, and 4) paleoscarps. An interpretation is proposed that relates specific omission surface styles to different diagenetic-depositional processes that took place in separate terrestrial-peritidal-shallow neritic zones. Such processes were linked to fluctuations in relative sea level with specific zones of diagenesis such as; 1) karst corrosion, 2) peritidal erosion, 3) subtidal seawater flushing and cementation, and 4) shallow subtidal deposition. Most surfaces are interpreted to have been the result of initial extensive shallow-water synsedimentary lithification that were, as sea level fell, altered by exposure and subaerial corrosion, only to be buried by sediments as sea level rose again. This succession was repeated several times resulting in a suite of recurring polyphase omission surfaces through many meters of stratigraphic section. Synsedimentary cloudy marine cements are well preserved and are thus interpreted to have been calcitic originally. Aragonite components are rare and thought to have to have been dissolved just below the Silurian seafloor. Large molluscs that survived such seafloor removal were nonetheless leached and the resultant megamoulds were filled with synsedimentary calcite cement. These Silurian inner neritic-strandline omission surfaces are temporally unique. They are part of a suite of marine omission surfaces that are mostly found in early Paleozoic neritic carbonate sedimentary rocks. These karsted hardgrounds formed during a calcite-sea time of elevated marine carbonate saturation and extensive marine cement precipitation. The contemporaneous greenhouse

Climatic fluctuations and seasonality during the Late Jurassic (Oxfordian-Early Kimmeridgian) inferred from δ18O of Paris Basin oyster shells

NASA Astrophysics Data System (ADS)

Brigaud, Benjamin; Pucéat, Emmanuelle; Pellenard, Pierre; Vincent, Benoît; Joachimski, Michael M.

2008-08-01

Oxygen isotope data from biostratigraphically well-dated oyster shells from the Late Jurassic of the eastern Paris Basin are used to reconstruct the thermal evolution of western Tethyan surface waters during the Early Oxfordian-Early Kimmeridgian interval. Seventy eight oyster shells were carefully screened for potential diagenetic alteration using cathodoluminescence microscopy. Isotope analyses were performed on non-luminescent parts of shells (n = 264). Intra-shell δ18O variability was estimated by microsampling along a transect perpendicular to the growth lines of the largest oyster shell. The sinusoidal distribution of the δ18O values along this transect and the dependence of the amplitude of variations with bathymetry suggest that intra-shell variability reflects seasonal variations of temperature and/or salinity. Average amplitudes of about 5 °C in shallow water environments and of about 2-3 °C in deeper offshore environments are calculated. These amplitudes reflect minimum seasonal temperature variation. Our new data allow to constrain existing paleotemperature trends established from fish tooth and belemnite δ18O data and are in better agreement with paleontological data. More specifically, a warming trend of about 3 °C is reconstructed for oceanic surface waters during the Early to Middle Oxfordian transition, with maximum temperatures reaching 24 °C in the transversarium Zone (late Middle Oxfordian). From the transversarium Zone to the bimmamatum Zone, a cooling of about 7 °C is indicated, whereas from the bimmamatum Zone, temperatures increased again by about 7 °C to reach 24 °C in average during the cymodoce Zone (Early Kimmeridgian).

Recovery of Copper from Cyanidation Tailing by Flotation

NASA Astrophysics Data System (ADS)

Qiu, Tingsheng; Huang, Xiong; Yang, Xiuli

2016-02-01

In this work, sodium hypochlorite, hydrogen peroxide, sodium metabisulfite and copper sulfate as activators were investigated to lessen the depression effect of cyanide for deep-depressing chalcopyrite. The experimental results indicate that the copper recovery exceeded 94%, 84% and 97% at the dosage: sodium hypochlorite 3 mL/L, hydrogen peroxide 2 mL/L, sodium metabisulfite 2 × 10-3 mol/L and copper sulfate 1.67 × 10-4 mol/L, respectively. According to the results of zeta potential and Fourier transform infrared spectrum, it is suggested that chalcopyrite was depressed because of the chemical adsorption of cyanide on the chalcopyrite surfaces. Sodium hypochlorite, hydrogen peroxide and sodium metabisulfite can destroy Cu-C bond on the deep-depressing chalcopyrite surface by chemical reaction. Copper sulfate can activate deep-depressing chalcopyrite by copper ion adsorption.

Pyrolytic indices of diagenetic transformation of lignin as biogeochemical proxies for soil organic matter quality and C storage potential

NASA Astrophysics Data System (ADS)

Jiménez-González, Marco A.; Almendros, Gonzalo; Álvarez, Ana M.; Jiménez-Morillo, Nicasio T.; González-Vila, Francisco J.

2017-04-01

The environmental factors involved in soil organic carbon sequestration remain unclear. The functional relationships between the macromolecular structure of the soil organic matter (SOM) and its resilience has been a constant in classical biogeochemical models. Other more recent hypotheses have postulated that preservation by soil minerals may play a chief role in the accumulation of stable SOM forms. However, additional experimental data are required to demonstrate a cause-to-effect relationship between preservation and stabilization. Some authors might consider that models neglecting the role of macromolecular structure are swapping cause and effect i.e., that SOM structurally flexible, weakly condensed and having 'open' structures is the one with high potential to interact with the soil mineral matrix, leading to stable microaggregates. In this study up to 35 topsoil samples (0-5 cm) were collected from different Spanish soils with contrasted values of organic C (the dependent variable), geological substrate and vegetation type. A wide array of uni- and multivariate chemometric models were applied to independent variables consisting of total abundances of the major aromatic compounds, i.e., alkylbenzenes and methoxyphenols released from whole soil samples using pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). These two families of compounds were selected since they are classically considered to inform on the degree of microbial reworking of lignins, which is an important precursor of the aromatic moiety of the SOM. A series of pyrolytic surrogate indices (aiming to express SOM diagenetic transformation in relation to the original biogenic molecular composition) were especially successful in forecasting SOC, viz: a) ratio between alkylbenzenes and methoxyphenols, b) ratio between short-chain (C0-C4) and long-chain (>C4) alkylbenzenes, c) ratio between methoxyphenols and short-chain alkylbenzenes, and d) ratios between methoxyphenols with different side

Gold and trace element zonation in pyrite using a laser imaging technique: Implications for the timing of gold in orogenic and carlin-style sediment-hosted deposits

USGS Publications Warehouse

Large, R.R.; Danyushevsky, L.; Hollit, C.; Maslennikov, V.; Meffre, S.; Gilbert, S.; Bull, S.; Scott, R.; Emsbo, P.; Thomas, H.; Singh, B.; Foster, J.

2009-01-01

Laser ablation ICP-MS imaging of gold and other trace elements in pyrite from four different sediment- hosted gold-arsenic deposits has revealed two distinct episodes of gold enrichment in each deposit: an early synsedimentary stage where invisible gold is concentrated in arsenian diagenetic pyrite along with other trace elements, in particular, As, Ni, Pb, Zn, Ag, Mo, Te, V, and Se; and a later hydrothermal stage where gold forms as either free gold grains in cracks in overgrowth metamorphic and/or hydrothermal pyrite or as narrow gold- arsenic rims on the outermost parts of the overgrowth hydrothermal pyrite. Compared to the diagenetic pyrites, the hydrothermal pyrites are commonly depleted in Ni, V, Zn, Pb, and Ag with cyclic zones of Co, Ni, and As concentration. The outermost hydrothermal pyrite rims are either As-Au rich, as in moderate- to high- grade deposits such as Carlin and Bendigo, or Co-Ni rich and As-Au poor as in moderate- to low-grade deposits such as Sukhoi Log and Spanish Mountain. The early enrichment of gold in arsenic-bearing syngenetic to diagenetic pyrite, within black shale facies of sedimentary basins, is proposed as a critical requirement for the later development of Carlin-style and orogenic gold deposits in sedimentary environments. The best grade sediment-hosted deposits appear to have the gold climax event, toward the final stages of deformation-related hydrothermal pyrite growth and fluid flow. ?? 2009 Society of Economic Geologists, Inc.

Calcium isotopes in fossil bones and teeth — Diagenetic versus biogenic origin

NASA Astrophysics Data System (ADS)

Heuser, Alexander; Tütken, Thomas; Gussone, Nikolaus; Galer, Stephen J. G.

2011-06-01

primary δ44/40Ca is actually preserved in most of the fossil teeth is a difference in δ44/40Ca of about 0.35 ± 0.10‰ (1SD) between dentin and enamel, based upon 11 of 16 analyzed dentin-enamel pairs. This difference is close to that found in modern reptiles (0.28 ± 0.05‰), and strongly suggests that this tell-tale signature is a primary feature of the fossilized dinosaur material as well. Furthermore, simple mass balance calculations show that changes of the original δ44/40Ca in bones and teeth by diagenetically-formed calcium-bearing minerals are either small or would require implausible high original δ44/40Ca values in the skeletal apatite.

Diagenetic trends of a tertiary low-rank coal series

NASA Astrophysics Data System (ADS)

Boudou, Jean-Paul; Durand, Bernard; Oudin, Jean-Louis

1984-10-01

The Mahakam delta (Kalimantan, Indonesia) coals represent all the evolution stages between freshly-deposited plant/peat material, lignites and bituminous coals. The geochemical techniques used to study this coal series included elemental analysis, extraction of humic compounds, infrared spectroscopy and 13C nuclear magnetic resonance of the total coal. The main mechanisms of early maturation in this series are loss of oxygenated compounds, aromatisation and condensation of the organic matter. These changes, which have already been suggested for other coal series and partially reported for sedimentary organic matter, were confirmed and described in more detail for the Mahakam coal series.

Magnetic Hysteresis Parameters and Day-Plot Analysis to Delineate Diagenetic Alteration in Gas Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

Enkin, R. J.; Baker, J.; Nourgaliev, D.; Iassonov, P.

2005-12-01

Gas hydrates are naturally occurring cage structures of ice found in continental slope and permafrost sediments. They contain vast quantities of methane which is important both as a climate driver and an energy resource. Hydrate formation alters the redox potential of interstitial fluids which can in turn alter magnetic minerals. Thus magnetic methods can help delineate diagenetic pathways, provide a proxy method to map out past hydrate occurrences, and eventually lead to new remote sensing methods in prospecting for gas hydrates. We present data acquired using a J-Meter Coercivity Spectrometer. Induced and remanent magnetism are simultaneously measured on 1.5 cc samples as they spin on a 50 cm diameter disk, 20 times per second. The applied field ramps between ± 500 mT to produce a hysteresis loop in 7 minutes. Sub-second viscous decay is measured to provide a proxy for the amount of superparamagnetism present. The rapid and simple measurements made possible by this robust machine are ideal for core logging. Measurements made on frozen core from the Mallik permafrost gas hydrate field in Canada's Northwest Territories demonstrates that the magnetic properties are dependent on the concentration of gas hydrate present. Day-plots of magnetic hysteresis parameter ratios distinguish the magnetic carriers in gas hydrate rich sediments. The original magnetite is often reduced to sulphide when gas hydrate concentration exceeds 40%. In other high-concentration gas hydrate horizons, fine single-domain (SD) grains of magnetite apparently dissolve leaving nothing but large multi-domain (MD) magnetite grains. Independently measured superparamagnetism is shown to push hysteresis ratios off the hyperbola expected for SD-MD mixtures, as predicted by Dunlop [JGR, 10.10291/2001JB000486, 2002]. Magnetic study of host sediments in gas hydrate systems provides a powerful core-logging tool, offers a window into the processes of gas hydrate formation, and forms the basis for

The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

NASA Technical Reports Server (NTRS)

Freeman, K. H.; Boreham, C. J.; Summons, R. E.; Hayes, J. M.

1994-01-01

Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.

Constraints on Early Triassic carbon cycle dynamics from paired organic and inorganic carbon isotope records

NASA Astrophysics Data System (ADS)

Meyer, K. M.; Yu, M.; Lehrmann, D.; van de Schootbrugge, B.; Payne, J. L.

2013-01-01

Large δ13C excursions, anomalous carbonate precipitates, low diversity assemblages of small fossils, and evidence for marine euxinia in uppermost Permian and Lower Triassic strata bear more similarity to Neoproterozoic carbonates than to the remainders of the Permian and Triassic systems. Middle Triassic diversification of marine ecosystems coincided with the waning of anoxia and stabilization of the global carbon cycle, suggesting that environment-ecosystem linkages were important to biological recovery. However, the Earth system behavior responsible for these large δ13C excursions remains poorly constrained. Here we present a continuous Early Triassic δ13Corg record from south China and use it to test the extent to which Early Triassic excursions in δ13Ccarb record changes in the δ13C of marine dissolved inorganic carbon (DIC). Regression analysis demonstrates a significant positive correlation between δ13Corg and δ13Ccarb across multiple sections that span a paleoenvironmental gradient. Such a correlation is incompatible with diagenetic alteration because no likely mechanism will alter both δ13Corg and δ13Ccarb records in parallel and therefore strongly indicates a primary depositional origin. A simple explanation for this correlation is that a substantial portion of the preserved Corg was derived from the contemporaneous DIC pool, implying that the observed excursions reflect variation in the δ13C of the exogenic carbon reservoir (ocean, atmosphere, biomass). These findings support existing evidence that large δ13C excursions are primary and therefore strengthen the case that large-scale changes to the carbon cycle were mechanistically linked to the low diversity and small size of Early Triassic fossils. Associated sedimentary and biogeochemical phenomena further suggest that similar associations in Neoproterozoic and Cambrian strata may reflect the same underlying controls.

Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

NASA Technical Reports Server (NTRS)

Beukes, N. J.; Klein, C.; Kaufman, A. J.; Hayes, J. M.

1990-01-01

The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic

The Amorphous Composition of Three Mudstone Samples from Gale Crater: Implications for Weathering and Diagenetic Processes on Mars

NASA Technical Reports Server (NTRS)

Achilles, C. N.; Downs, R. T.; Rampe, E. B.; Morris, R. V.; Bristow, T. F.; Ming, D. W.; Blake, D. F.; Vaniman, D. T.; Morrison, S. M.; Sutter, B.;

Sedimentological context of the continental sabkhas of Abu Dhabi

NASA Astrophysics Data System (ADS)

Lokier, Stephen; Paul, Andreas; Bixiao, Xin

2017-04-01

For more than half a century, the coastal sabkhas of Abu Dhabi have been the focus of intensive research focusing on deposition, early diagenesis and the role of microbial communities. Given all of this activity, it is somewhat surprising that their continental counterparts have been largely neglected with only a brief mention in larger-scale regional studies. This study redresses this imbalance by documenting the sedimentological, mineralogical and early diagenetic characteristics of continental sabkhas that are hosted in the Rub al Khali desert of the United Arab Emirates. During reconnaissance surveys it has been established that organic-rich microbial mats and evaporite minerals, both similar to those observed in the coastal sabkha, also occur in these continental sabkha settings. Satellite imagery was utilised to identify potential field locations for surface and shallow sub surface investigation; subsequent field reconnaissance established the validity of sites in terms of anthropogenic disruption and accessibility. At each site, surface features were described in detail, particularly with reference to any microbial communities or evaporite crusts; sample pits were dug in order to document sub-surface facies geometries and to recover both sediment and pore water samples for subsequent analysis. In each pit, a range of environmental parameters was measured over a prolonged period, including surface and sub-surface temperatures, ground water salinity and dissolved oxygen. Sediment samples were subjected to a range of analyses in order to establish and quantify primary sediment composition and any early diagenetic mineral phases. The results of this study are used to build an atlas of sedimentary structures and textures that are associated with continental sabkha settings. These observations allow us to establish the defining sedimentological and early diagenetic characteristics that can be employed to identify similar depositional environments in ancient

Zinc and germanium in the sedimentary rocks of Gale Crater on Mars indicate hydrothermal enrichment followed by diagenetic fractionation

NASA Astrophysics Data System (ADS)

Berger, Jeff A.; Schmidt, Mariek E.; Gellert, Ralf; Boyd, Nicholas I.; Desouza, Elstan D.; Flemming, Roberta L.; Izawa, Matthew R. M.; Ming, Douglas W.; Perrett, Glynis M.; Rampe, Elizabeth B.; Thompson, Lucy M.; VanBommel, Scott J. V.; Yen, Albert S.

2017-08-01

Zinc and germanium enrichments have been discovered in sedimentary rocks in Gale Crater, Mars, by the Alpha Particle X-ray Spectrometer on the rover Curiosity. Concentrations of Zn (910 ± 840 ppm) and Ge (65 ± 58 ppm) are tens to hundreds of times greater than in Martian meteorites and estimates for average silicate Mars. Enrichments occur in diverse rocks including minimally to extensively altered basaltic and alkalic sedimentary rocks. The magnitude of the enrichments indicates hydrothermal fluids, but Curiosity has not discovered unambiguous hydrothermal mineral assemblages. We propose that Zn- and Ge-rich hydrothermal deposits in the source region were dispersed in siliciclastic sediments during transport into the crater. Subsequent diagenetic mobilization and fractionation of Zn and Ge is evident in a Zn-rich sandstone (Windjana; Zn 4000 ppm, Ge 85 ppm) and associated Cl-rich vein (Stephen; Zn 8000 ppm, Ge 60 ppm), in Ge-rich veins (Garden City; Zn 2200 ppm, Ge 650 ppm), and in silica-rich alteration haloes leached of Zn (30-200 ppm). In moderately to highly altered silica-rich rocks, Ge remained immobile relative to leached elements (Fe, Mn, Mg, and Ca), consistent with fluid interaction at pH ≪ 7. In contrast, crosscutting Ge-rich veins at Garden City suggest aqueous mobilization as Ge-F complexes at pH < 2.5. Multiple jarosite detections by the CheMin X-ray diffractometer and variable Zn concentrations indicate diagenesis of lower Mount Sharp bedrock under acidic conditions. The enrichment and fractionation of Zn and Ge constrains fluid events affecting Gale sediments and can aid in unraveling fluid histories as Curiosity's traverse continues.

Early diagenesis of vascular plant tissues: Lignin and cutin decomposition and biogeochemical implications

NASA Astrophysics Data System (ADS)

Opsahl, Stephen; Benner, Ronald

1995-12-01

Long-term subaqueous decomposition patterns of five different vascular plant tissues including mangrove leaves and wood ( Avicennia germinans), cypress needles and wood ( Taxodium distichum) and smooth cordgrass ( Spartina alternifora) were followed for a period of 4.0 years, representing the longest litter bag decomposition study to date. All tissues decomposed under identical conditions and final mass losses were 97, 68, 86, 39, and 93%, respectively. Analysis of the lignin component of herbaceous tissues using alkaline CuO oxidation was complicated by the presence of a substantial ester-bound phenol component composed primarily of cinnamyl phenols. To overcome this problem, we introduce a new parameter to represent lignin, Λ6. Λ6 is comprised only of the six syringyl and vanillyl phenols and was found to be much less sensitive to diagenetic variation than the commonly used parameter Λ, which includes the cinnamyl phenols. Patterns of change in lignin content were strongly dependent on tissue type, ranging from 77% enrichment in smooth cordgrass to 6% depletion in cypress needles. In contrast, depletion of cutin was extensive (65-99%) in all herbaceous tissues. Despite these differences in the overall reactivity of lignin and cutin, both macromolecules were extensively degraded during the decomposition period. The long-term decomposition series also provided very useful information about the compositional parameters which are derived from the specific oxidation products of both lignin and cutin. The relative lability of ester-bound cinnamyl phenols compromised their use in parameters to distinguish woody from herbaceous plant debris. The dimer to monomer ratios of lignin-derived phenols indicated that most intermonomeric linkages in lignin degraded at similar rates. Acid to aldehyde ratios of vanillyl and syringyl phenols became elevated, particularly during the latter stages of decomposition supporting the use of these parameters as indicators of diagenetic

Synthesis and Characterization of Chalcopyrite (CuInS2 and CuhInSe2) Colloidal Nanoparticles for Optoelectronic Applications via Low-Temperature Pyrolysis of Single-Source Precursors

NASA Technical Reports Server (NTRS)

Castro, S. L.; Bailey, S. G.; Raffaelle, R. P.; Banger, K. K.; Fahey, Stephen; Hepp, A. F.

2003-01-01

Nanocrystalline (or quantum dot) materials hold potential as components of next-generation photovoltaic (PV) devices. The inclusion of quantum dots in PV devices has been proposed as a means to improve the efficiency of photon conversion (quantum dot solar cell), enable low-cost deposition of thin-films, provide sites for exciton dissociation, and pathways for electron transport. Quantum dots are also expected to be more resistant to degradation from electron, proton, and alpha particle radiation than the corresponding bulk material, a requirement for use in space solar sells. Chalcopyrite nanocrystals can be produced by low-temperature thermal decomposition of single-source precursors such as (PR3)2CuIn(ER')4 (R = Ph, R' = Et, E = S; R = R' = Ph, E = Se). Single-source precursors are molecules which contain all the necessary elements for synthesis of a desired material. Thermal decomposition of the precursor results in the formation of material with the correct stoichiometry as a nanocrystalline powder or a thin film, often at significantly lower temperatures than those typically employed for thin-film deposition by multi-source evaporation techniques, typically less than 500 C. We show that CuInSz and CuInSe2 nanocrystals can be synthesized from the precursors at temperatures as low as 250 C. The nanocrystals are characterized by optical spectroscopy, X-ray diffraction, and electron microscopy.

Copper-nickel-rich, amalgamated ferromanganese crust-nodule deposits from Shatsky Rise, NW Pacific

USGS Publications Warehouse

Hein, J.R.; Conrad, T.A.; Frank, M.; Christl, M.; Sager, W.W.

2012-01-01

A unique set of ferromanganese crusts and nodules collected from Shatsky Rise (SR), NW Pacific, were analyzed for mineralogical and chemical compositions, and dated using Be isotopes and cobalt chronometry. The composition of these midlatitude, deep-water deposits is markedly different from northwest-equatorial Pacific (PCZ) crusts, where most studies have been conducted. Crusts and nodules on SR formed in close proximity and some nodule deposits were cemented and overgrown by crusts, forming amalgamated deposits. The deep-water SR crusts are high in Cu, Li, and Th and low in Co, Te, and Tl concentrations compared to PCZ crusts. Thorium concentrations (ppm) are especially striking with a high of 152 (mean 56), compared to PCZ crusts (mean 11). The deep-water SR crusts show a diagenetic chemical signal, but not a diagenetic mineralogy, which together constrain the redox conditions to early oxic diagenesis. Diagenetic input to crusts is rare, but unequivocal in these deep-water crusts. Copper, Ni, and Li are strongly enriched in SR deep-water deposits, but only in layers older than about 3.4 Ma. Diagenetic reactions in the sediment and dissolution of biogenic calcite in the water column are the likely sources of these metals. The highest concentrations of Li are in crust layers that formed near the calcite compensation depth. The onset of Ni, Cu, and Li enrichment in the middle Miocene and cessation at about 3.4 Ma were accompanied by changes in the deep-water environment, especially composition and flow rates of water masses, and location of the carbonate compensation depth.

Nanometer-scale features in dolomite from Pennsylvanian rocks, Paradox Basin, Utah

NASA Astrophysics Data System (ADS)

Gournay, Jonas P.; Kirkland, Brenda L.; Folk, Robert L.; Lynch, F. Leo

1999-07-01

Scanning electron microscopy reveals an association between early dolomite in the Pennsylvanian Desert Creek (Paradox Fm.) and small (approximately 0.1 μm) nanometer-scale textures, termed `nannobacteria'. Three diagenetically distinct dolomites are present: early dolomite, limpid dolomite, and baroque dolomite. In this study, only the early dolomite contained nanometer-scale features. These textures occur as discrete balls and rods, clumps of balls, and chains of balls. Precipitation experiments demonstrate that these textures may be the result of precipitation in an organic-rich micro-environment. The presence of these nanometer-scale textures in Pennsylvanian rocks suggests that these early dolomites precipitated in organic-rich, bacterial environments.

Study of Diagenetic Features in Rudist Buildups of Cretaceous Edwards Formation Using Ground Based Hyperspectral Scanning and Terrestrial LiDAR

NASA Astrophysics Data System (ADS)

Krupnik, D.; Khan, S.; Okyay, U.; Hartzell, P. J.; Biber, K.

2015-12-01

Ground based remote sensing is a novel technique for development of digital outcrop models which can be instrumental in performing detailed qualitative and quantitative sedimentological analysis for the study of depositional environment, diagenetic processes, and hydrocarbon reservoir characterization. For this investigation, ground-based hyperspectral data collection is combined with terrestrial LiDAR to study outcrops of Late Albian rudist buildups of the Edwards formation in the Lake Georgetown Spillway in Williamson County, Texas. The Edwards formation consists of shallow water deposits of reef and associated inter-reef facies, including rudist bioherms and biostromes. It is a significant aquifer and was investigated as a hydrocarbon play in south central Texas. Hyperspectral data were used to map compositional variation in the outcrop by distinguishing spectral properties unique to each material. Lithological variation was mapped in detail to investigate the structure and composition of rudist buildups. Hyperspectral imagery was registered to a 3D model produced from the LiDAR point cloud with an accuracy of up to one pixel. Flat-topped toucasid-rich bioherm facies were distinguished from overlying toucasid-rich biostrome facies containing chert nodules, overlying sucrosic dolostones, and uppermost peloid wackestones and packstones of back-reef facies. Ground truth was established by petrographic study of samples from this area and has validated classification products of remote sensing data. Several types of porosity were observed and have been associated with increased dolomitization. This ongoing research involves integration of remotely sensed datasets to analyze geometrical and compositional properties of this carbonate formation at a finer scale than traditional methods have achieved and seeks to develop a workflow for quick and efficient ground based remote sensing-assisted outcrop studies.

Elemental geochemistry of sedimentary rocks at Yellowknife Bay, Gale crater, Mars.

PubMed

McLennan, S M; Anderson, R B; Bell, J F; Bridges, J C; Calef, F; Campbell, J L; Clark, B C; Clegg, S; Conrad, P; Cousin, A; Des Marais, D J; Dromart, G; Dyar, M D; Edgar, L A; Ehlmann, B L; Fabre, C; Forni, O; Gasnault, O; Gellert, R; Gordon, S; Grant, J A; Grotzinger, J P; Gupta, S; Herkenhoff, K E; Hurowitz, J A; King, P L; Le Mouélic, S; Leshin, L A; Léveillé, R; Lewis, K W; Mangold, N; Maurice, S; Ming, D W; Morris, R V; Nachon, M; Newsom, H E; Ollila, A M; Perrett, G M; Rice, M S; Schmidt, M E; Schwenzer, S P; Stack, K; Stolper, E M; Sumner, D Y; Treiman, A H; VanBommel, S; Vaniman, D T; Vasavada, A; Wiens, R C; Yingst, R A

2014-01-24

Sedimentary rocks examined by the Curiosity rover at Yellowknife Bay, Mars, were derived from sources that evolved from an approximately average martian crustal composition to one influenced by alkaline basalts. No evidence of chemical weathering is preserved, indicating arid, possibly cold, paleoclimates and rapid erosion and deposition. The absence of predicted geochemical variations indicates that magnetite and phyllosilicates formed by diagenesis under low-temperature, circumneutral pH, rock-dominated aqueous conditions. Analyses of diagenetic features (including concretions, raised ridges, and fractures) at high spatial resolution indicate that they are composed of iron- and halogen-rich components, magnesium-iron-chlorine-rich components, and hydrated calcium sulfates, respectively. Composition of a cross-cutting dike-like feature is consistent with sedimentary intrusion. The geochemistry of these sedimentary rocks provides further evidence for diverse depositional and diagenetic sedimentary environments during the early history of Mars.

Early dolomitization in the Lower Cretaceous shallow-water carbonates of Southern Apennines (Italy): Clues about palaeoclimatic fluctuations in western Tethys

NASA Astrophysics Data System (ADS)

Vinci, Francesco; Iannace, Alessandro; Parente, Mariano; Pirmez, Carlos; Torrieri, Stefano; Giorgioni, Maurizio

2017-12-01

diagenetic dolomite may be used as proxy to define the climatic fluctuations that have influenced the sedimentary dynamics in the Early Cretaceous. Moreover, considering that a comparable early dolomite distribution is present also in the Dinaric Platform, we suggest that a regional scale climate control acted on early dolomite formation and distribution. Refining the knowledge of such a key control may have a significative impact on hydrocarbon reservoir characterization and exploration in the Periadriatic area.

The origin of decoupled carbonate and organic carbon isotope signatures in the early Cambrian (ca. 542-520 Ma) Yangtze platform

NASA Astrophysics Data System (ADS)

Jiang, Ganqing; Wang, Xinqiang; Shi, Xiaoying; Xiao, Shuhai; Zhang, Shihong; Dong, Jin

2012-02-01

The early Cambrian (ca. 542-520 Ma) strata in South China record two prominent negative carbonate carbon isotope (δ13Ccarb) excursions of early Nemakit-Daldynian (N-D) and early Tommotian ages. Across each of these excursions, carbonate and organic carbon isotopes (δ13Ccarb and δ13Corg) are strongly decoupled. Regional correlation across a shelf-to-basin transect shows lateral heterogeneity of δ13Corg during the early-middle N-D but more homogenized δ13Corg values across the basin during the late N-D and Tommotian. The temporal and lateral variations in δ13Corg suggest that decoupled δ13Ccarb and δ13Corg across the N-D δ13Ccarb excursion were possibly caused by diagenetic alteration of organic matter and/or amplification of detrital organic carbon isotope signature in low-TOC carbonates. In contrast, decoupled δ13Ccarb and δ13Corg of the upper N-D and Tommotian were likely resulted from chemoautotrophic-methanotrophic biomass contribution to TOC in organic-rich black shale and carbonates. The decoupled δ13Ccarb-δ13Corg pattern from the lower N-D strata (ca. 542 Ma) shows striking similarities with those from the basal (ca. 635 Ma) and upper (ca. 551 Ma) Doushantuo Formation. In all three cases, decoupled δ13Ccarb-δ13Corg are seen in organic-poor carbonates (TOC ≤ 0.1‰) and coupled δ13Ccarb-δ13Corg occur in organic-rich black shale and carbonates at the end of the negative δ13Ccarb excursion. These similarities suggest that the shift from decoupled to coupled δ13Ccarb-δ13Corg has no causal link with the terminal oxidation of a large oceanic DOC reservoir. Given the pervasive anoxia/euxinia in Ediacaran-early Cambrian oceans, local DOC-rich environments may have been common, but a large oceanic DOC reservoir capable of buffering the δ13C of marine organic matter requires independent evidence.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruno, C.; Eichenseer, H.; Calatayud, P.

The poster illustrates how the recent developments in genetic stratigraphy have contributed to constrain reservoir layering and to improve prediction of reservoir quality in the oil-bearing reservoir of N`KOSSA. The mixed lithology deposits formed during Albian times. Thanks to the excellent core coverage of the reservoir (4 cored wells over the entire reservoir interval), continuous sedimentological examination and interpretation of the facies succession have been carried out. The reservoir can be subdivided into composite sequences (50 to 150 in thick) which are made up of stacked metre-scale genetic units. Three different stacking patterns of genetic units have been identified; retrogradation,more » aggradation and progradation. These patterns reflect a gradual change of depositional regimes through time. Facies variations (texture, bio-association, geometry, spatial distribution) and early diagenetic overprints can be related to each type of stacking pattern. One additional model illustrates the depositional regime corresponding to low accomodation periods which mainly record siliciclastic input and extensive carbonate diagenesis by meteoric waters The resulting four models show the overall distribution of the main depositional units, the diagenetic zonations and the resulting overall reservoir qualities. This above approach have contributed to a more detailed reservoir architecture and a better delineation of reservoir heterogeneity due to both depositional and diagenetic regimes.« less

Petrography, geochemistry and geochronology of the host porphyries and associated alteration at the Tuwu Cu deposit, NW China: a case for increased depositional efficiency by reaction with mafic hostrock?

NASA Astrophysics Data System (ADS)

Shen, Ping; Pan, Hongdi; Zhou, Taofa; Wang, Jingbin

2014-08-01

Tuwu is the largest porphyry copper deposit discovered in the Eastern Tianshan Mountains, Xinjiang, China. A newly recognized volcanic complex in the Early Carboniferous Qi'eshan Group at Tuwu consists of basalt, andesite, and diorite porphyry. The plagiogranite porphyry was emplaced into this complex at 332.8±2.5 Ma (U-Pb zircon SIMS determination). Whole-rock element geochemistry shows that the volcanic complex and plagiogranite porphyry formed in the same island arc, although the complex was derived by partial melting of the mantle wedge and the plagiogranite porphyry by partial melting of a subducting slab. The diorite and the plagiogranite porphyries have both been subjected to intense hydrothermal alteration and associated mineralization, but the productive porphyry is the plagiogranite porphyry. Three alteration and mineralization stages, including pre-, syn- and post-ore stages, have been recognized. The pre-ore stage formed a barren propylitic alteration which is widespread in the volcanic complex. The syn-ore stage is divided into three sub-stages: Stage 1 is characterized by potassic alteration with chalcopyrite + bornite + chalcocite; Stage 2 is marked by chlorite-sericite-albite alteration with chalcopyrite ± pyrite ± bornite; Stage 3 is represented by phyllic alteration with chalcopyrite + pyrite ± molybdenite. The post-ore stage produced a barren argillic alteration limited to the diorite porphyry. A specific feature of the Tuwu deposit is that the productive porphyry was emplaced into a very mafic package, and reaction of the resulting fluids with the ferrous iron-rich hostrocks was a likely reason that Tuwu is the largest porphyry in the district.

Early-mid-Cretaceous evolution in Tethyan reef communities and sea level

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scott, R.W.

1988-01-01

The replacement of corals by rudists in Early Cretaceous reefal communities spanned a 30-m.y. period when sea level rose and drowned continental shelves. During this time corals formed communities in the deeper parts of reefs and rudists occupied the shallow, high-energy habitats. By Aptian time rudists dominated reefs that fringed interior shelf basins and corals formed reefs with rudists on the outer shelf margins. By late Albian coral communities had virtually disappeared, presumably because of complex environmental changes and cycles of organic productivity. Two important events of eustatic sea level rise are represented by unconformities separating carbonate depositional sequences onmore » the Arabian platform that correlate with sequence boundaries on the Gulf Coast platform. Graphic correlation techniques test the synchroneity of these events. A composite standard time scale dates these sea level rises at 115.8 Ma and 94.6 Ma; a third, intra-Albian event at 104.3 Ma is present in many places and may also be eustatic. Associated with these sea level rises were apparent changes in ocean water chemistry as evidenced by changes in isotopes and trace elements, where diagenetic effects can be discounted. During this time the climate became more humid and atmospheric CO/sub 2/ increased. The concomitant environmental changes in the oceanic conditions presumably stressed the deeper coral communities on reefs. The emergence of rudists as reef contributors had a profound effect on Late Cretaceous depositional conditions and the development of hydrocarbon reservoirs.« less

Early-mid-Cretaceous evolution in Tethyan reef communities and sea level

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scott, R.W.

1988-02-01

The replacement of corals by rudists in Early Cretaceous reefal communities spanned a 30-m.y. period when sea level rose and drowned continental shelves. During this time corals formed communities in the deeper parts of reefs and rudists occupied the shallow, high-energy habitats. By Aptian time rudists dominated reefs that fringed interior shelf basins and corals formed reefs with rudists on the outer shelf margins. By late Albian coral communities had virtually disappeared, presumably because of complex environmental changes and cycles of organic productivity. Two important events of eustatic sea level rise are represented by unconformities separating carbonate depositional sequences onmore » the Arabian platform that correlate with sequence boundaries on the Gulf Coast platform. Graphic correlation techniques test the synchroneity of these events. A composite standard time scale dates these sea level rises at 115.8 Ma and 94.6 Ma; a third, intra-Albian event at 104.3 Ma is present in many places and may also be eustatic. Associated with these sea level rises were apparent changes in ocean water chemistry as evidenced by changes in isotopes and trace elements, where diagenetic effects can be discounted. During this time the climate became more humid and atmospheric CO/sub 2/ increased. The concomitant environmental changes in the oceanic conditions presumably stressed the deeper coral communities on reefs. The emergence of rudists as reef contributors had a profound effect on Late Cretaceous depositional conditions and the development of hydrocarbon reservoirs.« less

Impact of diagenesis and low grade metamorphosis on Triassic sabkha dolomite δ26Mg

NASA Astrophysics Data System (ADS)

Immenhauser, A.; Geske, A.; Richter, D.; Buhl, D.; Niedermayr, A.

2012-12-01

Dolomite is a common rock forming mineral in the geological record but its value as archive of ancient seawater δ26Mg signatures and their variations in time are at present underexplored. Unknown factors include the sensitivity of δ26Mg ratio to processes in the diagenetic and low grade metamorphic domain. Here, we document and discusses the first detailed δ26Mg data set from early diagenetic and burial dolomites. Samples come from the Upper Triassic Hauptdolomit (Dolomia Principale; The Dolomites, Italy) and include coeval dolmicrites that underwent differential burial diagenesis in a temperature range between about 100 and more than 350°C. As indicated by dolmicrite 87/86Sr ratios, sabkha calcian D1 dolomites precipitated from evaporated seawater and stabilized at an early diagenetic stage to D2 dolomites analysed here. With increasing burial temperature, dolomite δ26Mg ratio scatter in the data set decreases with increasing Mg/Ca ratio and degree of order. Specifically, δ26Mg ratio variability is reduced from ~0.7‰ at burial temperatures beneath 100°C to about ~0.2‰ at temperatures in excess of 350°C, respectively, with mean δ26Mg values ranging constantly near -1.9‰. This suggests that, at least for the rock buffered system investigated here, dolmicrite δ26Mg proxy data are conservative and preserve near pristine values even at elevated burial temperatures. At present, the main element of uncertainty is the Mg-isotope fractionation factor between (evaporated) seawater and dolomite. A possible solution to this problem includes the compilation of a data from modern sabkha environments including pore water and calcian dolomite δ26Mg isotope signatures.

Dolomites and Early Mississippian bioherms, Leadville Formation, Molas Lake, Colorado

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, L.M.

Two dolomite facies that exhibit little petrographic evidence of their original textures are interpreted to be integral parts of two bioherms. A core facies of rugose corals (Vesiculophylum), pelmatozoans, cephalopods, and brachiopods in a peloid wackestone-packstone matrix forms two mounds 50 x 40 m and 110 x 75 m in diameter and 7 and 20 m high, resting on a basal unit of foraminiferal (endothyrid) ooid, coated-grain grainstone. These mounds are surrounded and onlapped by a bedded flank facies with relic cross-bedding that forms a halo 15-40 m wide around each mound. The facies consists of very coarsely to coarselymore » crystalline dolomite, but field evidence shows that it was originally detrital and is coeval with the core facies. It grades laterally away from the core into a distal flank-intermound facies of dolomudstone interbedded with millimeter-thick laminae of dolomite peloid packstone. This facies occurs up to 100 m from the mounds. Corals in the core facies have been replaced and cemented by nonferroan, nonluminescent sparry calcite at temperatures of at least 200/sup 0/C. The matrix of micrite and skeletal grains is composed of nonferroan, red-orange luminescent calcite. Diagenetic changes have been modest. In contrast, the two flank facies show obliteration of original textures and replacement by inclusion-rich, nonferroan, red-luminescent, anhedral to subhedral dolomite at temperatures of a least 165/sup 0/C. Other than appealing to differences in original porosity and susceptibility to subsurface fluids, it is difficult to explain why these closely associated facies have followed such divergent diagenetic paths.« less

Towards a High-resolution Time Scale for the Early Devonian

NASA Astrophysics Data System (ADS)

Dekkers, M. J.; da Silva, A. C.

2017-12-01

High-resolution time scales are crucial to understand Earth's history in detail. The construction of a robust geological time scale, however, inevitably becomes increasingly harder further back in time. Uncertainties associated with anchor radiometric ages increase in size, not speaking of the mere presence of suitable datable strata. However, durations of stages can be tightly constrained by making use of cyclic expressions in sediments, an approach that revolutionized the Cenozoic time scale. When precisely determined durations are stitched together, ultimately, a very precise time scale is the result. For the Mesozoic and Paleozoic an astronomical solution as a tuning target is not available but the dominant periods of eccentricity, obliquity and precession are reasonably well constrained for the entire Phanerozoic which enables their detection by means of spectral analysis. Eccentricity is time-invariant and is used as the prime building block. Here we focus on the Early Devonian, on its lowermost three stages: the Lochkovian, Pragian and Emsian. The uncertainties on the Devonian stage boundaries are currently in the order of several millions of years. The preservation of climatic cycles in diagenetically or even anchimetamorphically affected successions, however, is essential. The fit of spectral peak ratios with those calculated for orbital cycles, is classically used as a strong argument for a preserved climatic signal. Here we use primarily the low field magnetic susceptibility (MS) as proxy parameter, supported by gamma-ray spectrometry to test for consistency. Continuous Wavelet Transform, Evolutive Harmonic Analysis, Multitaper Method, and Average Spectral Misfit are used to reach an optimal astronomical interpretation. We report on classic Early Devonian sections from the Czech Republic: the Pozar-CS (Lochkovian and Pragian), Pod Barrandovem (Pragian and Lower Emsian), and Zlichov (Middle-Upper Emsian). Also a Middle-Upper Emsian section from the US

Potassium metasomatism of volcanic and sedimentary rocks in rift basins, calderas and detachment terranes

NASA Technical Reports Server (NTRS)

Chapin, C. E.; drographic basins.

1985-01-01

The chemical, mineralogical, and oxygen-isotopic changes accompanying K-metasomatism are described. The similarities with diagenetic reactions in both deep marine and alkaline, saline-lake environments are noted. The common occurrence of K-metasomatism in upper-plate rocks of detachment terranes indicates that the early stage of severe regional extension causes crustal downwarping and, in arid to semi-arid regions, development of closed hydrographic basins.

Significance of nodule formation for the interpretation of matrix micrite C and O isotope ratios in Upper Jurassic Ammonitico Rosso limestones (Betic Cordillera, SE Spain)

NASA Astrophysics Data System (ADS)

Coimbra, R.; Immenhauser, A.; Olóriz, F.

2009-04-01

latter diagenesis. In this context, paleoenvironmental considerations are available, and the oxygen curve is interpreted as reasonable approximation of seawater paleo-temperatures and relative depth. Very early marine nodule formation is thought to be determinant for the high isotope values found at these locations. It is proposed that early diagenetic nodule formation preserved near-seawater isotopic signals and inhibited subsequent diagenetic overprint as revealed by several proxies retrieved from intra-nodule samples.

Dolomitization in Late Jurassic-Early Cretaceous Platform Carbonates (Berdiga Formation), Ayralaksa Yayla (Trabzon), NE Turkey

NASA Astrophysics Data System (ADS)

Yıldız, Merve; Ziya Kırmacı, Mehmet; Kandemir, Raif

2017-04-01

ABSTRACT Pontides constitute an E-W trending orogenic mountain belt that extends about 1100 km along the northern side of Turkey from the immediate east of Istanbul to the Georgian border at the east. Tectono-stratigraphically, the Pontides are divided into three different parts: Eastern, Central, and Western Pontides. The Eastern Pontides, including the studied area, comprise an area of 500 km in length and 100 km in width, extending along the southeast coast of the Black Sea from the Kizilirmak and Yesilirmak Rivers in the vicinity of Samsun to the Little Caucasus. This area is bordered by the Eastern Black Sea basin to the north and the Ankara-Erzincan Neotethyan suture zone to the south. The Late Jurassic-Early Cretaceous platform carbonates are widely exposed in E-W direction in the Eastern Pontides (NE Turkey). The Platform carbonates shows varying lithofacies changing from supratidal to platform margin reef laterally and vertically, and was buried until the end of Late Cretaceous. The studied Ayralaksa Yayla (Trabzon, NE Turkey) area comprises one of the best typical exposures of formation in northern zone of Eastern Pontides. In this area, the lower parts of the formation are pervasively dolomitized by fabric-destructive and fabric-preserving replacement dolomite which are Ca-rich and nonstoichiometric (Ca56-66Mg34-44). Replacement dolomites (Rd) are represented by D18O values of -19.0 to -4.2 (VPDB), D13C values of 4.4 to 2.1 \\permil (VPDB) and 87Sr/86Sr ratios of 0.70889 to 0.70636. Petrographic and geochemical data indicate that Rd dolomites are formed prior to compaction at shallow-moderate burial depths from Late Jurassic-Early Cretaceous seawater and/or partly modified seawater as a result of water/rock interaction and they were recrystallized at elevated temperatures during subsequent burial. In the subsequent diagenetic process during the Late Cretaceous when the region became a magmatic arc, as a result of interaction with Early Jurassic volcanic

Sedimentary environment and diagenesis of the Lower Cretaceous Chaswood Formation, southeastern Canada: The origin of kaolin-rich mudstones

NASA Astrophysics Data System (ADS)

Pe-Piper, Georgia; Dolansky, Lila; Piper, David J. W.

2005-07-01

The Lower Cretaceous fluvial sandstone-mudstone succession of the Chaswood Formation is the proximal equivalent of offshore deltaic rocks of the Scotian Basin that are reservoirs for producing gas fields. This study interprets the mineralogical consequences of Cretaceous weathering and early diagenesis in a 130-m core from the Chaswood Formation in order to better understand detrital and diagenetic minerals in equivalent rocks offshore. Mineralogy was determined by X-ray diffraction, electron microprobe analysis and scanning electron microscopy. The rocks can be divided into five facies associations: light gray mudstone, dark gray mudstone, silty mudstone and muddy sandstone, sorted sandstone and conglomerate, and paleosols. Facies transitions in coarser facies are related to deposition in and near fluvial channels. In the mudstones, they indicate an evolutionary progression from the dark gray mudstone facies association (swamps and floodplain soils) to mottled paleosols (well-drained oxisols and ultisols following syntectonic uplift). Facies transitions and regional distribution indicate that the light gray mudstone facies association formed from early diagenetic oxidation and alteration of the dark gray mudstone facies association, probably by meteoric water. Principal minerals in mudstones are illite/muscovite, kaolinite, vermiculite and quartz. Illite/muscovite is of detrital origin, but variations in abundance show that it has altered to kaolinite in the light gray mudstone facies association and in oxisols. Vermiculite developed from the weathering of biotite and is present in ultisols. The earliest phase of sandstone cementation in reducing conditions in swamps and ponds produced siderite nodules and framboidal pyrite, which were corroded and oxidized during subsequent development of paleosols. Kaolinite is an early cement, coating quartz grains and as well-crystallized, pore-filling booklets that was probably synchronous with the formation of the light gray

Depositional Architecture of Late Cambrian-Early Ordovician Siliciclastic Barik Formation; Al Huqf Area, Oman

NASA Astrophysics Data System (ADS)

Abbasi, Iftikhar Ahmed

2017-04-01

Early Paleozoic siliciclastics sediments of the Haima Supergroup are subdivided into a number of formations and members based on lithological characteristics of various rock sequences. One of the distinct sandstone sequence, the Barik Formation (Late Cambrian-Early Ordovician) of the Andam Group is a major deep gas reservoir in central Oman. The sandstone bodies are prospective reservoir rocks while thick shale and clay interbeds act as effective seal. Part of the Barik Formation (lower and middle part) is exposed in isolated outcrops in Al Huqf area as interbedded multistoried sandstone, and green and red shale. The sandstone bodies are up to 2 meters thick and can be traced laterally for 300 m to over 1 km. Most of sandstone bodies show both lateral and vertical stacking. Two types of sandstone lithofacies are identified on the basis of field characteristics; a plane-bedded sandstone lithofacies capping thick red and green color shale beds, and a cross-bedded sandstone lithofacies overlying the plane-bedded sandstone defining coarsening upward sequences. The plane-bedded sandstone at places contains Cruziana ichnofacies and bivalve fragments indicating deposition by shoreface processes. Thick cross-bedded sandstone is interpreted to be deposited by the fluvial dominated deltaic processes. Load-casts, climbing ripples and flaser-bedding in siltstone and red shale indicate influence of tidal processes at times during the deposition of the formation. This paper summarizes results of a study carried out in Al Huqf area outcrops to analyze the characteristics of the sandstone-body geometry, internal architecture, provenance and diagenetic changes in the lower and middle part of the formation. The study shows build-up of a delta complex and its progradation over a broad, low-angle shelf where fluvial processes operate beside shoreface processes in a vegetation free setting. Keywords: Andam Group, Barik Formation, Ordovician sandstone, Al Huqf, Central Oman,

Early Diagenetic Changes of Sediment Pore Properties Beneath the Seafloor and Their Contributions to Gas Hydrate Concentration in the Eastern Margin of Japan Sea

NASA Astrophysics Data System (ADS)

Uchida, T.; Horiuchi, S.; Kato, Y.; Matsumoto, R.

2014-12-01

Recently many of the chimney-shape gas hydrate concentrated beneath the seafloor have been confirmed off Shimane and off Akita as well as off Joetsu in the eastern margin of Japan Sea, which are quite different from the occurrences of pore space hydrate filling the intergranular pore system of sands recognized in Nankai Trough, Mallik and other sites. Sediment samples below the seafloor were retrieved in 2010 up to 40 m long at the Umitaka Spur, Joetsu Channel, Toyama Trough, Japan Basin, Nishi Tsugaru and Okushiri Ridge areas. Small amounts of sandy sediment have been retrieved as thin intercalations in Pleistocene and Holocene muddy layers transported approximately around 3 to 30 ka according to the tephra ages, where supplying sediments might have not been abundant due to sea level fluctuation during the Pleistocene ice age. It is important to clarify the relationship between burial depths and absolute porosities of the argillaceous sediments in relation to early diagenesis. Macroscopic observations and descriptions, measurements of porosity and permeability, SEM (scanning electron microscope) observations, and X-ray diffraction analyses have been performed. They consist of silt- to clay-grained particles, and they sometimes contain very fine- to medium-grained thin sandy layers. Average porosities of these fine-grained sediments are 50 % in all study areas, which quickly reduce from 60% to less than 50% within 10 meters and gradually decrease to the depth. However, mean pore sizes in the Nishi Tsugaru are around 1000 nm while 100 nm in the other areas, which tend to decrease with depth. It is suggested that repacking of the muddy particles gradually advances by mechanical compaction, which may crucially influence permeability. They usually contain much opal-A, quartz, feldspar, illite and smectite that do not change definitely with depth. By optical and microscopic observations, diatom tests, foraminifers and framboidal pyrites are commonly observed, and, in

Magnetic history of Early and Middle Ordovician sedimentary sequence, northern Estonia

NASA Astrophysics Data System (ADS)

Plado, J.; Preeden, U.; Pesonen, L. J.; Mertanen, S.; Puura, V.

2010-01-01

Alternating field and thermal demagnetization of lime- and dolostones from the Lower and Middle Ordovician (Floian to Darriwilian stages) subhorizontally bedded sequences in NW and NE Estonia reveal two characteristic magnetization components (named P and S). The intermediate-coercivity (demagnetized at 30-60 mT, up to 300-350°C) reversed polarity component P (mean of Floian Stage: Dref = 147.8 +/- 10.8°, Iref = 65.8 +/- 5.4° combined mean of Dapingian and Darriwilian stages: Dref = 166.0 +/- 8.4°, Iref = 56.1 +/- 6.5°) is regarded as the primary remanence of early diagenetic (chemical) origin. On the Baltica's apparent polar wander path (APWP), the palaeopoles (Floian: Plat = 25.0°N, Plon = 50.8°E, K = 52.7, A95 = 7.2° Dapingian and Darriwilian: Plat = 11.4°N, Plon = 39.1°E, K = 33.8, A95 = 6.7°) are placed on the Lower and Middle Ordovician segment. The poles indicate that Estonia was located at southerly latitudes, decreasing with time (Floian: ~48°S Dapingian and Darriwilian: ~37°S), when the remanence was acquired. A high-coercivity and high-unblocking-temperature component S (mean of samples: Dref = 33.7 +/- 6.3°, Iref = 51.9 +/- 5.7°) that is regarded as a secondary remanence has both normal and reversed polarities. On the European APWP, its palaeopole (Plat = 52.5°N, Plon = 157.9°E, K = 38.9, A95 = 5.3°) gives middle to late Permian age. According to mineralogical (SEM and optical microscopy) and rock magnetic (three-component induced remnant magnetization) studies, component P is carried by magnetite (coexisting with glauconite) and component S by haematite. Magnetite is of chemical origin, formed in the course of early diagenesis and/or dolomitization. During the Permian continental period haematite, the carrier of component S, was likely precipitated from oxidizing meteoric fluids in the already existing or simultaneously formed pore space between the dolomite crystals.

Assessing past and present P Retention in Sediments in Lake Ontario (Bay of Quinte) by Reaction-Transport Diagenetic Modeling

NASA Astrophysics Data System (ADS)

Doan, Phuong; Berry, Sandra; Markovic, Stefan; Watson, Sue; Mugalingam, Shan; Dittrich, Maria

2016-04-01

Phosphorus (P) is an important macronutrient that can limit aquatic primary production and the risk of harmful algal blooms. Although there is considerable evidence that P release from sediments can represent a significant source of P and burial in sediments returns P to the geological sink; these processes have been poorly characterised. In this study, we applied a non-steady state reactive transport diagenetic model to gain insights into the dynamics of phosphorus binding forms in sediments and the phosphorus cycling of the Bay of Quinte, an embayment of Lake Ontario, Canada. The three basins of the bay (Belleville, Hay Bay and Napanee) that we investigated had differences in their phosphorus binding forms and phosphorus release, reflecting the distinct spatial temporal patterns of land use and urbanization levels in the watershed. Sediment cores from the three stations were collected during summer and under ice cover in 2013-14. Oxygen, pH and redox potential were monitored by microsensors; porewater and sediment solid matter were analyzed for P content, and a sequential extraction was used to analyze P binding forms. In the reaction-transport model, total phosphorus was divided into adsorbed phosphorus, phosphorus bound with aluminium, organic phosphorus, redox sensitive and apatite phosphorus. Using the fluxes of organic and inorganic matter as dynamic boundary conditions, we simulated the depth profiles of solute and solid components. The model closely reproduced the fractionation data of phosphorus binding forms and soluble reactive phosphorus. The past and present P fluxes were calculated and estimated; they related to geochemical conditions, and P binding forms in sediments. Our results show that P release from sediments is dominated by the redox-sentive P fraction accounting for higher percentage at Napanee station. The main P binding form that can be immobilized through diagenesis is apatite P contributing highest P retention at HayBay station. The mass

Sulphur isotope constraints on formation conditions of the Luiswishi ore deposit, Democratic Republic of Congo (DRC)

NASA Astrophysics Data System (ADS)

Lerouge, C.; Cailteux, J.; Kampunzu, A. B.; Milesi, J. P.; Fléhoc, C.

2005-07-01

Luiswishi is a Congo-type Neoproterozoic sediment-hosted stratiform Cu-Co ore deposit of the Central Africa Copperbelt, located northwest of Lubumbashi (DRC). The ores form two main Cu-Co orebodies hosted by the Mines Subgroup, one in the lower part of the Kamoto Formation and the other at the base of the Dolomitic Shales Formation. Sulphides occur essentially as early parallel layers of chalcopyrite and carrolite, and secondarily as late stockwork sulphides cross-cutting the bedding and the early sulphide generation. Both types of stratiform and stockwork chalcopyrite and carrolite were systematically analyzed for sulphur isotopes, along the lithostratigraphic succession of the Mine Series. The quite similar δ 34S values of stratiform sulphides and late stockwork sulphides suggest an in situ recrystallization or a slight remobilization of stockwork sulphides without attainment of isotopic equilibrium between different sulphide phases (chalcopyrite and carrolite). The distribution of δ 34S values (-14.4‰ to +17.5‰) combined with the lithology indicates a strong stratigraphic control of the sulphur isotope signature, supporting bacterial sulphate reduction during early diagenesis of the host sediments, in a shallow marine to lacustrine environment. Petrological features combined with sulphur isotopic data of sulphides at Luiswishi and previous results on nodules of anhydrite in the Mine Series indicate a dominant seawater/lacustrine origin for sulphates, precluding a possible hydrothermal participation. The high positive δ 34S values of sulphides in the lower orebody at Luiswishi, hosted in massive chloritic-dolomitic siltite (known as Grey R.A.T.), fine-grained stratified dolostone (D.Strat.) and silicified-stromatolitic dolomites alternating with chloritic-dolomitic silty beds (R.S.F.), suggest that they were probably deposited during a period of regression in a basin cut off from seawater. The variations of δ 34S values (i.e. the decrease of δ 34S values

Geochemical imprint of depositional conditions on organic matter in laminated-Bioturbated interbeds from fine-grained marine sequences

USGS Publications Warehouse

Pratt, L.M.; Claypool, G.E.; King, J.D.

1986-01-01

Laminated organic-rich shales are interbedded at a scale of centimeters to a few meters with bioturbated organic-poor mudstones or limestones in some fine-grained marine sequences. We have analyzed the organic matter in pairs of laminated/bioturbated interbeds from Cretaceous and Devonian rocks deposited in epicontinental and oceanic settings for the purpose of studying the influence of depositional and early diagenetic environment on the organic geochemical properties of marine shales. Results of these analyses indicate that for rocks that are still in a diagenetic stage of thermal alteration, the relative abundance of biomarker compounds and specific biomarker indices can be useful indicators of depositional and early diagenetic conditions. Pristane/phytane ratios are generally highest for laminated rocks from epicontinental basins and appear to reflect the input of isoprenoid precursors more than oxygenated versus anoxic depositional conditions. The thermally immature laminated rocks are characterized by relatively high contents of 17??(H), 21??(H)-hopanes, hopenes, sterenes and diasterenes, and by strong predominance of the 22R over 22S homohopane isomers. Thermally immature bioturbated samples are characterized by absence of the ??,??-hopanes, by low contents of both saturated and unsaturated polycyclic hydrocarbons, and by slight or no predominance of the 22R over 22S homohopane isomers. There are less obvious compositional differences between the saturated hydrocarbons in the laminated and bioturbated units from the thermally mature sequences. For both the thermally mature and immature laminated samples, the degree of isomerization at the 22C position for hopanes and at the 20C position for steranes is generally consistent with the degree of thermal maturity interpreted from other properties of the organic matter. The bioturbated samples, however, exhibit inconsistent and anomalously high degrees of isomerization for the homohopanes, resulting either from

Dolomitization and neomorphism of Mississippian (Visean) upper debolt formation, Blueberry field, northeastern British Columbia: Geologic, petrologic, and chemical evidence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durocher, S.; Al-Aasm, I.S.

1997-06-01

Petrographic, chemical, and isotopic studies of the Mississippian (Visean) upper Debolt Formation in the Blueberry field, British Columbia, Canada, reveal that dolomitization was the result of several diagenetic events and that neomorphic alteration of these dolomites significantly modified their original chemical signatures. These studies also demonstrate how tectonics play an important role in controlling and modifying reservoir dolomites in the area. Petrographic investigations have documented two early dolomite phases, (1) early matrix dolomite and (2) pervasive dolomite, and two later generations, (3) coarse cement and (4) pseudomorphic replacement of crinoids. Early matrix dolomite occurs as small (average 25 {mu}m) subhedralmore » to euhedral crystals that replace the matrix of carbonate mudstones, wackestones, and packstones. Petrographic evidence suggests that early matrix dolomite had a relatively early, precompaction origin, possibly from marine fluids. However, geochemical evidence indicates that later fluids have altered their original geochemical signatures. Pervasive dolomite, which forms the reservoir intercrystalline porosity, occurs with planar-s and planar-e textures. Planar-s crystals typically have a dirty appearance and exhibit homogeneous dull brown/red cathodoluminescence colors. Planar-e crystals may appear with a cloudy core and a clear rim, and under cathodoluminescence display an irregular dull brown/red core and a thin, bright red rim. Due to the spatial distribution pattern of pervasive dolomite with respect to the overlying unconformity surface, its paleogeographic distribution and close temporal relationship with meteoric diagenetic events, pervasive dolomite formed from a mixture of seawater and meteoric fluids. However, alteration of their primary chemistry by later fluids is indicated by their depleted {delta}{sup 18}O values and radiogenic {sup 87}Sr/{sup 86}Sr ratios.« less

Geochemical signatures of copper redistribution in IOCG-type mineralisation, Gawler Craton, South Australia

NASA Astrophysics Data System (ADS)

Uvarova, Yulia A.; Pearce, Mark A.; Liu, Weihua; Cleverley, James S.; Hough, Robert M.

2018-04-01

The Emmie Bluff iron oxide, copper, gold (IOCG) prospect is located in the Olympic Dam district, South Australia, and hosts sub-economic 150-m-thick Cu-Au mineralisation associated with the hematite-chlorite-sericite alteration with chalcopyrite commonly replacing pre-existing pyrite at a depth of 800 m. With the use of cutting-edge synchrotron X-ray fluorescence microscopy and field emission gun-scanning electron microscopy, it is shown for the first time that sub-economic IOCG mineralisation in the Olympic Dam district was affected by a late fluid event, which resulted in partial dissolution of Cu mineralisation and transport of Cu in the form of chloride complexes. The porous chlorite-sericite matrix associated with the late alteration of chalcopyrite hosts a Cu-Cl-OH phase previously undescribed in IOCG rocks, which was identified as one of the polymorphs of the atacamite group of minerals, Cu2Cl(OH)3. Thermodynamic modelling shows that "atacamite" is produced during dissolution of chalcopyrite by an oxidised, Cl-bearing fluid. An acidic environment is produced within millimetres of the chalcopyrite grains during oxidation. This process drives chlorite recrystallisation that is recorded by compositional variation of chlorite proximal to chalcopyrite. The existence of the atacamite is discussed in the context of fluid evolution and interaction with IOCG-type mineralisation and its implications to ore preservation versus destruction and remobilisation.

Mineralogy, chemical composition and structure of the MIR Mound, TAG Hydrothermal Field

NASA Astrophysics Data System (ADS)

Stepanova, T. V.; Krasnov, S. G.; Cherkashev, G. A.

The study of samples collected from the surface of the MIR mound (TAG Hydrothermal Field) by video-controlled hydraulic grab allowed identification of a number of mineralogical types. These include pyrite-chalcopyrite (Py-Cp), bornite-chalcopyrite-opaline (Bn-Cp-Op) and sphalerite-opaline (Sp-Op) sulfide chimneys, massive sulfides composed of pyrite (Py), chalcopyrite-pyrite (Cp-Py), marcasite-pyrite-opaline (Mc-Py-Op), sphalerite-pyrite-opaline (Sp-Py-Op) and sphalerite-chalcopyrite-pyrite-opaline (Sp-Cp-Py-Op), as well as siliceous and Fe-Mn oxide hydrothermal deposits. Most of the minor elements (Ag, Au, Cd, Ga, Hg, Sb and Pb) are associated with Zn-rich massive sulfides, Co Bi, Pb, and As with Ferich ones, while Cu-rich sulfides are depleted of trace metals. Cu-enriched assemblages are concentrated in the northern part, Zn-enriched in the center, and siliceous rocks in the south of the MIR mound. According to paragenetic relations, the development of the mound started with the formation of quartz (originally opaline) rocks and dendritic assemblages of melnikovite-pyrite, followed by deposition of chalcopyrite and recrystallization of primary pyrite, subsequent generation of sphalerite-rich assemblages and final deposition of opaline rocks. The late renewal of hydrothermal activity led to local formation of Cu-rich chimneys enriched in Au, Ag, Hg and Pb probably due to their remobilization from inner parts of the deposit.

Textural and stable isotope studies of the Big Mike cupriferous volcanogenic massive sulfide deposit, Pershing County, Nevada.

USGS Publications Warehouse

Rye, R.O.; Roberts, R.J.; Snyder, W.S.; Lahusen, G.L.; Motica, J.E.

1984-01-01

The Big Mike deposit is a massive sulphide lens entirely within a carbonaceous argillite of the Palaeozoic Havallah pelagic sequence. The massive ore contains two generations of pyrite, a fine- and a coarse-grained variety; framboidal pyrite occurs in the surrounding carbonaceous argillite. Coarse grained pyrite is largely recrystallized fine-grained pyrite and is proportionately more abundant toward the margins of the lens. Chalcopyrite and sphalerite replace fine-grained pyrite and vein-fragmented coarse-grained pyrite. Quartz fills openings in the sulphide fabric. S-isotope data are related to sulphide mineralogy and textures. Isotopically light S in the early fine-grained pyrite was probably derived from framboidal biogenic pyrite. The S-isotope values of the later coarse-grained pyrite and chalcopyrite probably reflect a combination of reduced sea-water sulphate and igneous S. Combined S- and O-isotope and textural data accord with precipitation of fine-grained pyrite from a hydrothermal plume like those at the East Pacific Rise spreading centre at lat. 21oN. The primary material was recystallized and mineralized by later fluids of distinctly different S-isotope composition. -G.J.N.

Open system sulphate reduction in a diagenetic environment - Isotopic analysis of barite (δ34S and δ18O) and pyrite (δ34S) from the Tom and Jason Late Devonian Zn-Pb-Ba deposits, Selwyn Basin, Canada

NASA Astrophysics Data System (ADS)

Magnall, J. M.; Gleeson, S. A.; Stern, R. A.; Newton, R. J.; Poulton, S. W.; Paradis, S.

2016-05-01

Highly positive δ34S values in sulphide minerals are a common feature of shale hosted massive sulphide deposits (SHMS). Often this is attributed to near quantitative consumption of seawater sulphate, and for Paleozoic strata of the Selwyn Basin (Canada), this is thought to occur during bacterial sulphate reduction (BSR) in a restricted, euxinic water column. In this study, we focus on drill-core samples of sulphide and barite mineralisation from two Late Devonian SHMS deposits (Tom and Jason, Macmillan Pass, Selwyn Basin), to evaluate this euxinic basin model. The paragenetic relationship between barite, pyrite and hydrothermal base metal sulphides has been determined using transmitted and reflected light microscopy, and backscatter electron imaging. This petrographic framework provides the context for in-situ isotopic microanalysis (secondary ion mass spectrometry; SIMS) of barite and pyrite. These data are supplemented by analyses of δ34S values for bulk rock pyrite (n = 37) from drill-core samples of un-mineralised (barren), siliceous mudstone, to provide a means by which to evaluate the mass balance of sulphur in the host rock. Three generations of barite have been identified, all of which pre-date hydrothermal input. Isotopically, the three generations of barite have overlapping distributions of δ34S and δ18O values (+22.5‰ to +33.0‰ and +16.4‰ to +18.3‰, respectively) and are consistent with an origin from modified Late Devonian seawater. Radiolarian tests, enriched in barium, are abundant within the siliceous mudstones, providing evidence that primary barium enrichment was associated with biologic activity. We therefore propose that barite formed following remobilisation of productivity-derived barium within the sediment, and precipitated within diagenetic pore fluids close to the sediment water interface. Two generations of pyrite are texturally associated with barite: framboidal pyrite (py-I), which has negative δ34S values (-23‰ to -28�

Mineralogy and diagenesis of low-permeability sandstones of Late Cretaceous age, Piceance Creek Basin, northwestern Colorado

USGS Publications Warehouse

Hansley, Paula L.; Johnson, Ronald C.

1980-01-01

This report presents preliminary results of a mineralogic and diagenetic study of some low-permeability sandstones from measured surface sections and cores obtained from drill holes in the Piceance Creek Basin of northwestern Colorado. A documentation of the mineralogy and diagenetic history will aid in the exploration for natural gas and in the development of recovery technology in these low-permability sandstones. These sandstones are in the nonmarine upper part of the Mesaverde Formation (or Group) of Late Cretaceous age and are separated from overlying lower Tertiary rocks by a major regional unconformity. Attention is focused on the sandstone units of the Ohio Creek Member, which directly underlies the unconformity; however, comparisons between the mineralogy of the Ohio Creek strata and that of the underlying sandstone units are made whenever possible. The Ohio Creek is a member of the Hunter Canyon Formation (Mesaverde Group) in the southwestern part of the basin, and the Mesaverde Formation in the southern and central parts of the basin. The detrital mineralogy is fairly constant throughout all of these nonrnarine Cretaceous sandstone units; however, in the southeastern part of the basin, there is an increase in percentage of feldspar, quartzite, and igneous rock fragments in sandstones of the Ohio Creek Member directly underlying the unconformity. In the southwestern part of the basin, sandstones of the Ohio Creek Member are very weathered and are almost-entirely comprised of quartz, chert, and kaolinite. A complex diagenetic history, partly related to the overlying unconformity, appears to be responsible for transforming these sandstones into potential gas reservoirs. The general diagenetic sequence for the entire Upper Cretaceous interval studied is interpreted to be (early to late): early(?) calcite cement, chlorite, quartz overgrowths, calcite cement, secondary porosity, analcime (surface only), kaolinite and illite, and late carbonate cements

Prokaryotic algae associated with Australian proterozoic stromatolites.

NASA Technical Reports Server (NTRS)

Licari, G. R.; Cloud, P.

1972-01-01

The most favorable sites in which to study the associations between stromatolites and the algae responsible for them are places where a variety of stromatolites of possibly early diagenetic or primary silica occupy a layer of substantial thickness of little metamorphosed ancient sediments. One such place is in northwestern Queensland, Australia. Five cases of association between stromatolites and blue-green algal nannofossils were observed within a 100-m sequence of carbonate rocks in that area.

Development of Proxies for Vent Fluid Trace Metal Concentrations and pH through Study of Sulfide Chimney Linings

NASA Astrophysics Data System (ADS)

Evans, G. N.; Tivey, M. K.; Seewald, J.; Rouxel, O. J.; Monteleone, B.

2016-12-01

Analyses of trace elements (Ag, As, Co, Mn, and Zn) hosted in the chalcopyrite linings of `black smoker' chimneys using secondary ion mass spectrometry (SIMS) have been combined with data for trace metal concentrations in corresponding vent fluids to investigate fluid-mineral partitioning of trace elements. Goals of this research include development of proxies for fluid chemistry based on mineral trace element content. The use of SIMS allows for the measurement of trace elements below the detection limits of electron microprobe and at the necessary spatial resolution (20 microns) to examine fine-grained and mixed-mineral samples. Results indicate that the chalcopyrite linings of many `black smoker' chimneys are homogeneous with respect to Ag, Mn, Co, and Zn. Minerals picked from samples exhibiting homogeneity with respect to specific elements were dissolved and analyzed by solution inductively coupled plasma mass spectrometry (ICP-MS) for use as working standards. Results also document a strong correlation between the Ag content of chalcopyrite and the Ag:Cu ratio of the corresponding hydrothermal fluid. This supports systematic partitioning of Ag into chalcopyrite as a substitute for Cu, providing a proxy for fluid Ag concentration. Additionally, the Ag content of chalcopyrite correlates with fluid pH, particularly at pH>3, and thus represents an effective proxy for fluid pH. Application of these proxies to chimney samples provides an opportunity to better identify hydrothermal conditions even when fluids have not been sampled, or not fully analyzed.

Metal Resistance and Lithoautotrophy in the Extreme Thermoacidophile Metallosphaera sedula

PubMed Central

Maezato, Yukari; Johnson, Tyler; McCarthy, Samuel; Dana, Karl

2012-01-01

Archaea such as Metallosphaera sedula are thermophilic lithoautotrophs that occupy unusually acidic and metal-rich environments. These traits are thought to underlie their industrial importance for bioleaching of base and precious metals. In this study, a genetic approach was taken to investigate the specific relationship between metal resistance and lithoautotrophy during biotransformation of the primary copper ore, chalcopyrite (CuFeS2). In this study, a genetic system was developed for M. sedula to investigate parameters that limit bioleaching of chalcopyrite. The functional role of the M. sedula copRTA operon was demonstrated by cross-species complementation of a copper-sensitive Sulfolobus solfataricus copR mutant. Inactivation of the gene encoding the M. sedula copper efflux protein, copA, using targeted recombination compromised metal resistance and eliminated chalcopyrite bioleaching. In contrast, a spontaneous M. sedula mutant (CuR1) with elevated metal resistance transformed chalcopyrite at an accelerated rate without affecting chemoheterotrophic growth. Proteomic analysis of CuR1 identified pleiotropic changes, including altered abundance of transport proteins having AAA-ATPase motifs. Addition of the insoluble carbonate mineral witherite (BaCO3) further stimulated chalcopyrite lithotrophy, indicating that carbon was a limiting factor. Since both mineral types were actively colonized, enhanced metal leaching may arise from the cooperative exchange of energy and carbon between surface-adhered populations. Genetic approaches provide a new means of improving the efficiency of metal bioleaching by enhancing the mechanistic understanding of thermophilic lithoautotrophy. PMID:23065978

High-resolution Campanian-Maastrichtian carbon and oxygen stable isotopes of bulk-rock and skeletal components: palaeoceanographic and palaeoenvironmental implications for the Boreal shelf sea

NASA Astrophysics Data System (ADS)

Wilmsen, Markus; Niebuhr, Birgit

2017-03-01

A high-resolution latest Early Campanian to Early Maastrichtian carbon and oxygen stable isotope record from the northern German Boreal shelf sea based on 537 analyses of co-occurring belemnites, brachiopods, inoceramids, oysters, and bulk rock samples is presented. All samples are precisely related to their stratigraphic, systematic and facies backgrounds and form an integrated, nearly 10-myr-long dataset with considerable palaeoenvironmental and palaeoceanographical implications. Petrographic studies indicate that low-magnesium calcitic coccoliths and calcispheres (i.e., planktic carbonate) predominate the bulk-rock data (marl-limestone rhythmites and chalks), thus representing a sea-surface water signal, and that only minor diagenetic alteration of the carbonate muds took place. Based on TL and CL microscopy, the investigated belemnites are extraordinarily well preserved, which may in part be explained by their early diagenetic surficial silicification (container effect), while the other macroinvertebrate groups are all less well preserved. The (plankton-dominated) δ13C values of the marl-limestone rhythmites and chalks (+1.1 to +2.5 ‰), recording a surface water signal, compare well with the δ18C data of inoceramids while δ13Cbrach. values (+1.5 to +3.0 ‰) are heavier than the bulk rock data. The large variation in the δ13Cbel. (-0.1 to +3.6 ‰) is attributed to isotopic disequilibrium of the biogenic carbonate formed by the belemnite animal. The bulk rock δ18O values show a remarkable low scatter, supporting petrographic observation of only minor diagenetic stabilisation/cementation, and can be approximated with northern German shelf sea-surface temperatures of ca. 20°C for the Late Campanian (ca. -2 ‰ δ18O), being slightly cooler during the Early Maastrichtian. The δ18O values of the belemnite rostra are even less variable and quite rich in heavier 18O (-0.7 to +0.6 with a mean of -0.1 ‰ δ18Obel.) in comparison to bulk rock and other

The Niassa Gold Belt, northern Mozambique - A segment of a continental-scale Pan-African gold-bearing structure?

NASA Astrophysics Data System (ADS)

Bjerkgard, T.; Stein, H. J.; Bingen, B.; Henderson, I. H. C.; Sandstad, J. S.; Moniz, A.

2009-01-01

The Niassa Gold Belt, in northernmost Mozambique, is hosted in the Txitonga Group, a Neoproterozoic rift sequence overlying Paleoproterozoic crust of the Congo-Tanzania Craton and deformed during the Pan-African Orogeny. The Txitonga Group is made up of greenschist-facies greywacke and schist and is characterized by bimodal, mainly mafic, magmatism. A zircon U-Pb age for a felsic volcanite dates deposition of the sequence at 714 ± 17 Ma. Gold is mined artisanally from alluvial deposits and primary chalcopyrite-pyrite-bearing quartz veins containing up to 19 ppm Au have been analyzed. In the Cagurué and M'Papa gold fields, dominantly N-S trending quartz veins, hosted in metagabbro and schist, are regarded as tension gashes related to regional strike-slip NE-SW-trending Pan-African shear zones. These gold deposits have been classified as mesozonal and metamorphic in origin. Re-Os isotopic data on sulfides suggest two periods of gold deposition for the Cagurué Gold Field. A coarse-crystalline pyrite-chalcopyrite assemblage yields an imprecise Pan-African age of 483 ± 72 Ma, dating deposition of the quartz veins. Remobilization of early-formed sulfides, particularly chalcopyrite, took place at 112 ± 14 Ma, during Lower Cretaceous Gondwana dispersal. The ˜483 Ma assemblage yields a chondritic initial 187Os/ 188Os ratio of 0.123 ± 0.058. This implies a juvenile source for the ore fluids, possibly involving the hosting Neoproterozoic metagabbro. The Niassa Gold Belt is situated at the eastern end of a SW-NE trending continental-scale lineament defined by the Mwembeshi Shear Zone and the southern end of a NW-SE trending lineament defined by the Rukwa Shear Zone. We offer a review of gold deposits in Zambia and Tanzania associated with these polyphase lineaments and speculate on their interrelation.

Characteristics of the Late Devonian Tsagaan Suvarga Cu-Mo deposit, Southern Mongolia

NASA Astrophysics Data System (ADS)

Tungalag, Naidansuren; Jargalan, Sereenen; Khashgerel, Bat-Erdene; Mijiddorj, Chuluunbaatar; Kavalieris, Imants

2018-05-01

The Late Devonian Tsagaan Suvarga deposit (255 Mt at 0.55% Cu, 0.02% Mo) is located on the NW margin of the Tsagaan Suvarga Complex (TSC), which extends ENE over 15 × 10 km and comprises mainly medium-grained equigranular hornblende-biotite quartz monzonite and monzodiorite. Distinct mineralized intrusions are inferred from distribution of Cu-Mo mineralization but are not clearly discernible. The Tsagaan Suvarga Complex is a window within Carboniferous volcanic and sedimentary rocks, and wall rocks to the TSC are not known or exposed in the nearby district. Whole-rock analyses and Sr-Nd isotopes, 87Sr/86Sr0 = 0.7027 to 0.7038 (n = 12) and ɛNd0 = + 4.26 to + 2.77 (n = 12), show that the granitoids are subduction-related I-type, high K-calc-alkaline to shoshonitic series and derived from a mantle source. They exhibit fractionated light rare earth elements, without depleted Eu and depleted middle heavy rare earth elements and Y, typical of oxidized, fertile porphyry magmatic suites. Early porphyry-style quartz veins include A- and B-type. Molybdenite occurs in monomineralic veins (1-5 mm) or A veins. Copper mineralization occurs mainly as chalcopyrite and subordinate bornite, disseminated and associated with quartz-muscovite veins. Pyrite (vol%) content is less than chalcopyrite and bornite combined. Deep oxidation to about 50 m depth has formed zones of malachite and covellite in late fractures. The most important alteration is actinolite-biotite-chlorite-magnetite replacing hornblende and primary biotite. Quartz-K-feldspar alteration is minor. Late albite replaces primary K-feldspar and enhances sodic rims on plagioclase crystals. Quartz-muscovite (or sericitic alteration) overprints actinolite-biotite and porphyry-type quartz veins. Field observations and petrographic studies suggest that the bulk of the chalcopyrite-bornite mineralization at the Tsagaan Suvarga formed together with coarse muscovite alteration.

Involvement of magmatic fluids at the Laloki and Federal Flag massive sulfide Cu-Zn-Au-Ag deposits, Astrolabe mineral district, Papua New Guinea: sulfur isotope evidence

NASA Astrophysics Data System (ADS)

Noku, Shadrach K.; Espi, Joseph O.; Matsueda, Hiroharu

2015-01-01

We present the first sulfur (S) isotope data of sulfides, sulfates, pyrite in host mudstone, and bulk sulfur of gabbroic rocks from the Laloki and Federal Flag massive Cu-Zn-Au-Ag deposits in the Astrolabe mineral district, Papua New Guinea. Early-stage pyrite-marcasite, chalcopyrite, and sphalerite from Laloki display wide range of δ34S values from -4.5 to +7.0 ‰ ( n = 16). Late-stage pyrite, chalcopyrite, and sphalerite have restricted δ34S values of -1.9 to +4.7 ‰ ( n = 16). The mineralizing stage these correspond to had moderately saline (5.9-8.4 NaCl eq. wt%) mineralizing fluids of possible magmatic origin. A single analysis of late-stage barite has a value of δ34S +17.9 ‰, which is likely similar to coexisting seawater sulfate. Pyrite from the foot-wall mudstone at Laloki has very light δ34S values of -36.1 to -33.8 ‰ ( n = 2), which suggest an organic source for S. Pyrite-marcasite and chalcopyrite from Federal Flag show δ34S values of -2.4 to -1.9 ‰ ( n = 2), consistent with a magmatic origin, either leached from intrusive magmatic rocks or derived from magmatic-hydrothermal fluids. The very narrow range and near-zero δ34S values (-1.0 to +0.6 ‰) of bulk gabbroic samples is consistent with mantle-derived magmatic S. Sulfur isotope characteristics of sulfides and sulfates are, however, very similar to base metal sulfide accumulations associated with modern volcanic arcs and sedimented mid-ocean ridges. The most reasonable interpretation is that the range of the sulfide and sulfate δ34S values from both Laloki and Federal Flag massive sulfide deposits is indicative of the complex interaction of magmatic fluids, seawater, gabbroic rocks, and mudstone.

First find of platinum group metals in the ore of Kirganik copper-porphyry deposit (Kamchatka)

NASA Astrophysics Data System (ADS)

Sidorov, E. G.; Ignatyev, E. K.; Chubarov, V. M.

2017-08-01

The Kirganik copper-porphyry deposit is situated in the central part of the Sredinnyi Mountain Range of Kamchatka and is confined to fields of development of potassic orthoclase metasomatite and hypabyssal intrusions of shonkinite. Platinum group metals (PGMs), such as merenskyite, kotulskite, keithconnite, and temagamite, were discovered in the chalcopyrite-bornite and chalcopyrite-bornite-chalcosine ore of the deposit for the first time.

The evolution of Phanerozoic seawater - Isotope paleothermometry finds consensus on Early Paleozoic warmth and constant seawater δ18O

NASA Astrophysics Data System (ADS)

Grossman, E. L.; Henkes, G. A.; Passey, B. H.; Shenton, B.; Yancey, T. E.; Perez-Huerta, A.

2015-12-01

Evolution of metazoan life is closely linked to the Phanerozoic evolution of ocean temperatures and chemistry. Oxygen isotopic evidence for early Phanerozoic paleotemperatures has been equivocal, with decreasing δ18O values with age being interpreted as warmer early oceans, decreasing seawater δ18O with age, or increasing diagenetic alteration in older samples. Here we compare an updated compilation of oxygen isotope data for carbonate and phosphate fossils and microfossils (Grossman, 2012, Geol. Time Scale, Elsevier, 195-220) with a compilation of new and existing clumped isotope data. Importantly, these data are curated based on sample preservation with special consideration given to screening techniques, and tectonic and burial history. Burial history is critical in the preservation of carbonate clumped isotope temperatures in particular, which can undergo reordering in the solid state. We use a model derived for reordering kinetics (Henkes et al., 2014, Geochim. Cosmochim. Acta 139:362-382) to screen clumped isotope data for the effects of solid-state burial alteration. With minor but significant exceptions (Late Cretaceous, Early Triassic), average δ18O values (4 m.y. window, 2 m.y. steps) for post-Devonian brachiopods, belemnites, and foraminifera, representing tropical-subtropical surface ocean conditions, yield average isotopic temperatures below 30°C (assuming a seawater δ18O value [ -1‰ VSMOW] of an "ice-free" world). In contrast, Ordovician to Devonian data show sustained temperatures of 35-40°C. Likewise, isotopic paleotemperatures from conodont apatite, known to be resistant to isotopic exchange, follow the same pattern. Clumped isotope data derived from Paleozoic brachiopod shells that experienced minimal burial (< 100 °C) and <1% reordering according to the taxon-specific clumped isotope reordering model yield typical temperatures of 25-30°C for the Carboniferous, and 35-40°C for the Ordovician-Silurian. Inserting clumped temperatures and

Organic matter mineralization and trace element post-depositional redistribution in Western Siberia thermokarst lake sediments

NASA Astrophysics Data System (ADS)

Audry, S.; Pokrovsky, O. S.; Shirokova, L. S.; Kirpotin, S. N.; Dupré, B.

2011-11-01

This study reports the very first results on high-resolution sampling of sediments and their porewaters from three thermokarst (thaw) lakes representing different stages of ecosystem development located within the Nadym-Pur interfluve of the Western Siberia plain. Up to present time, the lake sediments of this and other permafrost-affected regions remain unexplored regarding their biogeochemical behavior. The aim of this study was to (i) document the early diagenesic processes in order to assess their impact on the organic carbon stored in the underlying permafrost, and (ii) characterize the post-depositional redistribution of trace elements and their impact on the water column. The estimated organic carbon (OC) stock in thermokarst lake sediments of 14 ± 2 kg m-2 is low compared to that reported for peat soils from the same region and denotes intense organic matter (OM) mineralization. Mineralization of OM in the thermokarst lake sediments proceeds under anoxic conditions in all the three lakes. In the course of the lake development, a shift in mineralization pathways from nitrate and sulfate to Fe- and Mn-oxyhydroxides as the main terminal electron acceptors in the early diagenetic reactions was suggested. This shift was likely promoted by the diagenetic consumption of nitrate and sulfate and their gradual depletion in the water column due to progressively decreasing frozen peat lixiviation occurring at the lake's borders. Trace elements were mobilized from host phases (OM and Fe- and Mn-oxyhydroxides) and partly sequestered in the sediment in the form of authigenic Fe-sulfides. Arsenic and Sb cycling was also closely linked to that of OM and Fe- and Mn-oxyhydroxides. Shallow diagenetic enrichment of particulate Sb was observed in the less mature stages. As a result of authigenic sulfide precipitation, the sediments of the early stage of ecosystem development were a sink for water column Cu, Zn, Cd, Pb and Sb. In contrast, at all stages of ecosystem development

Organic matter mineralization and trace element post-depositional redistribution in Western Siberia thermokarst lake sediments

NASA Astrophysics Data System (ADS)

Audry, S.; Pokrovsky, O. S.; Shirokova, L. S.; Kirpotin, S. N.; Dupré, B.

2011-08-01

This study reports the very first results on high-resolution sampling of sediments and their porewaters from three thermokarst (thaw) lakes representing different stages of ecosystem development located within the Nadym-Pur interfluve of the Western Siberia plain. Up to present time, the lake sediments of this and other permafrost-affected regions remain unexplored regarding their biogeochemical behavior. The aim of this study was to (i) document the early diagenesic processes in order to assess their impact on the organic carbon stored in the underlying permafrost, and (ii) characterize the post-depositional redistribution of trace elements and their impact on the water column. The estimated organic carbon (OC) stock in thermokarst lake sediments of 14 ± 2 kg m-2 is low compared to that reported for peat soils from the same region and denotes intense organic matter (OM) mineralization. Mineralization of OM in the thermokarst lake sediments proceeds under anoxic conditions in all the three lakes. In the course of the lake development, a shift in mineralization pathways was evidenced from nitrate and sulfate to Fe- and Mn-oxyhydroxides as the main terminal electron acceptors in the early diagenetic reactions. This shift was promoted by the diagenetic consumption of nitrate and sulfate and their gradual depletion in the water column due to progressively decreasing frozen peat lixiviation occurring at the lake's borders. Trace elements were mobilized from host phases (OM and Fe- and Mn-oxyhydroxides) and partly sequestered in the sediment in the form of authigenic Fe-sulfides. Arsenic and Sb cycling was also closely linked to that of OM and Fe- and Mn-oxyhydroxides. Shallow diagenetic enrichment of particulate Sb was observed in the less mature stages. As a result of authigenic sulfide precipitation, the sediments of the early stage of ecosystem development were a sink for water column Cu, Zn, Cd, Pb and Sb. In contrast, at all stages of ecosystem development, the

Stable isotopic compositions of early calcite cements in the Middle Devonian Coralville Formation (Cedar Valley Group), eastern Iowa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ludvigson, G.A.; Gonzalez, L.S.; Witzke, B.J.

1993-03-01

The Middle-Upper Devonian Cedar Valley Gp in Iowa is subdivided into four formations each representing a broad transgressive-regressive (T-R) cycle of deposition. Cycles consist of basal open marine facies that shallow upward into capping peritidal facies. Results from ongoing diagenetic studies of the Coralville Fm (late Givetian), the second T-R cycle of the Cedar Valley Gp, have focused attention on the origins of early cements. Early calcite cements in the Coralville Fm of Johnson County, Iowa, include blocky equant spars filling fenestral voids in birdseye limestones of the Iowa City Mbr and isopachous bladed spars that occur throughout the Coralville.more » Bladed spars fill stromatactis and microkarstic voids in the Iowa City Mbr, and sheltered voids in underlying open-marine skeletal packstones of the Cou Falls Mbr (lower Coralville cycle). The bladed spars include nonluminescent inclusion-free domains that contain up to 4,000 ppm Mg, and luminescent inclusion-rich domains that contain less than 2,000 ppm Mg. Birdseye spars have a constructive oscillatory luminescent-nonluminescent zonation controlled by Mn contents and contain less than 1,000 ppm Mg. Nonluminescent domains in bladed spars have the heaviest oxygen isotopic compositions of all components in the Coralville, similar to the isotopically heaviest nonluminescent brachiopods but have [delta][sup 13]C values ranging from [minus]3 to [minus]5 [per thousand]. They are interpreted to have precipitated from marine fluids saturated by CO[sub 2] produced from bacterial oxidation of organic matter. Altered luminescent domains in the bladed spars have the same [delta][sup 13]C compositions, but have widely varying [delta][sup 18]O compositions, ranging to [minus]9 [per thousand].« less

Geology and ore deposits of the Mahd Adh Dhahab District, Kingdom of Saudi Arabia

USGS Publications Warehouse

Luce, Robert W.; Bagdady, Abdulaziz; Roberts, Ralph Jackson

1976-01-01

The principal ore minerals are pyrite, chalcopyrite, sphalerite, galena, and minor tetrahedrite, argentite, and native gold and silver. The gold and silver occurs finely disseminated in the veins and in the altered selvages of the veins. Widespread potassic and propylitic alteration accompanied the ore-forming processes. Potassium feldspar was introduced during an early stage of vein formation. Isotopic analyses of lead in vein potassium feldspar and galena yield a model age of about 900-1050 million years with the possibility of the original lead source having been remobilized about 600 million years ago. Chlorite and carbonate are also prominent vein minerals.

The Sanfengshan copper deposit and early Carboniferous volcanogenic massive sulfide mineralization in the Beishan orogenic belt, Northwestern China

NASA Astrophysics Data System (ADS)

Wang, Jialin; Gu, Xuexiang; Zhang, Yongmei; Zhou, Chao; He, Ge; Liu, Ruiping

2018-03-01

The Sanfengshan copper deposit, located in the Beishan orogenic belt, Northwestern China, is hosted in the lower member of the Hongliuyuan Formation, an early Carboniferous metavolcanic-sedimentary sequence. Mineralization occurs as stratiform, stratiform-like and lenticular orebodies, and comprises of laminated, brecciated, banded, massive, and disseminated ores. The mineralogy is dominated by pyrite, chalcopyrite and sphalerite. Fe-Mn chert is widely distributed and generally occurs as massive, laminated, bands or lenses, which are consistent with the orebody. Alteration at Sanfengshan displays a clear concentric zoning pattern and the footwall alteration is more intense and somewhat thicker than the hanging-wall alteration. Systematic geochemical investigation on the volcanic rocks in this area shows that the basalts of the Hongliuyuan Formation (HLY) are predominantly tholeiites with nearly flat rare earth element (REE) pattern, insignificant negative anomalies of high field strength elements (HFSEs), and low Ti/V and Th/Nb ratios. They were most likely derived from partial melting of depleted asthenospheric mantle and formed in a fore-arc setting during initiation of the southward subduction of the Paleo-Asian Ocean. The basalts of the Maotoushan Formation (MTS) display a calc-alkaline nature and are enriched in large ion lithophile elements (LILEs) and depleted in HFSEs, suggesting an active continental margin setting. Sulfur isotope (δ34S) values of the sulfide and sulfate minerals vary between 0‰ and 5.4‰, which are consistent with sulfur derivation from leaching of the host volcanic rocks, although a direct magmatic contribution cannot be ruled out. The Re-Os isotope data of pyrite yield an isochron age of 353 ± 35 Ma, consistent with the age of the host HLY basalts. Thus, a syngenetic (volcanogenic massive sulfide) model is proposed and it is concluded that the Sanfengshan copper deposit is a typical Cyprus-type VMS deposit that formed in an early

Textures and compositions of cobalt pentlandite and cobaltian mackinawite from the Madan-Kudan copper deposit, Khetri Copper Belt, Rajasthan, India

NASA Astrophysics Data System (ADS)

Baidya, Abu Saeed; Sen, Atlanta; Pal, Dipak C.

2018-06-01

The Khetri Copper Belt (KCB), a part of the Proterozoic Delhi-Aravalli fold belt in western India, hosts several Cu deposits, which are known to contain considerable Au, Ag, Co and Ni. Although many Co-bearing phases have been reported from the KCB and adjacent areas, detailed textural and geochemical data are either unavailable or scant except for mackinawite. In this study, we describe the textures and compositions (determined by EPMA) of two very rare Co-rich phases, namely cobaltian mackinawite (containing up to 12.68 wt.% Co, 1.90 wt.% Ni and 2.52 wt.% Cu) and cobalt-pentlandite (containing up to 49.30 wt.% Co and 10.19 wt.% Ni), identified based on composition, from the Madan-Kudan deposit. To the best of our knowledge, neither cobalt-pentlandite nor such highly Co-rich mackinawite have previously been reported from this area. The common sulphide minerals viz. chalcopyrite, pyrrhotite and rare pyrite occur in chalcopyrite-pyrrhotite ± pyrite-magnetite-chlorite-blue amphibole (Cl-rich hastingsite-pargasite-sadanagaite) ± marialitic scapolite ± allanite ± uraninite veins in amphibole-bearing feldspathic quartzite and garnetiferous chlorite schist. Cobaltian mackinawite is invariably associated with chalcopyrite and occurs as exsolution and inclusion within chalcopyrite or outside, but at the contact of chalcopyrite. On the other hand, cobalt-pentlandite is invariably associated with pyrrhotite and shows similar textural relation with pyrrhotite as that of mackinawite with chalcopyrite. Mineralogically diverse undeformed sulphide veins comprising Cl-rich amphibole and locally Cl-rich marialitic scapolite suggests epigenetic hydrothermal mineralization involving Cl-rich saline fluid in the Madan-Kudan deposit. Transport of metals, derived from a mafic source rock with high intrinsic Ni:Co ratio, by Cl-rich fluid can suitably explain the high Co:Ni ratio of the studied ore minerals. Presence of such highly Co-rich phases and other circumstantial evidences

Crystallographic and optical properties and band diagrams of CuGaS2 and CuGa5S8 phases in Cu-poor Cu2S-Ga2S3 pseudo-binary system

NASA Astrophysics Data System (ADS)

Maeda, Tsuyoshi; Yu, Ying; Chen, Qing; Ueda, Kenta; Wada, Takahiro

2017-04-01

We synthesized Cu-poor Cu-Ga-S samples such, as CuGaS2 and CuGa5S8 with the composition of (1 - x)Cu2S-(x)Ga2S3 with 0.5 ≤ x ≤ 1.0, by a mechanochemical process and sequential heating. The crystal structure changes from tetragonal chalcopyrite-type CuGaS2 (0.5 ≤ x ≤ 0.55) to tetragonal stannite-type CuGa5S8 (x = 0.8). For samples with 0.60 ≤ x ≤ 0.75, the diffraction peaks were identified to be those of a mixed phase of the chalcopyrite- and stannite-type structures. The band-gap energies of Cu-poor Cu-Ga-S samples increase in a stepwise manner with increasing x. The band-gap energy of CuGa5S8 (x = 0.8) with the tetragonal stannite-type structure is approximately 2.66 eV, which is wider than that of chalcopyrite-type CuGaS2 (2.45 eV). The energy levels of valence band maxima (VBMs) were estimated from the ionization energies measured by photoemission yield spectroscopy (PYS). The energy levels of the VBM and conduction band minimum (CBM) of the Cu-poor Cu-Ga-S samples decrease significantly with increasing x (decreasing Cu/Ga ratio). The energy level of the VBM of CuGaS2 (-5.8 eV) is considerably deeper than those of CuInSe2 (-5.2 eV) and CuInS2 (-5.5 eV). The VBM of stannite-type CuGa5S8 with x = 0.8 (-6.4 eV) is much deeper than that of chalcopyrite-type CuGaS2 (-5.8 eV) and stannite-type CuIn3Se5 (-5.6 eV). In order to understand the band structures of chalcopyrite-type CuGaS2 and stannite-type CuGa5S8, we performed first-principles calculations using the Heyd-Scuseria-Ernzerhof (HSE06), nonlocal screened hybrid density functional method. The theoretical band-gap energy of stannite-type CuGa5S8 (2.2 eV) is wider than that of chalcopyrite-type CuGaS2 (2.0 eV). Both the theoretical and experimental band gaps of stannite-type CuGa5S8 are about 0.2 eV wider than those of chalcopyrite-type CuGaS2.

Investigations of CuFeS{sub 2} semiconductor mineral from ocean rift hydrothermal vent fields by Cu NMR in a local field

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matukhin, V. L.; Pogoreltsev, A. I.; Gavrilenko, A. N., E-mail: ang-2000@mail.ru

The results of investigating natural samples of chalcopyrite mineral CuFeS{sub 2} from massive oceanic sulfide ores of the Mid-Atlantic ridge by the {sup 63}Cu nuclear magnetic resonance (NMR {sup 63}Cu) in a local field at room temperature are presented. The significant width of the resonance lines found in the {sup 63}Cu NMR spectrum directly testifies to a wide distribution of local magnetic and electric fields in the investigated chalcopyrite samples. This distribution can be the consequence of an appreciable deviation of the structure of the investigated chalcopyrite samples from the stoichiometric one. The obtained results show that the pulsed {supmore » 63}Cu NMR can be an efficient method for studying the physical properties of deep-water polymetallic sulfides of the World Ocean.« less

Genesis of sediment-hosted stratiform copper cobalt deposits, central African Copperbelt

NASA Astrophysics Data System (ADS)

Cailteux, J. L. H.; Kampunzu, A. B.; Lerouge, C.; Kaputo, A. K.; Milesi, J. P.

2005-07-01

The Neoproterozoic central African Copperbelt is one of the greatest sediment-hosted stratiform Cu-Co provinces in the world, totalling 140 Mt copper and 6 Mt cobalt and including several world-class deposits (⩾10 Mt copper). The origin of Cu-Co mineralisation in this province remains speculative, with the debate centred around syngenetic-diagenetic and hydrothermal-diagenetic hypotheses. The regional distribution of metals indicates that most of the cobalt-rich copper deposits are hosted in dolomites and dolomitic shales forming allochthonous units exposed in Congo and known as Congolese facies of the Katangan sedimentary succession (average Co:Cu = 1:13). The highest Co:Cu ratio (up to 3:1) occurs in ore deposits located along the southern structural block of the Lufilian Arc. The predominantly siliciclastic Zambian facies, exposed in Zambia and in SE Congo, forms para-autochthonous sedimentary units hosting ore deposits characterized by lower a Co:Cu ratio (average 1:57). Transitional lithofacies in Zambia (e.g. Baluba, Mindola) and in Congo (e.g. Lubembe) indicate a gradual transition in the Katangan basin during the deposition of laterally correlative clastic and carbonate sedimentary rocks exposed in Zambia and in Congo, and are marked by Co:Cu ratios in the range 1:15. The main Cu-Co orebodies occur at the base of the Mines/Musoshi Subgroup, which is characterized by evaporitic intertidal-supratidal sedimentary rocks. All additional lenticular orebodies known in the upper part of the Mines/Musoshi Subgroup are hosted in similar sedimentary rocks, suggesting highly favourable conditions for the ore genesis in particular sedimentary environments. Pre-lithification sedimentary structures affecting disseminated sulphides indicate that metals were deposited before compaction and consolidation of the host sediment. The ore parageneses indicate several generations of sulphides marking syngenetic, early diagenetic and late diagenetic processes. Sulphur isotopic

Combining Textural Techniques to Explore Effects of Diagenesis and Low-grade Metamorphism on Iron Mineralogy and Iron Speciation

NASA Astrophysics Data System (ADS)

Slotznick, S. P.; Webb, S.; Eiler, J. M.; Kirschvink, J. L.; Fischer, W. W.

2016-12-01

Iron chemistry and mineralogy in the sedimentary rocks provide a valuable tool for studying paleoenvironmental conditions due to the fact that iron atoms can take on either the +II or +III valence state under geological redox conditions. One method utilizing this redox chemistry is `iron speciation', a bulk chemical sequential extraction technique that maps proportions of iron species to redox conditions empirically calibrated from modern sediments. However, all Precambrian and many Phanerozoic rocks have experienced post-depositional processes; it is vital to explore their effects on iron mineralogy and speciation. We combined light and electron microscopy, magnetic microscopy, (synchrotron-based) microprobe x-ray spectroscopy, and rock magnetic measurements in order to deconvolve secondary overprints from primary phases and provide quantitative measurement of iron minerals. These techniques were applied to excellently-preserved shale and siltstone samples of the 1.4 Ga lower Belt Supergroup, Montana and Idaho, USA, spanning a metamorphic gradient from sub-biotite to garnet zone. Previously measured Silurian-Devonian shales, sandstones, and carbonates in Maine and Vermont, USA spanning from the chlorite to kyanite zone provided additional well-constrained, quantitative data for comparison and to extend our analysis. In all of the studied samples, pyrrhotite formation occurred at the sub-biotite or sub-chlorite zone. Pyrrhotite was interpreted to form from pyrite and/or other iron phases based on lithology; these reactions can affect the paleoredox proxy. Iron carbonates can also severely influence iron speciation results since they often form in anoxic pore fluids during diagenesis; textural analyses of the Belt Supergroup samples highlighted that iron-bearing carbonates were early diagenetic cements or later diagenetic overprints. The inclusion of iron from diagenetic minerals during iron speciation analyses will skew results by providing a view of pore

In situ study of the factors controlling Fe, Cu and Zn scavenging during the early mixing between hydrothermal fluids and seawater

NASA Astrophysics Data System (ADS)

Cathalot, C.; Laes-Huon, A.; Pelleter, E.; Maillard, L.; Chéron, S.; Boissier, A.; Waeles, M.; Cotte, L.; Pernet-Coudrier, B.; Gayet, N.; Sarrazin, J.; Sarradin, P. M.

2016-12-01

Despite the importance of trace metals for marine ecosystems and in the global carbon cycle, dissolved metal sources in the deep ocean and their export mechanism are, today, still unconstrained. The historical view that dissolved metals are largely removed from hydrothermal plumes through precipitation of a range of iron-bearing minerals is now being challenged. Several potential mechanisms for the delivery of hydrothermally sourced metals to the open ocean have been suggested and require a thorough documentation of the early mixing processes between the hydrothermal fluids and the ambient seawater. The geochemistry of a plume, and specially the rising plume, is dictated by the nature and composition of the host rock, fluid temperature, phase separation at depth and subsurface mixing processes, and thus can vary in temperature, pH, metal and dissolved gases content between spatially close hydrothermal vents. Here, we present in situ chemical conditions during the early mixing gradient between hydrothermal fluids and seawater at the Lucky Strike site (Mid-Atlantic Ridge), using a multi proxy approach targeting both the dissolved and particulate phase and combining in situ measurements and analysis back in the lab. Indeed, in situ O2, H2S and temperature measurements were performed at a 1Hz frequency, coupled to lower frequency analysis of in situ Fe2+. In addition, particulate material filtered in situ was analyzed using Inductive Coupled Plasma - Mass Spectrometry, X-Ray Diffraction, X-Ray Fluorescence and Scanning Electron Microscopy and provided useful insights regarding the reactivity of metals during the mixing processes. Our results show different behavior within the Lucky Strike vent field. Fe and S co-precipitation through chalcopyrite formation at the newly discovered Capelinhos site seem to be the main process. At the White Caste site, on the other hand, wurzite and sphalerite precipitation seems to dominate the dilution processes, H2S being rapidly

Distal alluvial fan sediments in early Proterozoic red beds of the Wilgerivier formation, Waterberg Group, South Africa

NASA Astrophysics Data System (ADS)

Van Der Neut, M.; Eriksson, P. G.; Callaghan, C. C.

The 1900 - 1700 M.a. Waterberg Group belongs to a series of southern African cratonic cover sequences of roughly equivalent age. Red beds of the Wilgerivier Formation comprise sandstones, interbedded with subordinate conglomerates and minor mudrocks. These immature sedimentary rocks exhibit lenticular bedding, radial palaeocurrent patterns and features indicative of both streamflow and gravity-flow deposition. A distal wet alluvial fan palaeoenvironmental setting is envisaged, with fan-deltas forming where alluvial lobes prograded into a lacustrine basin. Intrastratal, diagenetic alteration of ferromagnesian detrital grains and ferruginous grain coatings led to the red colouration of the Wilgerivier sediments.

Bio- and chemostratigraphy of the Early Aptian Oceanic Anoxic Event 1a within the mid-latitudes of northwest Europe (Germany, Lower Saxony Basin)

NASA Astrophysics Data System (ADS)

Heldt, Matthias; Mutterlose, Joerg; Berner, Uli; Erbacher, Jochen

2013-04-01

The Mid-Cretaceous period was characterised by a series of prominent anoxic events, one of these was the late Early Aptian Oceanic Anoxic Event 1a (OAE 1a). The Fischschiefer horizon is the regional sedimentary expression of this event in a small epicontinental sea in northwest Europe (Germany, Lower Saxony Basin). In the present study, two sediment cores of Lower to Upper Aptian age (Hoheneggelsen KB 9 and 40) from the Brunswick area, north Germany, have been investigated in detail with respect to their lithostratigraphy, geochemistry (CaCO3, TOC), biostratigraphy (coccoliths, nannoliths) and high-resolution chemostratigraphy (^13Ccarb and ^13Corg). Together with separately published new planktonic foraminifer data of the cores it was possible to establish a detailed time frame and to recognise the OAE 1a. The ^13C data enabled us to subdivide the deposits into isotope segments (C2-C7), which are commonly used as stratigraphic markers in coeval sediments around the world. The carbon isotope curves are compared to recently published Aptian curves from other parts of the Lower Saxony Basin, all of which record the prominent carbon isotope anomaly of the OAE 1a. A high-resolution correlation of the typical isotope trends of OAE 1a (segments C3-6) across the Lower Saxony Basin appears difficult due to an early diagenetic overprint of the primary isotope signal. These alterations can be explained by the temporary establishment of euxinic conditions the Lower Saxony Basin during OAE 1a as consequence of an interplay of different factors, such as global warming, restricted palaeogeography, increased fluvial input and intensified stable water stratification, which is supported by several lines of regional evidence.

Methods for forming particles

DOEpatents

Fox, Robert V.; Zhang, Fengyan; Rodriguez, Rene G.; Pak, Joshua J.; Sun, Chivin

2016-06-21

Single source precursors or pre-copolymers of single source precursors are subjected to microwave radiation to form particles of a I-III-VI.sub.2 material. Such particles may be formed in a wurtzite phase and may be converted to a chalcopyrite phase by, for example, exposure to heat. The particles in the wurtzite phase may have a substantially hexagonal shape that enables stacking into ordered layers. The particles in the wurtzite phase may be mixed with particles in the chalcopyrite phase (i.e., chalcopyrite nanoparticles) that may fill voids within the ordered layers of the particles in the wurtzite phase thus produce films with good coverage. In some embodiments, the methods are used to form layers of semiconductor materials comprising a I-III-VI.sub.2 material. Devices such as, for example, thin-film solar cells may be fabricated using such methods.

Early Silurian (Llandoverian) Leask Point and Charlton Bay bioherms, Manitoulin Island, Ontario, Canada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mielczarek, W.; Copper, P.

1986-08-01

About 300 bioherms are known in the Llandoverian Manitoulin Formation of eastern Manitoulin Island. In the South Bay area, the large Leask Piont bioherm and Charlton Bay patch-reef complex lack a distinct skeletal growth framework. Bioherms consist of mudstone and wackestone, with isolated lenses of bafflestone, boundstone, floatstone. Fossils are scarce, but crinozoans and bryozoans comprise about 90% of the bioclasts. Other fauna include stromatoporoids, corals, brachiopods, gastropods, trilobites, and probable algae (algae are difficult to identify and may have played a significant role). Faunal ratios remained relatively constant during mound growth. Soft substrates with sedimentation rates of a fewmore » millimeters per year are suggested by bedding type and morphologic dominance of lamellar and tabular corals and stromatoporoids. An increased sedimentation rate, resulting from shoaling, is indicated by more overturned, broadly conical corals in the upper parts of the mounds. Shoaling may be responsible for cessation of mound growth. Lithoclasts are more common in the upper parts of the mounds. They formed when semiconsolidated muds were disturbed and redeposited during storms. Megarippled interreef surface areas, largely devoid of coral growth, indicate mud instability at Charlton Bay. Lack of suitable stable substrates may have hampered coral development. Dolomitization was postdepositional. The diagenetic sequence occurred in three stages: 1)selective pyritization and silicification, formation of an early muddy dolomite replacing the mud fraction of the dolostone, lithification and formation of rare calcite cement and neomorphic syntaxial rims; 2)clear, coarse dolomite replacing pore-filling calcite cement, syntaxial rims, and unaltered macrofossils, stylolitization, grain-to-grain dissolution; and 3)a late dolomite found mainly as fine rhombs in stylolites, solution seams, and intraskeletal pore space.« less

A ground-water mixing model for the origin of the Imini manganese deposit (Cretaceous) of Morocco.

USGS Publications Warehouse

Force, E.R.; Back, W.; Spiker, E. C.; Knauth, L.P.

1986-01-01

Three beds of manganese oxide ore in a 10 m-thick dolomite unit are associated with diagenetic features, and, are accordingly also diagenetic in their present aspect. Whether primary or introduced, the Mn mineralogy is attributed to reactions between fresh and saline ground-waters as the zone of mixing passed through the dolomite unit during a period of falling sea-level. The succession of diagenetic changes is: 1) precursor carbonates, 2) dolomite-janggunite, 3) hollandite-pyrolusite-chert-calcite.-G.J.N.

Early diagenesis and authigenic mineral formation in mobile muds of the Changjiang Estuary and adjacent shelf

NASA Astrophysics Data System (ADS)

Zhao, Bin; Yao, Peng; Bianchi, Thomas S.; Xu, Yahong; Liu, Hui; Mi, Tiezhu; Zhang, Xiao-Hua; Liu, Jiwen; Yu, Zhigang

2017-08-01

Large-river delta-front estuaries (LDEs) and their adjacent shelf margins are sites of dynamic diagenetic processes that play a significant role in coastal biogeochemical cycling. In this study, we used dissolved inorganic carbon (DIC), redox sensitive elements (Fe2 + and Mn2 +), dissolved inorganic nitrogen (DIN) nutrients (NH4+, NO3-, and NO2-), major cations and anions (K+, Ca2 +, Mg2 +, SO42 -, and Cl-) in bottom-water and sediment pore-waters, to investigate the early chemical diagenesis and authigenic mineral formation in mobile-mud deposits of the Changjiang Estuary and adjacent inner shelf of the East China Sea (ECS). Vertical profiles of DIC and NH4+ in pore-waters had similar trends at most sites, showing a significant increase with depth near the Changjiang Estuary and being relatively constant at offshore sites. Higher pore-water DIC and NH4+ concentrations were observed in nearshore sites in winter, which were likely attributed to exposure of deeper deposits by winter coastal erosion. Nitrification was observed at most sites, and AOB (ammonia-oxidizing bacteria) played a leading role in ammonia oxidation in the study areas. The nitrification-denitrification was likely important in contributing to the loss of DIN in offshore sites during summer. Large inputs of organic carbon (OC) and terrestrial materials from Changjiang River resulted in intense sulfate reduction and Fe and Mn reduction in nearshore sites. Lower C/N and C/S ratios coupled with an apparent decrease in pore-water Ca2 + and Mg2+ concentrations with depth near the Changjiang Estuary, which indicated that authigenic carbonate formation occurs in these sediments. Decreases in K+ and Mg2 + with depth reflected that reverse weathering was an important process of authigenic mineral formation in these sediments. We conclude that adsorption process, seasonal erosion-redeposition, and summer hypoxic conditions of bottom-waters may play an important role in early diagenesis processes and

Orogenic-type copper-gold-arsenic-(bismuth) mineralization at Flatschach (Eastern Alps), Austria

NASA Astrophysics Data System (ADS)

Raith, Johann G.; Leitner, Thomas; Paar, Werner H.

2015-10-01

Structurally controlled Cu-Au mineralization in the historic Flatschach mining district (Styria, Austria) occurs in a NE-SW to NNE-WSW oriented vein system as multiple steep-dipping calcite-(dolomite)-quartz veins in amphibolite facies metamorphic rocks (banded gneisses/amphibolites, orthogneisses, metagranitoids) of the poly-metamorphosed Austroalpine Silvretta-Seckau nappe. Vein formation postdated ductile deformation events and Eoalpine (Late Cretaceous) peak metamorphism but predated Early to Middle Miocene sediment deposition in the Fohnsdorf pull-apart basin; coal-bearing sediments cover the metamorphic basement plus the mineralized veins at the northern edge of the basin. Three gold-bearing ore stages consist of a stage 1 primary hydrothermal (mesothermal?) ore assemblage dominated by chalcopyrite, pyrite and arsenopyrite. Associated minor minerals include alloclasite, enargite, bornite, sphalerite, galena, bismuth and matildite. Gold in this stage is spatially associated with chalcopyrite occurring as inclusions, along re-healed micro-fractures or along grain boundaries of chalcopyrite with pyrite or arsenopyrite. Sericite-carbonate alteration is developed around the veins. Stage 2 ore minerals formed by the replacement of stage 1 sulfides and include digenite, anilite, "blue-remaining covellite" (spionkopite, yarrowite), bismuth, and the rare copper arsenides domeykite and koutekite. Gold in stage 2 is angular to rounded in shape and occurs primarily in the carbonate (calcite, Fe-dolomite) gangue and less commonly together with digenite, domeykite/koutekite and bismuth. Stage 3 is a strongly oxidized assemblage that includes hematite, cuprite, and various secondary Cu- and Fe-hydroxides and -carbonates. It formed during supergene weathering. Stage 1 and 2 gold consists mostly of electrum (gold fineness 640-860; mean = 725; n = 46), and rare near pure gold (fineness 930-940; n = 6). Gold in stage 3 is Ag-rich electrum (fineness 350-490, n = 12), and has a

The influence of seawater carbonate chemistry, mineralogy, and diagenesis on calcium isotope variations in Lower-Middle Triassic carbonate rocks

DOE PAGES

Lau, Kimberly V.; Maher, Kate; Brown, Shaun T.; ...

2017-11-01

various geological ages. By using a model of early marine diagenetic water-rock interaction, we illustrate that this general correlation can be explained by the chemical evolution of bulk carbonate sediment samples with different initial mineralogical compositions that subsequently underwent recrystallization. Although early diagenetic resetting and carbonate mineralogy strongly influence the carbonate δ 44/40 Ca values, the relationship between [Sr] and δ 44/40 Ca holds potential for reconstructing first-order secular changes in seawater δ 44/40 Ca composition.« less

The influence of seawater carbonate chemistry, mineralogy, and diagenesis on calcium isotope variations in Lower-Middle Triassic carbonate rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lau, Kimberly V.; Maher, Kate; Brown, Shaun T.

various geological ages. By using a model of early marine diagenetic water-rock interaction, we illustrate that this general correlation can be explained by the chemical evolution of bulk carbonate sediment samples with different initial mineralogical compositions that subsequently underwent recrystallization. Although early diagenetic resetting and carbonate mineralogy strongly influence the carbonate δ 44/40 Ca values, the relationship between [Sr] and δ 44/40 Ca holds potential for reconstructing first-order secular changes in seawater δ 44/40 Ca composition.« less

Effects of early sea-floor processes on the taphonomy of temperate shelf skeletal carbonate deposits

NASA Astrophysics Data System (ADS)

Smith, Abigail M.; Nelson, Campbell S.

2003-10-01

Cool-water shelf carbonates differ from tropical carbonates in their sources, modes, and rates of deposition, geochemistry, and diagenesis. Inorganic precipitation, marine cementation, and sediment accumulation rates are absent or slow in cool waters, so that temperate carbonates remain longer at or near the sea bed. Early sea-floor processes, occurring between biogenic calcification and ultimate deposition, thus take on an important role, and there is the potential for considerable taphonomic loss of skeletal information into the fossilised record of cool-water carbonate deposits. The physical breakdown processes of dissociation, breakage, and abrasion are mediated mainly by hydraulic regime, and are always destructive. Impact damage reduces the size of grains, removes structure and therefore information, and ultimately may transform skeletal material into anonymous particles. Abrasion is highly selective amongst and within taxa, their skeletal form and structure strongly influencing resistance to mechanical breakdown. Dissolution and precipitation are the end-members of a two-way chemical equilibrium operating in sea water. In cool waters, inorganic precipitation is rare. There is conflicting opinion about the importance of diagenetic dissolution of carbonate skeletons on the temperate sea floor, but test maceration and early loss of aragonite in particular are reported. Dissolution may relate to undersaturated acidic pore waters generated locally by a combination of microbial metabolisation of organic matter, strong bioturbation, and oxidation of solid phase sulphides immediately beneath the sea floor in otherwise very slowly accumulating skeletal deposits. Laboratory experiments demonstrate that surface-to-volume ratio and skeletal mineralogy are both important in determining skeletal resistance to dissolution. Biological processes on the sea floor include encrustation and bioerosion. Encrustation, a constructive process, may be periodic or seasonal, and can be

Compression-cuticle relationship of seed ferns: Insights from liquid-solid states FTIR (Late Palaeozoic-Early Mesozoic, Canada-Spain-Argentina)

USGS Publications Warehouse

Zodrow, E.L.; D'Angelo, J. A.; Mastalerz, Maria; Keefe, D.

2009-01-01

Cuticles have been macerated from suitably preserved compressed fossil foliage by Schulze's process for the past 150 years, whereas the physical-biochemical relationship between the "coalified layer" with preserved cuticle as a unit has hardly been investigated, although they provide complementary information. This relationship is conceptualized by an analogue model of the anatomy of an extant leaf: "vitrinite (mesophyll) + cuticle (biomacropolymer) = compression". Alkaline solutions from Schulze's process as a proxy for the vitrinite, are studied by means of liquid-solid states Fourier transform infrared spectroscopy (FTIR). In addition, cuticle-free coalified layers and fossilized cuticles of seed ferns mainly from Canada, Spain and Argentina of Late Pennsylvanian-Late Triassic age are included in the study sample. Infrared data of cuticle and alkaline solutions differ which is primarily contingent on the mesophyll +biomacropolymer characteristics. The compression records two pathways of organic matter transformation. One is the vitrinized component that reflects the diagenetic-post-diagenetic coalification history parallel with the evolution of the associated coal seam. The other is the cuticle that reflects the sum-total of evolutionary pathway of the biomacropolymer, its monomeric, or polymeric fragmentation, though factors promoting preservation include entombing clay minerals and lower pH conditions. Caution is advised when interpreting liquid-state-based FTIR data, as some IR signals may have resulted from the interaction of Schulze's process with the cuticular biochemistry. A biochemical-study course for taphonomy is suggested, as fossilized cuticles, cuticle-free coalified layers, and compressions are responses to shared physicogeochemical factors. ?? 2009 Elsevier B.V. All rights reserved.

Occurrence of silver minerals in a silver-rich pocket in the massive sulfide zinc-lead ores in the Edwards mine, New York

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serviss, C.R.; Grout, C.M.; Hagni, R.D.

1985-01-01

Ore microscopic examination of uncommon silver-rich ores from the Edwards mine has detected three silver minerals, native silver, freibergite, and argentite, that were previously unreported in the literature from the Balmat-Edwards district. The zinc-lead ore deposits of the Balmat-Edwards District in northern New York are composed of very coarse-grained massive sulfides, principally sphalerite, galena, and pyrite. The typical ores contain small amounts of silver in solid solution galena. Galena concentrates produced from those ores have contained an average of 15 ounces of silver per ton of 60% lead concentrates. In contrast to the typical ore a silver-rich pocket, that measuredmore » three feet by three feet on the vertical mine face and was the subject of this study, contained nearly 1% silver in a zinc ore. Ore microscopic study shows that this ore is especially characterized by abundant, relatively fine-grained chalcopyrite with anhedral pyrite inclusions. Fine-grained sphalerite, native silver, argentite, freibergite and arsenopyrite occur in association with the chalcopyrite and as fracture-fillings in gangue minerals. Geochemically anomalous amounts of tin, barium, chromium, and nickel also are present in the silver-rich pocket. The silver-rich pocket may mark the locus of an early feeder vent or alternatively it may record a hydrothermal event that was superimposed upon the event responsible for the metamorphic ore textures.« less

A critical evaluation of carbon isotope stratigraphy and biostratigraphic implications for Late Cretaceous global correlation

NASA Astrophysics Data System (ADS)

Wendler, Ines

2013-11-01

carbonate, and in partitioning of carbon between organic carbon and carbonate sinks. These variations are mainly controlled by changes in climate and eustasy. Additionally, some globally synchronous shifts in the bulk δ13Ccarb records could result from parallel variation in the contribution of authigenic carbonate to the sediment. Formation of these cements through biologically mediated early diagenetic processes is related to availability of oxygen and organic material and, thus, can be globally synchronized by fluctuations in eustasy, atmospheric and oceanic oxygen levels or in large-scale oceanic circulation. Because the influence of early diagenetic cements on the bulk δ13Ccarb signal can, but need not be synchronized, chemostratigraphy should not be used as a stand-alone method for trans-continental correlation, and especially minor isotopic shifts have to be interpreted with utmost care. Nevertheless, the observed consistency of the δ13C correlations confirms global scale applicability of bulk sediment δ13C chemostratigraphy for the Late Cretaceous, including sediments that underwent lithification and burial diagenesis such as the sediments from the Himalayan and Alpine sections. Limitations arise from increased uncertainties (1) in sediments with very low carbonate content, (2) from larger δ13C variability in sediments from very shallow marine environments, (3) from unrecognized hiatuses or strong changes in sedimentation rates, and (4) in sections with short stratigraphic coverage or with few biostratigraphic marker horizons.

Sedimentology, petrography and early diagenesis of a travertine-colluvium succession from Chusang (southern Tibet)

NASA Astrophysics Data System (ADS)

Wang, Zhijun; Meyer, Michael C.; Hoffmann, Dirk L.

2016-08-01

The Chusang travertine is situated in southern Tibet at an altitude of ~ 4200 m asl. in a cold-arid, periglacial environment and is characterized by interbedding of hydrothermal carbonate with colluvium. Here we present sedimentological and petrographical data to elucidate the depositional environment and sedimentary processes responsible for hydrothermal carbonate precipitation and early diagenetic alteration as well as clastic sediment accumulation and provide initial 230Th/U ages to constrain the time-depth of this travertine-colluvium succession. Three main travertine lithofacies have been identified: 1) a dense laminated lithofacies, 2) a porous layered lithofacies and 3) an intraclastic lithofacies that results from erosion of pre-existing hot spring carbonate. The colluvium is composed of cohesive debris flow layers that derived from mass-wasting events from the adjacent hillslopes. Micro-fabric analyses suggest that dense laminated travertine forms via rapid calcite precipitation from hot spring water seasonally subjected to severe winter cooling, while porous layered travertine results from seasonal dilution of hot spring water with rain water during the summer monsoon months, which in turn stimulates biological productivity and gives rise to a porous summer layer. Early diagenesis in the form of recrystallization and extensive formation of pore cements is common in the Chusang travertine, but never eradicates the original crystal fabrics completely. The sedimentary architecture of the deposit is conditioned by (i) the gently dipping (~ 10°) pre-existing terrain on which hot spring water is discharged from multiple travertine mounds causing laterally extensive travertine sheets to precipitate, and (ii) the adjacent much steeper (up to 30°) periglacial hillslopes that are the source area of repeated debris flows that accumulate on the travertine surface. The resulting travertine-colluvium succession has a total thickness of ~ 24 m and 230Th/U dating

Sulphur and oxygen sequestration of n-C37 and n-C38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

USGS Publications Warehouse

Koopmans, M.P.; Schaeffer-Reiss, C.; De Leeuw, J. W.; Lewan, M.D.; Maxwell, J.R.; Schaeffer, P.; Sinninghe, Damste J.S.

1997-01-01

Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature (Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330??C for 72 h to study the diagenetic fate of n-C37 and n-C38 di-and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260??C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S-and O-bound n-C37 and n-C38 skeletons, saturated n-C37 and n-C38 methyl, ethyl, and mid-chain ketones, C37 and C38 mid-chain 2,5-di-n-alkylthiophenes, C37 and C38 1,2-di-n-alkylbenzenes, and C37 and C38 n-alkanes. With increasing thermal maturation, three forms of the n-C37 and n-C38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di-n-alkylbenzenes and saturated ketones), whereas the S-and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C37 and n-C38 skeleton can be expected as well as the corresponding hydrocarbons. Copyright ?? 1997 Elsevier Science Ltd.

Sulphur and oxygen sequestration of n-C 37 and n-C 38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

NASA Astrophysics Data System (ADS)

Koopmans, Martin P.; Schaeffer-Reiss, Christine; de Leeuw, Jan W.; Lewan, Michael D.; Maxwell, James R.; Schaeffer, Philippe; Sinninghe Damsté, Jaap S.

1997-06-01

Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature ( Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330°C for 72 h to study the diagenetic fate of n-C 37 and n-C 38 di- and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260°C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S- and O-bound n-C 37 and n-C 38 skeletons, saturated n-C 37 and n-C38 methyl, ethyl, and mid-chain ketones, C 37 and C 38 mid-chain 2,5-di- n-alkylthiophenes, C 37 and C 38 1,2-di- n-alkylbenzenes, and C 37 and C 38n-alkanes. With increasing thermal maturation, three forms of the n-C 37 and n-C 38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di- n-alkylbenzenes and saturated ketones), whereas the S- and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C 37 and n-C 38 skeleton can be expected as well as the corresponding hydrocarbons.

Impact of Diagenesis on Biosignature Preservation Potential in Playa Lake Evaporites in Verde Formation, Arizona: Implications for Mars Exploration

NASA Astrophysics Data System (ADS)

Shkolyar, S.; Farmer, J. D.

2015-12-01

Major priorities for Mars science include assessing the preservation potential and impact of diagenesis on biosignature preservation in aqueous sedimentary environments. We address these priorities with field and lab studies of playa evaporites of the Verde Formation (upper Pliocene) in Arizona. Evaporites studied include bottom-nucleated halite and displacive growth gypsum in magnesite-rich mudstone. These lithotypes are potential analogs for ancient lacustrine habitable environments on Mars. This study aimed to understand organic matter preservation potential under different diagenetic histories. Methods combined outcrop-scale field observations and lab analyses, including: (1) thin-section petrography to understand diagenetic processes and paragenesis; (2) X-ray powder diffraction to obtain bulk mineralogy; (3) Raman spectroscopy to identify and place phases (and kerogenous fossil remains) within a microtextural context; (4) Total Organic Carbon (TOC) analyses to estimate weight percentages of preserved organic carbon for each subfacies endmember; and (5) electron microprobe to create 2D kerogen maps semi-quantifying kerogen preservation in each subfacies. Results revealed complex diagenetic histories for each evaporite subfacies and pathways for organic matter preservation. Secondary gypsum grew displacively within primary playa lake mudstones during early diagenesis. Mudstones then experienced cementation by Mg-carbonates. Displacive-growth gypsum was sometimes dissolved, forming crystal molds. These molds were later either infilled by secondary sulfates or recrystallized to gypsum pseudomorphs with minor phases present (i.e., glauberite). These observations helped define taphonomic models for organic matter preservation in each subfacies. This work has the potential to inform in situ target identification, sampling strategies, and data interpretations for future Mars Sample Return missions (e.g., sample caching strategies for NASA's Mars 2020 mission).

Factors influencing the biogeochemistry of sedimentary carbon and phosphorus in the Sacramento-San Joaquin Delta

USGS Publications Warehouse

Nilsen, E.B.; Delaney, M.L.

2005-01-01

This study characterizes organic carbon (Corganic) and phosphorus (P) geochemistry in surface sediments of the Sacramento-San Joaquin Delta, California. Sediment cores were collected from five sites on a sample transect from the edge of the San Francisco Bay eastward to the freshwater Consumnes River. The top 8 cm of each core were analyzed (in 1-cm intervals) for Corganic, four P fractions, and redox-sensitive trace metals (uranium and manganese). Sedimentary Corganic concentrations and Corganic:P ratios decreased, while reactive P concentrations increased moving inland in the Delta. The fraction of total P represented by organic P increased inland, while that of authigenic P was higher bayward than inland reflecting increased diagenetic alteration of organic matter toward the bayward end of the transect. The redox indicator metals are consistent with decreasing sedimentary suboxia inland. The distribution of P fractions and C:P ratios reflect the presence of relatively labile organic matter in upstream surface sediments. Sediment C and P geochemistry is influenced by site-specific particulate organic matter sources, the sorptive power of the sedimentary material present, physical forcing, and early diagenetic transformations presumably driven by Corganic oxidation. ?? 2005 Estuarine Research Federation.

Evidence for early life in Earth's oldest hydrothermal vent precipitates.

PubMed

Dodd, Matthew S; Papineau, Dominic; Grenne, Tor; Slack, John F; Rittner, Martin; Pirajno, Franco; O'Neil, Jonathan; Little, Crispin T S

2017-03-01

Although it is not known when or where life on Earth began, some of the earliest habitable environments may have been submarine-hydrothermal vents. Here we describe putative fossilized microorganisms that are at least 3,770 million and possibly 4,280 million years old in ferruginous sedimentary rocks, interpreted as seafloor-hydrothermal vent-related precipitates, from the Nuvvuagittuq belt in Quebec, Canada. These structures occur as micrometre-scale haematite tubes and filaments with morphologies and mineral assemblages similar to those of filamentous microorganisms from modern hydrothermal vent precipitates and analogous microfossils in younger rocks. The Nuvvuagittuq rocks contain isotopically light carbon in carbonate and carbonaceous material, which occurs as graphitic inclusions in diagenetic carbonate rosettes, apatite blades intergrown among carbonate rosettes and magnetite-haematite granules, and is associated with carbonate in direct contact with the putative microfossils. Collectively, these observations are consistent with an oxidized biomass and provide evidence for biological activity in submarine-hydrothermal environments more than 3,770 million years ago.

Sequence-stratigraphic controls on sandstone diagenesis: An example from the Williams Fork formation, Piceance Basin, Colorado

NASA Astrophysics Data System (ADS)

Aboktef, Adel

This study documents the distribution of diagenetic alterations in Williams Fork fluvial sandstones, assess sequence stratigraphic controls on diagenetic features, and addresses diagenetic impacts on porosity. Petrographic point counts of 220 thin sections from six wells forms the database. The near absence of potassium feldspar and volcanic rock fragments in the lower Williams Fork interval and increasing plagioclase content upward represent changes in sediment provenance rather than stratigraphic variability in diagenesis. The lower Williams Fork sands are from sedimentary sources whereas middle and upper Williams Fork sands include input from magmatic arcs and basement uplifts. Compaction, early and late cementation, dissolution, and replacement by calcite or clay minerals combined to alter Williams Fork sandstones. Infiltration of clays occurred prior to any burial. Chlorite, quartz, non-ferroan calcite, compaction and dissolution features, and kaolinite formed during eo-diagenesis at <70°C. More quartz, compaction and dissolution features, plus albite, illite, mixed-layer illite/smectite, ferroan calcite, and dolomite formed in the meso-diagenetic realm (>70°C). Four of these features show spatial variability with respect to systems tracts. Infiltrated clays are concentrated in lowstand systems tracts (LST) and highstand systems tracts (HST) because accommodation space rose slow or fell during deposition of those sands, which led to prolonged sand body exposure on floodplain and ample opportunities for downward percolation of mud during flood events. Concentration of pseudomatrix (mud intraclasts) in HST and LST deposits resulted from floodplain erosion when base-level fell with decreasing accommodation space. Authigenic chlorite formed in the HST and transgressive systems tracts (TST) of the upper half of the Williams Fork Formation because volcanic clasts are abundant in that interval. Quartz overgrowths are more likely to exceed 7% in TST deposits for

Origin of limestone-marlstone cycles: Astronomic forcing of organic-rich sedimentary rocks from the Cenomanian to early Coniacian of the Cretaceous Western Interior Seaway, USA

NASA Astrophysics Data System (ADS)

Eldrett, James S.; Ma, Chao; Bergman, Steven C.; Ozkan, Aysen; Minisini, Daniel; Lutz, Brendan; Jackett, Sarah-Jane; Macaulay, Calum; Kelly, Amy E.

2015-08-01

We present an integrated multidisciplinary study of limestone-marlstone couplets from a continuously cored section including parts of the upper Buda Limestone, the entire Eagle Ford Group (Boquillas Formation) and lower Austin Chalk from the Shell Iona-1 research borehole (Texas, USA), which provides a >8 million year (myr) distal, clastic sediment-starved, intrashelf basin record of the early Cenomanian to the earliest Coniacian Stages. Results show that despite variable yet minimal diagenetic overprints, several unambiguous primary environmental signals are preserved and support greater water-mass ventilation and current activity promoting increased silica/carbonate productivity during the deposition of limestone beds compared to deposition of marlstone beds which reflect greater organic matter productivity and preservation. Furthermore, our astronomical analyses demonstrate that the limestone-marlstone couplets in the Iona-1 core reflect climatic forcing driven by solar insolation resulting from integrated Milankovitch periodicities. In particular, we propose that obliquity and precession forcing on the latitudinal distribution of solar insolation may have been responsible for the observed lithological and environmental variations through the Cenomanian, Turonian and Coniacian in this mid-latitude epicontinental sea setting. Our data also suggests that rhythmic lithological alternations deposited in Greenhouse periods, in general, may simply reflect climate-driven cycles related to Earth-Sun dynamics without the need to invoke significant sea-level variations.

Illite polytype quantification using Wildfire© calculated x-ray diffraction patterns

USGS Publications Warehouse

Grathoff, Georg H.; Moore, D.M.

1996-01-01

Illite polytype quantification allows the differentiation of diagenetic and detrital illite components. In Paleozoic shales from the Illinois Basin, we observe 3 polytypes: 1Md, 1M and 2M1. 1Md and 1M are of diagenetic origin and 2M1 is of detrital origin. In this paper, we compare experimental X-ray diffraction (XRD) traces with traces calculated using WILDFIRE© and quantify mixtures of all 3 polytypes, adjusting the effects of preferred orientation and overlapping peaks. The broad intensity (“illite hump”) around the illite 003, which is very common in illite from shales, is caused by the presence of 1Md illite and mixing of illite polytypes and is not an artifact of sample preparation or other impurities in the sample. Illite polytype quantification provides a tool to extrapolate the K/Ar age and chemistry of the detrital and diagenetic end-members by analysis of different size fractions containing different proportions of diagenetic and detrital illite polytypes.

Lithology, petrography and Cu occurrence of the Neoproterozoic glacial Mwale Formation at the Shanika syncline (Tenke Fungurume, Congo Copperbelt; Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Mambwe, Pascal; Milan, Luke; Batumike, Jacques; Lavoie, Sébastien; Jébrak, Michel; Kipata, Louis; Chabu, Mumba; Mulongo, Sonya; Lubala, Toto; Delvaux, Damien; Muchez, Philippe

2017-05-01

The Mwale Formation that constitutes the base of the Nguba Group in the Neoproterozoic Katanga Supergroup has recently attracted renewed interest for copper mineral exploration. We present new field observations combined with detailed logging and petrography of MWAS0001 drill hole at Shanika syncline in the Tenke Fungurume Mining District. Our study has enabled us to subdivide the Mwale Formation into 7 distinct sequences. This succession is host to glaciogenic, glaciomarine, glaciofluvial and glaciolacustrine deposits. Glaciomarine beds are typically a deposit by debris flow in deep water marine environment, induced by basin wide tectonics and glaciation influence. Glaciofluvial beds were deposited in shallow water, fluvial deltaic environment. The glaciolacustrine environment is indicated by dropstones occurring in the laminated mudstone and rhythmites with dispersed clasts observed in the siltstone and conglomerate. These beds are interlayered within the glaciogenic beds, and are characterised by variable clast composition (felsic, mafic and metamorphic). The clasts are very poorly sorted, angular, rounded to moderately rounded, faceted or striated, and supported in a sandy argillaceous or mud matrix. Two main episodes of sulphide mineralisation are distinguished in the Mwale Formation. The diagenetic episode consists of disseminated euhedral and framboidal pyrites. The hydrothermal episode is associated with Mg-metasomatism and characterised by low grade copper mineralisation that occurs (i) in veins filled with carbonate-chlorite and carbonate-quartz-chlorite-Cu sulphides, such as chalcocite, chalcopyrite and bornite, and (ii) as disseminated sulphides within the host rock. This second episode is late to post-orogenic and can be correlated with late brittle tectonics within the Lufilian arc. The other alteration types include silicification and potassic alteration; however, these alterations are not associated with mineralisation.

Lithofacies and Diagenetic Controls on Formation-scale Mechanical, Transport, and Sealing Behavior of Caprocks: A Case Study of the Morrow shale and Thirteen Finger Limestone, Farnsworth Unit, Texas

NASA Astrophysics Data System (ADS)

Trujillo, N. A.; Heath, J. E.; Mozley, P.; Dewers, T. A.; Cather, M.

2016-12-01

Assessment of caprock sealing behavior for secure CO2 storage is a multiscale endeavor. Sealing behavior arises from the nano-scale capillarity of pore throats, but sealing lithologies alone do not guarantee an effective seal since bypass systems, such as connected, conductive fractures can compromise the integrity of the seal. We apply pore-to-formation-scale data to characterize the multiscale caprock sealing behavior of the Morrow shale and Thirteen Finger Limestone. This work is part of the Southwest Regional Partnership on Carbon Sequestration's Phase III project at the Farnsworth Unit, Texas. The caprock formations overlie the Morrow sandstone, the target for enhanced oil recovery and injection of over one million metric tons of anthropogenically-sourced CO2. Methods include: focused ion beam-scanning electron microscopy; laser scanning confocal microscopy; electron and optical petrography; multi-stress path mechanical testing and constitutive modeling; core examinations of sedimentary structures and fractures; and a noble gas profile for formation-scale transport of the sealing lihologies and the reservoir. We develop relationships between diagenetic characteristics of lithofacies to mechanical and petrophysical measurements of the caprocks. The results are applied as part of a caprock sealing behavior performance assessment. Funding for this project is provided by the U.S. Department of Energy's National Energy Technology Laboratory through the Southwest Regional Partnership on Carbon Sequestration (SWP) under Award No. DE-FC26-05NT42591. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Does burial diagenesis reset pristine isotopic compositions in paleosol carbonates?

NASA Astrophysics Data System (ADS)

Bera, M. K.; Sarkar, A.; Tandon, S. K.; Samanta, A.; Sanyal, P.

2010-11-01

Sedimentological study of early Oligocene continental carbonates from the fluvial Dagshai Formation of the Himalayan foreland basin, India resulted in the recognition of four different types namely, soil, palustrine, pedogenically modified palustrine and groundwater carbonates. Stable oxygen and carbon isotopic ( δ18O and δ13C) analyses of fabric selective carbonate microsamples show that although the pristine isotopic compositions are largely altered during deep-burial diagenesis, complete isotopic homogenization does not occur. δ18O and δ13C analyses of ~ 200 calcrete and palustrine carbonates from different stratigraphic horizons and comparison with δ18O of more robust bioapatite (fossil vertebrate tooth) phase show that dense micrites (~ > 70% carbonate) invariably preserve the pristine δ18O value (mean) of ~ - 9.8‰, while altered carbonates show much lower δ18O value ~ - 13.8‰. Such inhomogeneity causes large intra-sample and intra-soil profile variability as high as > 5‰, suggesting that soils behave like a closed system where diagenetic overprinting occurs in local domains. A simple fluid-rock interaction model suggests active participation of clay minerals to enhance the effect of fluid-rock ratio in local domains during diagenesis. This places an upper limit of 70% micrite concentration above which the effect of diagenetic alteration is minimal. Careful sampling of dense micritic part of the soil carbonate nodules, therefore, does provide pristine isotopic composition and it is inappropriate, as proposed recently, to reject the paleoclimatic potential of all paleosol carbonates affected by burial diagenesis. Based on pristine δ13C value of - 8.8 ± 0.2‰ in soil carbonates an atmospheric CO 2 concentration between ~ 764 and ~ 306 ppmv is estimated for the early Oligocene (~ 31 Ma) Dagshai time. These data show excellent agreement between two independent proxy records (viz. soil carbonate and marine alkenone) and support early Oligocene

Geological features indicative of processes related to the hematite formation in Meridiani Planum and Aram Chaos, Mars: a comparison with diagenetic hematite deposits in southern Utah, USA

NASA Astrophysics Data System (ADS)

Ormö, Jens; Komatsu, Goro; Chan, Marjorie A.; Beitler, Brenda; Parry, William T.

2004-10-01

In order to understand the formation of the few but large, hematite deposits on Mars, comparisons are often made with terrestrial hematite occurrences. In southern Utah, hematite concretions have formed within continental sandstones and are exposed as extensive weathered-out beds. The hematite deposits are linked to geological and geomorphological features such as knobs, buttes, bleached beds, fractures and rings. These terrestrial features are visible in aerial and satellite images, which enables a comparison with similar features occurring extensively in the martian hematite-rich areas. The combination of processes involved in the movement and precipitation of iron in southern Utah can provide new insights in the context of the hematite formation on Mars. Here we present a mapping of the analogue geological and geomorphological features in parts of Meridiani Planum and Aram Chaos. Based on mapping comparisons with the Utah occurrences, we present models for the formation of the martian analogues, as well as a model for iron transport and precipitation on Mars. Following the Utah model, high albedo layers and rings in the mapped area on Mars are due to removal or lack of iron, and precipitation of secondary diagenetic minerals as fluids moved up along fractures and permeable materials. Hematite was precipitated intraformationally where the fluid transporting the reduced iron met oxidizing conditions. Our study shows that certain geological/geomorphological features can be linked to the hematite formation on Mars and that pH differences could suffice for the transport of the iron from an orthopyroxene volcanoclastic source rock. The presence of organic compounds can enhance the iron mobilization and precipitation processes. Continued studies will focus on possible influence of biological activity and/or methane in the formation of the hematite concretions in Utah and on Mars.

Depositional setting and early diagenesis of the dinosaur eggshell-bearing Aren Fm at Bastus, Late Campanian, south-central Pyrenees

NASA Astrophysics Data System (ADS)

Díaz-Molina, Margarita; Kälin, Otto; Benito, M. Isabel; Lopez-Martinez, Nieves; Vicens, Enric

2007-07-01

The Late Cretaceous Aren Fm exposed north of Bastus in the Tremp Basin (south-central Pyrenees) preserves an excellent record of dinosaur eggs laid in a marine littoral setting. Different from other cases reported in literature, at the Bastus site the preferential nesting ground was original beach sand. The coastal deposits of Aren Fm can be grouped into four facies assemblages, representing respectively shoreface, beachface, beach ridge plain and backbarrier lagoon environments. Shoreface deposits include fine- to coarse-grained hybrid arenites and subordinate quartz-dominated conglomerates with ripple structures of wave and wave-current origin. Beachface deposits are mainly storm beach conglomerates, but parallel-laminated foreshore arenites locally occur. Backbarrier lagoon deposits comprise of washover sandy conglomerates that grade laterally into sandy lime mudstones, biomicrites and marls. Beach ridge sediment, wherein the bulk of dinosaur eggs and eggshell debris occurs, predominantly is a reddish hybrid arenite that has undergone a complex early diagenetic evolution, including marine and meteoric cementation followed by soil development. The reddish arenites overlie wave-dominated shoreface deposits and in places pass laterally into lagoonal deposits. They originally formed shore ridges, that became stabilized during progradational episodes by pedogenesis (beach ridge, sensu [Otvos, E.G., 2000. Beach ridges—definitions and significance. Geomorphology 32, 83-108.]), which also affected the dinosaur eggs. The eggshell-bearing beach ridge arenites are typically preserved at the top of parasequences forming the systems tracts of a third-order sequence. Thick packages of this facies resulted from aggradation of barrier/beach ridge deposits, whose preservation below surfaces of transgressive erosion was favoured by incipient lithification.

Regional cement stratigraphy and diagenetic history of Waulsortian Limestones, eastern Midlands, Republic of Ireland

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, D.E.; Meyers, W.J.

1985-02-01

The Lower Carboniferous Waulsortian Limestones, eastern Midlands, Republic of Ireland, contain 7 distinct luminescent zones in clear calcite cements that overlie inclusion-rich, marine cements in cavities and also fill fractures and aragonite-skeleton molds. The luminescent sequence, which records precipitation from increasingly reducing pore waters, is regionally and stratigraphically consistent over an interval more than 1200 ft thick. Zone 1 cements are nonluminescent; zone 2 cements are brightly luminescent; and zones 3-7 cements are ferroan with a moderate to dull luminescence. Zone 1 cements (mean -2.6% delta/sup 18/O/ +3.3% delta/sup 13/C PDB) are slightly depleted in oxygen relative to radiaxial-fibrous cementsmore » (mean -1.8% delta/sup 18/O/ +3.5% delta/sup 13/C PDB) which have a composition that reflects Lower Carboniferous seawater. Zone 4 cements (mean -4.1% delta/sup 18/O/ +3.1% delta/sup 13/C PDB) are depleted in oxygen relative to zone 1, whereas zone 5 cements (mean -11.8% delta/sup 18/O/ +1.1 delta/sup 13/C PDB) are extremely depleted in oxygen and somewhat in carbon. Locally intense dolomitization includes 2 regionally extensive generations of ferroan saddle dolomite. Petrographic relationships demonstrate these dolomite generations were replaced by zone 5 cement. Sulfide mineralization, principally pyrite and sphalerite, occurred after the precipitation of zone 5 cement. Much of diagenesis occurred during a brief period in the Lower Carboniferous. Zones 1-6 and saddle dolomites are contained in Chadian (upper Osagean), shallow-marine facies overlying the Waulsortian. Fractures filled by zone 5 cements are truncated at the margins of Waulsortian clasts contained in a conglomerate overlying an early Arundian (early Meramecian) unconformity.« less

Evidence for early life in Earth’s oldest hydrothermal vent precipitates

USGS Publications Warehouse

Dodd, Matthew S.; Papineau, Dominic; Grenne, Tor; Slack, John F.; Rittner, Martin; Pirajno, Franco; O’Neil, Jonathan; Little, Crispin T.S.

2017-01-01

Although it is not known when or where life on Earth began, some of the earliest habitable environments may have been submarine-hydrothermal vents. Here we describe putative fossilized microorganisms that are at least 3,770 million and possibly 4,280 million years old in ferruginous sedimentary rocks, interpreted as seafloor-hydrothermal vent-related precipitates, from the Nuvvuagittuq belt in Quebec, Canada. These structures occur as micrometre-scale haematite tubes and filaments with morphologies and mineral assemblages similar to those of filamentous microorganisms from modern hydrothermal vent precipitates and analogous microfossils in younger rocks. The Nuvvuagittuq rocks contain isotopically light carbon in carbonate and carbonaceous material, which occurs as graphitic inclusions in diagenetic carbonate rosettes, apatite blades intergrown among carbonate rosettes and magnetite–haematite granules, and is associated with carbonate in direct contact with the putative microfossils. Collectively, these observations are consistent with an oxidized biomass and provide evidence for biological activity in submarine-hydrothermal environments more than 3,770 million years ago.

Platinum-group element concentrations in pyrite from the Main Sulfide Zone of the Great Dyke of Zimbabwe

NASA Astrophysics Data System (ADS)

Piña, R.; Gervilla, F.; Barnes, S.-J.; Oberthür, T.; Lunar, R.

2016-10-01

The Main Sulfide Zone (MSZ) of the Great Dyke of Zimbabwe hosts the world's second largest resource of platinum-group elements (PGE) after the Bushveld Complex in South Africa. The sulfide assemblage of the MSZ comprises pyrrhotite, pentlandite, chalcopyrite, and minor pyrite. Recently, several studies have observed in a number of Ni-Cu-PGE ore deposits that pyrite may host significant amounts of PGE, particularly Pt and Rh. In this study, we have determined PGE and other trace element contents in pyrite from the Hartley, Ngezi, Unki, and Mimosa mines of the Great Dyke by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Based on the textures and PGE contents, two types of pyrite can be differentiated. Py1 occurs as individual euhedral or subhedral grains or clusters of crystals mostly within chalcopyrite and pentlandite, in some cases in the form of symplectitic intergrowths, and is PGE rich (up to 99 ppm Pt and 61 ppm Rh; 1.7 to 47.1 ppm Ru, 0.1 to 7.8 ppm Os, and 1.2 to 20.2 ppm Ir). Py2 occurs as small individual euhedral or subhedral crystals within pyrrhotite, pentlandite, and less frequently within chalcopyrite and silicates and has low PGE contents (<0.11 ppm Pt, <0.34 ppm Rh, <2.5 ppm Ru, <0.37 ppm Ir, and <0.40 ppm Os). Py1 contains higher Os, Ir, Ru, Rh, and Pt contents than the associated pyrrhotite, pentlandite, and chalcopyrite, whereas Py2 has similar PGE contents as coexisting pyrrhotite and pentlandite. Based on the textural relationships, two different origins are attributed for each pyrite type. Py1 intergrowth with pentlandite and chalcopyrite is inferred to have formed by late, low temperature (<300 °C) decomposition of residual Ni-rich monosulfide solid solution, whereas Py2 is suggested to have formed by replacement of pyrrhotite and pentlandite caused by late magmatic/hydrothermal fluids.

Copper isotope fractionation in acid mine drainage

USGS Publications Warehouse

Kimball, B.E.; Mathur, R.; Dohnalkova, A.C.; Wall, A.J.; Runkel, R.L.; Brantley, S.L.

2009-01-01

We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The ??65Cu values (based on 65Cu/63Cu) of enargite (??65Cu = -0.01 ?? 0.10???; 2??) and chalcopyrite (??65Cu = 0.16 ?? 0.10???) are within the range of reported values for terrestrial primary Cu sulfides (-1??? < ??65Cu < 1???). These mineral samples show lower ??65Cu values than stream waters (1.38??? ??? ??65Cu ??? 1.69???). The average isotopic fractionation (??aq-min = ??65Cuaq - ??65Cumin, where the latter is measured on mineral samples from the field system), equals 1.43 ?? 0.14??? and 1.60 ?? 0.14??? for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in 65Cu relative to chalcopyrite (1.37 ?? 0.14???) and enargite (0.98 ?? 0.14???) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (??aq-mino = - 0.57 ?? 0.14 ???, where mino refers to the starting mineral) and no apparent fractionation for enargite (??aq-mino = 0.14 ?? 0.14 ???). Abiotic fractionation is attributed to preferential oxidation of 65Cu+ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of 65Cuaq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of ??65Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures

Fingerprinting two metal contaminants in streams with Cu isotopes near the Dexing Mine, China.

PubMed

Song, Shiming; Mathur, Ryan; Ruiz, Joaquin; Chen, Dandan; Allin, Nicholas; Guo, Kunyi; Kang, Wenkai

2016-02-15

Transition metal isotope signatures are becoming useful for fingerprinting sources in surface waters. This study explored the use of Cu isotope values to trace dissolved metal contaminants in stream water throughout a watershed affected by mining by-products of the Dexing Mine, the largest porphyry Cu operation in Asia. Cu isotope values of stream water were compared to potential mineral sources of Cu in the mining operation, and to proximity to the known Cu sources. The first mineral source, chalcopyrite, CuFeS2 has a 'tight' cluster of Cu isotope values (-0.15‰ to +1.65‰; +0.37 ± 0.6‰, 1σ, n=10), and the second mineral source, pyrite (FeS2), has a much larger range of Cu isotope values (-4‰ to +11.9‰; 2.7 ± 4.3‰, 1σ, n=16). Dissolved Cu isotope values of stream water indicated metal derived from either chalcopyrite or pyrite. Above known Cu mineralization, stream waters are approximately +1.5‰ greater than the average chalcopyrite and are interpreted as derived from weathering of chalcopyrite. In contrast, dissolved Cu isotope values in stream water emanating from tailings piles had Cu isotope values similar to or greater than pyrite (>+6‰, a common mineral in the tailings). These values are interpreted as sourced from the tailings, even in solutions that possess significantly lower concentrations of Cu (<0.05 ppm). Elevated Cu isotope values were also found in two soil and two tailings samples (δ(65)Cu ranging between +2 to +5‰). These data point to the mineral pyrite in tailings as the mineral source for the elevated Cu isotope values. Therefore, Cu isotope values of waters emanating from a clearly contaminated drainage possess different Cu isotope values, permitting the discrimination of Cu derived from chalcopyrite and pyrite in solution. Data demonstrate the utility of Cu isotopic values in waters, minerals, and soils to fingerprint metallic contamination for environmental problems. Copyright © 2015 Elsevier B.V. All rights reserved.

Numerical modelling of fluid-rock interactions: Lessons learnt from carbonate rocks diagenesis studies

NASA Astrophysics Data System (ADS)

Nader, Fadi; Bachaud, Pierre; Michel, Anthony

2015-04-01

Quantitative assessment of fluid-rock interactions and their impact on carbonate host-rocks has recently become a very attractive research topic within academic and industrial realms. Today, a common operational workflow that aims at predicting the relevant diagenetic processes on the host rocks (i.e. fluid-rock interactions) consists of three main stages: i) constructing a conceptual diagenesis model including inferred preferential fluids pathways; ii) quantifying the resulted diagenetic phases (e.g. depositing cements, dissolved and recrystallized minerals); and iii) numerical modelling of diagenetic processes. Most of the concepts of diagenetic processes operate at the larger, basin-scale, however, the description of the diagenetic phases (products of such processes) and their association with the overall petrophysical evolution of sedimentary rocks remain at reservoir (and even outcrop/ well core) scale. Conceptual models of diagenetic processes are thereafter constructed based on studying surface-exposed rocks and well cores (e.g. petrography, geochemistry, fluid inclusions). We are able to quantify the diagenetic products with various evolving techniques and on varying scales (e.g. point-counting, 2D and 3D image analysis, XRD, micro-CT and pore network models). Geochemical modelling makes use of thermodynamic and kinetic rules as well as data-bases to simulate chemical reactions and fluid-rock interactions. This can be through a 0D model, whereby a certain process is tested (e.g. the likelihood of a certain chemical reaction to operate under specific conditions). Results relate to the fluids and mineral phases involved in the chemical reactions. They could be used as arguments to support or refute proposed outcomes of fluid-rock interactions. Coupling geochemical modelling with transport (reactive transport model; 1D, 2D and 3D) is another possibility, attractive as it provides forward simulations of diagenetic processes and resulting phases. This

Early diagenesis of travertine deposits from the Tibetan Plateau - implications for 230Th/234U dating and palaeoenvironmental reconstruction

NASA Astrophysics Data System (ADS)

Wang, Zhijun; Meyer, Michael; Hoffmann, Dirk; Spötl, Christoph; Aldenderfer, Mark; Sanders, Diethard

2014-05-01

reconstructed for these Tibetan travertine samples with evidence for early diagenetic alteration. In particular the dendritic calcite is known to form under hydrothermal conditions and can thus be regarded as a primary hydrothermal fabric. However, this fabric is preserved as a relict in some samples only, suggestive of widespread early diagenesis. In other samples primary - biologically mediated - calcite precipitation can be inferred from microfabrics; however, recrystallization to mosaic sparite took place soon after deposition for most of them, too. Here we combine detailed petrographic investigations with XRD, microprobe as well as stable isotope analysis and a systematic 230Th/234U dating approach. We show that certain fabrics act as closed system with respect to radiogenic isotopes and are thus suitable for U-series dating. For the majority of fabrics encountered in our Tibetan samples, however, early diagenesis can be inferred and these fabrics also suffer from open-system behavior, hence, require and 'isochron' dating approach. Guidelines are established for identifying early diagenesis in these Tibetan travertine samples and implications for palaeoenvironmental reconstruction are discussed.

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile - Marine sources and diagenetic effects.

PubMed

Lucassen, Friedrich; Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A

2017-01-01

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very

Metallogeny of The Sierra de Guanajuato Range, Central México

NASA Astrophysics Data System (ADS)

Pedro F., Z. D.

2004-12-01

The Sierra de Guanajuato Range (SGR), trending N315° at Central México, is an orographic feature extending over a distance of 80 km. SGR comprises three well defined lithostratigraphic units: (1) a cretaceous basement including an arc-derived terrane named Guanajuato Arc (GA) made of gabbro, diorite and basaltic pillowed lava, and volcano-sedimentary rocks belonging to Arperos fore-arc basin which are geochemically anomalous in Au (0.15 ppm), Ag (3 ppm), Cu (40 ppm), Pb (50 ppm) and Zn (15 ppm); (2) Early Tertiary intrusive rocks, e.g., Comanja Granite which is affected by the presence of tourmalinized (schörl) aplito-pegmatite dykes mineralized with rare earths elements, and (3) Eocene redbeds (1,500-2000 m) and Oligocene-Miocene volcanics cover. The metallogeny of the SGR shows a multiple origin in time and space: volcano-sedimentary, granitic and volcanic, being possible to define three metallogenic epochs: cretaceous, paleocene and oligocene. Cretaceous epoch includes: (a) volcanogenic massive sulphide deposits (VMS) of bimodal-siliclastic type belonging to León-Guanajuato district; wallrock of VMS is made of felsic-internediate volcanics and black argillite; at Los Gavilanes deposit paragenesis is next: chalcopyrite > sphalerite > galena, pyrite > pyrrhotite > marcasite; grade is as follows: Au: .02-.07 g/t; Ag: 157-18.5 g/t; Cu: 2.24-0.81%, Pb: 4.16-0.03%; Zn: 10.35-3.02 %; (b) lens-shaped stratiform bodies of massive pyrite (i. ex., San Ignacio prospect; ˜ 4,000 ton) of exhalative-sedimentary origin with chalcopyrite and sphalerite microveins. Paleocene epoch includes both quartz-cordierite-sanidine veins and replacement bodies of hydrothermal metamorphic filliation (W +Se-Bi, Pb, Zn, Cu), and pyrometasomatic bodies [Cu, Pb, Zn (Ag), W] which genetically are linked to Comanja Granite emplacement. The wallrock at El Maguey mine (35,000 ton; 0.6% WO3) is made of hornfel and the vein (1.8-3.2m width) has a banding structure made of : \\{quartz & K

Effect of p–d hybridization, structural distortion and cation electronegativity on electronic properties of ZnSnX{sub 2} (X=P, As, Sb) chalcopyrite semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mishra, S.; Ganguli, B., E-mail: biplabg@nitrkl.ac.in

2013-04-15

Significant effects of p–d hybridization, structural distortion and cation-electro-negativity are found on band gap in ZnSnX{sub 2} (X=P, As, Sb). Our study suggests these compounds to be direct band gap semiconductors with band gaps of 1.23, 0.68 and 0.19 eV respectively. Lattice constants, tetragonal distortion (η), anion displacement, bond lengths and bulk moduli are calculated by Density Functional Theory based on Tight binding Linear Muffin-Tin orbital method. Our result of structural properties is in good agreement with the available experimental and other theoretical results. Calculated band gaps also agree well with the experimental works within LDA limitation. Unlike other semiconductorsmore » in the group II–IV–V{sub 2}, there is a reduction in the band gap of 0.22, 0.20 and 0.24 eV respectively in ZnSnX{sub 2} (X=P, As, Sb) due to p–d hybridization. Structural distortion decreases band gap by 0.20, 0.12 and 0.10 eV respectively. We find that cation electronegativity effect is responsible for increasing the band gap relative to their binary analogs GaInP{sub 2}, InGaAs{sub 2} and GaInSb{sub 2} respectively and increment are 0.13, 0.04 and 0.13 eV respectively. - Graphical abstract: One unit cell of ZnSnX{sub 2} (X=P, As, Sb) chalcopyrite semiconductor. Semiconductors ZnSnX{sub 2} (X=P, As, Sb) are found to be direct band gap semiconductors with band gaps 1.23, 0.68 and 0.19 eV respectively. The quantitative estimate of effects of p–d hybridization, structural distortion and cation electronegativity shows band gaps change significantly due to these effects. Highlights: ► ZnSnX{sub 2} (X=P, As, Sb) are direct band gap semiconductors. ► These have band gaps of 1.23 eV, 0.68 eV and 0.19 eV respectively. ► The band gap reduction due to p–d hybridization is 13.41%, 18.51% and 40% respectively. ► Band gap reduction due to structural distortion is 12.12%, 11.11% and 16.66% respectively. ► Band gap increases 8.38%, 3.70% and 21

Iron and Sulfur Species and Sulfur Isotopic Compositions of Authigenic Pyrite in Gas Hydrate-Bearing Sediments from Hydrate Ridge, Cascadia Margin (ODP Leg 204): A Proposal of Conceptual Models to Indicate the Non-Steady State Depositional and Diagenetic Processes

NASA Astrophysics Data System (ADS)

Liu, C.; Jiang, S. Y.; Su, X.

2017-12-01

Two accretionary sediment sequences from Sites 1245 and 1252 recovered during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge, Cascadia Margin were investigated to explore the non-steady state depositional and diagenetic history. Five iron species and three sulfur species were chemically extracted, and their concentrations and the sulfur isotopic compositions of pyrite were determined. After the mineral recognitions of these species and detailed comparative analyses, the aerobic history of bottom seawater has been determined. The formation of pyrite is thought to be controlled by the limited production of hydrogen sulfide relative to the supply of reactive iron. Also, the intrusion of oxygen by bioturbation would oxidize the reduced sulfur species and further suppress pyritization. To explain the geochemical relationship between pyrite and siderite and the sulfur isotope characteristics of pyrite, we propose seven conceptual models based on the variations in depositional rate and methane flux, and the models succeed in explaining the geochemical results and are validated by the observed non-steady state events. These models may contribute to the reconstruction of the non-steady state processes in other research areas in the future.

Chemical variations observed on Aeolis Mons in Gale Crater, Mars

NASA Astrophysics Data System (ADS)

Frydenvang, Jens; Gasda, Patrick J.; Thompson, Lucy; Hurowitz, Joel; Grotzinger, John P.; Blaney, Diana L.; Gellert, Ralf; Wiens, Roger; Vasavada, Ashwin R.; MSL Science Team

2016-10-01

The extraordinarily extensive exposure of hematite-, clay-, sulfate-bearing stratigraphic layers in the lower part of Aeolis Mons was the primary reason Gale Crater was selected as the landing site for the Mars Science Laboratory rover, Curiosity. 753 martian solar days (sols) after the Curiosity rover landed in Gale Crater in August 2012, and after driving more than 9 km, the Curiosity rover arrived at the first exposure of the Murray formation, the basal layer of Aeolis Mons. The Murray formation is a thinly laminated lacustrine mudstone showing stratification down to the millimeter scale. This supports the idea that the stratigraphic layers of Aeolis Mons are sedimentary, and likely deposited in a series of long-lived lakes extending into the early Hesperian time, as recently described by Grotzinger et al. (Science, vol. 350, 2015). The chemical variations observed throughout the Murray formation by the ChemCam and APXS instruments in the 600+ sols since first arriving at Aeolis Mons will be presented. While Murray remains thinly laminated throughout the 30+ vertical meters of stratigraphy explored, large chemical variations are observed. The most extreme variations arise from likely co-located detrital and diagenetic silica enrichments in Murray. Remarkably, an associated diagenetic silica enrichment is also observed in the unconformably overlying eolian sandstone of the Stimson formation in that location. The detrital enrichment provides evidence of how the source region chemistry varied as the sedimentary layers of Aeolis Mons were deposited. Conversely, the diagenetic enrichment observed across both the Murray and Stimson formations provides compelling evidence for the presence of subsurface fluids in Gale Crater, thousands to millions of years after the crater lakes disappeared. This evidence of liquid water greatly extends the timescale in which Gale Crater might have been habitable.

3D-Mapping of Dolomitized Structures in Lower Cambrian Phosphorites

NASA Astrophysics Data System (ADS)

Hippler, Dorothee; Stammeier, Jessica A.; Brunner, Roland; Rosc, Jördis; Franz, Gerhard; Dietzel, Martin

2016-04-01

Dolomitization is a widespread phenomenon in ancient sedimentary rocks, particularly close to the Precambrian-Cambrian boundary. Dolomite can form in synsedimentary or hydrothermal environments, preferentially via the replacement of solid carbonate precursor phases. Synsedimentary dolomite formation is often associated with microbial activity, such as bacterial sulfate reduction or methanogenesis. In this study, we investigate dolomitic phosphorites from the Lowermost Cambrian Tal Group, Mussoori Syncline, Lesser Himalaya, India, using micro-CT 3D-mapping, in order to unravel the complex diagenetic history of the rocks. The selected sample shows alternating layering of phosphatic mudstones and sparitic dolostone, in which brecciated layers of phosphorite or phosphatic mudstones are immersed in a dolomite-rich matrix. Lamination occurs on a sub-millimetre scale, with lamination sometimes wavy to crinkly. This fabric is interpreted as former microbial mats, providing the environment for early diagenetic phosphatization. Preliminary electron backscatter imaging with scanning microscopy revealed that dolomite crystals often occur in spherical to ellipsoidal structures, typically with a high porosity. This dolomite is associated with botryoidal apatite, organic matter and small amounts of calcite. Micro-CT 3D-mappings reveal that dolomite structures are cigar-shaped, elongated and up to 600 μm long. They are further arranged in a Mikado-like oriented framework spanning a layer thickness of a few millimetres. Analyses of ambient pore space, with similar elongated outlines and filled with organic matter, suggest a potential coherence of ambient pore space and shape of the dolomite structures. Allowing for other associated mineral phases, such as pyrite and silicates, and their spatial distribution, the present approach can be used to unravel distinct diagenetic reaction pathways, and might thus constrain the proxy potential of these Lower Cambrian dolomitic phosphorites

The occurrence and origin of celestite in the Abolfares region, Iran: Implications for Sr-mineralization in Zagros fold belt (ZFB)

NASA Astrophysics Data System (ADS)

Pourkaseb, Houshang; Zarasvandi, Alireza; Rezaei, Mohsen; Mahdavi, Reyhaneh; Ghanavati, Fatemeh

2017-10-01

The major celestite deposits in Zagros Fold belt are associated with coastal marine carbonate and evaporate sediments of Oligo-Miocene Asmari and Lower Miocene Ghachsaran Formations. In the Abolfares region, celestite mineralization is extended in the western limb of Bangestan anticline in the carbonates of Early Miocene (middle part of Asmari Formation), underlying by dolomitic carbonates of Burdigalian. From bottom to top three main types of mineralization can be distinguished in the study area: (1) layer texture resulting from replacement of algal limestone by celestite minerals with some parts showing idiomorphic crystals (geodes) along the walls of the cavities, (2) celestite occurrence as irregular massive shape interconnected small crystals and nodules, and (3) celestite mineralization associated with steeply dipping veins and open space fracture fillings, resulting from late-stage epigenetic processes. Highlightly, the ore-hosting carbonate rocks were deposited in an intertidal - supratidal protected setting with hypersaline conditions, in accordance with other celestite deposits of the Zagros Fold belt. The abundance of diagenetic crystallization rhythmites, carbonate and anhydrite inclusions as confirmed by Laser Raman spectroscopy analysis, high Sr/Ba values (average; 8726.1) and strong negative correlations between SO3 vs CaO (R2 = 0.98), SrO vs CaO (R2 = 0.96) with positive correlations between Ba vs SrO (R2 = 0.54) and SO3 vs SrO (R2 = 0.98) highlight the role of high Sr late-diagenetic brines in replacement of carbonates with celestite minerals. It seems that the inception of compressional folding during or soon after the deposition of the Asmari Formation in the carbonate platform at the margin of NW-trending basin in the foreland of the Zagros orogenic belt lead to the upward refluxing of penetrated high-Sr diagenetic brines and celestite mineralization.

The Ree and ɛNd of 40-70 Ma old fish debris from the west-African platform

NASA Astrophysics Data System (ADS)

Grandjean, Patricia; Cappetta, Henri; Albarède, Francis

1988-04-01

REE concentrations and Nd isotopic compositions have been determined in Late Cretaceous-Early Cenozoic fish debris from West African and Israeli platform sediments and show a strong regional control independent of time, except for those from the Northern Morocco. It is suggested that, although diagenetic fluids do not contribute REE's directly to the phosphatic debris, they may significantly change the Ce anomaly and the ɛNd(T) value of the epicontinental seas, which, in turn, control the REE in marine phosphates. It is shown that, over the investigated period, the North Moroccan shelf seawater was progressively flushed by deep North-Atlantic water.

Reliable wet-chemical cleaning of natively oxidized high-efficiency Cu(In,Ga)Se{sub 2} thin-film solar cell absorbers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lehmann, Jascha; Potsdam Institute for Climate Impact Research; Lehmann, Sebastian, E-mail: sebastian.lehmann@ftf.lth.se

2014-12-21

Currently, Cu-containing chalcopyrite-based solar cells provide the highest conversion efficiencies among all thin-film photovoltaic (PV) technologies. They have reached efficiency values above 20%, the same performance level as multi-crystalline silicon-wafer technology that dominates the commercial PV market. Chalcopyrite thin-film heterostructures consist of a layer stack with a variety of interfaces between different materials. It is the chalcopyrite/buffer region (forming the p-n junction), which is of crucial importance and therefore frequently investigated using surface and interface science tools, such as photoelectron spectroscopy and scanning probe microscopy. To ensure comparability and validity of the results, a general preparation guide for “realistic” surfacesmore » of polycrystalline chalcopyrite thin films is highly desirable. We present results on wet-chemical cleaning procedures of polycrystalline Cu(In{sub 1-x}Ga{sub x})Se{sub 2} thin films with an average x = [Ga]/([In] + [Ga]) = 0.29, which were exposed to ambient conditions for different times. The hence natively oxidized sample surfaces were etched in KCN- or NH{sub 3}-based aqueous solutions. By x-ray photoelectron spectroscopy, we find that the KCN treatment results in a chemical surface structure which is – apart from a slight change in surface composition – identical to a pristine as-received sample surface. Additionally, we discover a different oxidation behavior of In and Ga, in agreement with thermodynamic reference data, and we find indications for the segregation and removal of copper selenide surface phases from the polycrystalline material.« less

Mesozoic clay diagenesis in the Appalachian Plateau

NASA Astrophysics Data System (ADS)

Boles, A.; Mulch, A.; van der Pluijm, B.

2017-12-01

Integrated investigation of authigenic clays in the Appalachian Plateau of the northeastern US Midcontinent using X-ray goniometry, Rietveld-method based illite polytype analysis, and 40Ar/39Ar geochronology yields novel insights about the structural diagenetic history of the North American sedimentary cover sequence. Texture analysis by High Resolution X-ray Texture Goniometry records the presence of a bedding-parallel diagenetic fabric, corresponding to a burial depth of 2-5 km. New development of polytype modeling using BGMN®, a quantitative X-ray powder diffraction forward modeling and whole-pattern matching program matches mineralic characteristic of illite at those depths and reduces uncertainty estimates in age analysis. Based on dating size fractions, the diagenetic age is constrained to 225-250 Ma (Triassic) by four authigenic illite samples, reflecting protracted, regional diagenesis in the area. Preliminary H isotopic analysis points to a surface-derived diagenetic fluid with δD values ranging from -48 to -72‰ (in the range of predicted Pangea meteoric fluid), with a dependence on proximity to the Appalachian Mountains that may reflect a rain shadow effect.

Mineralized breccia clasts: a window into hidden porphyry-type mineralization underlying the epithermal polymetallic deposit of Cerro de Pasco (Peru)

NASA Astrophysics Data System (ADS)

Rottier, Bertrand; Kouzmanov, Kalin; Casanova, Vincent; Bouvier, Anne-Sophie; Baumgartner, Lukas P.; Wälle, Markus; Fontboté, Lluís

2018-01-01

Cerro de Pasco (Peru) is known for its large epithermal polymetallic (Zn-Pb-Ag-Cu-Bi) mineralization emplaced at shallow level, a few hundred meters below the paleo-surface, at the border of a large diatreme-dome complex. Porphyry-style veins crosscutting hornfels and magmatic rock clasts are found in the diatreme breccia and in quartz-monzonite porphyry dikes. Such mineralized veins in clasts allow investigation of high-temperature porphyry-style mineralization developed in the deep portions of magmatic-hydrothermal systems. Quartz in porphyry-style veins contains silicate melt inclusions as well as fluid and solid mineral inclusions. Two types of high-temperature (> 600 °C) quartz-molybdenite-(chalcopyrite)-(pyrite) veins are found in the clasts. Early, thin (1-2 mm), and sinuous HT1 veins are crosscut by slightly thicker (up to 2 cm) and more regular HT2 veins. The HT1 vein quartz hosts CO2- and sulfur-rich high-density vapor inclusions. Two subtypes of the HT1 veins have been defined, based on the nature of mineral inclusions hosted in quartz: (i) HT1bt veins with inclusions of K-feldspar, biotite, rutile, and minor titanite and (ii) HT1px veins with inclusions of actinolite, augite, titanite, apatite, and minor rutile. Using an emplacement depth of the veins of between 2 and 3 km (500 to 800 bar), derived from the diatreme breccia architecture and the supposed erosion preceding the diatreme formation, multiple mineral thermobarometers are applied. The data indicate that HT1 veins were formed at temperatures > 700 °C. HT2 veins host assemblages of polyphase brine inclusions, generally coexisting with low-density vapor-rich inclusions, trapped at temperatures around 600 °C. Rhyolitic silicate melt inclusions found in both HT1 and HT2 veins represent melt droplets transported by the ascending hydrothermal fluids. LA-ICP-MS analyses reveal a chemical evolution coherent with the crystallization of an evolved rhyolitic melt. Quartz from both HT1 and HT2 veins

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile – Marine sources and diagenetic effects

PubMed Central

Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A.

2017-01-01

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very

Pore network properties of sandstones in a fault damage zone

NASA Astrophysics Data System (ADS)

Bossennec, Claire; Géraud, Yves; Moretti, Isabelle; Mattioni, Luca; Stemmelen, Didier

2018-05-01

The understanding of fluid flow in faulted sandstones is based on a wide range of techniques. These depend on the multi-method determination of petrological and structural features, porous network properties and both spatial and temporal variations and interactions of these features. The question of the multi-parameter analysis on fluid flow controlling properties is addressed for an outcrop damage zone in the hanging wall of a normal fault zone on the western border of the Upper Rhine Graben, affecting the Buntsandstein Group (Early Triassic). Diagenetic processes may alter the original pore type and geometry in fractured and faulted sandstones. Therefore, these may control the ultimate porosity and permeability of the damage zone. The classical model of evolution of hydraulic properties with distance from the major fault core is nuanced here. The hydraulic behavior of the rock media is better described by a pluri-scale model including: 1) The grain scale, where the hydraulic properties are controlled by sedimentary features, the distance from the fracture, and the impact of diagenetic processes. These result in the ultimate porous network characteristics observed. 2) A larger scale, where the structural position and characteristics (density, connectivity) of the fracture corridors are strongly correlated with both geo-mechanical and hydraulic properties within the damage zone.

Mesozoic (Lower Jurassic) red stromatactis limestones from the Southern Alps (Arzo, Switzerland): calcite mineral authigenesis and syneresis-type deformation

NASA Astrophysics Data System (ADS)

Neuweiler, Fritz; Bernoulli, Daniel

2005-02-01

The Broccatello lithological unit (Lower Jurassic, Hettangian to lower parts of Upper Sinemurian) near the village of Arzo (southern Alps, southern Switzerland) is a mound-shaped carbonate deposit that contains patches of red stromatactis limestone. Within the largely bioclastic Broccatello unit, the stromatactis limestone is distinguished by its early-diagenetic cavity system, a relatively fine-grained texture, and an in-situ assemblage of calcified siliceous sponges (various demosponges and hexactinellids). A complex shallow subsurface diagenetic pathway can be reconstructed from sediment petrography in combination with comparative geochemical analysis (carbon and oxygen isotopes; trace and rare earth elements, REE + Y). This pathway includes organic matter transformation, aragonite and skeletal opal dissolution, patchy calcification and lithification, sediment shrinkage, sagging and collapse, partial REE remobilization, and multiple sediment infiltration. These processes occurred under normal-marine, essentially oxic conditions and were independent from local, recurring syn-sedimentary faulting. It is concluded that the stromatactis results from a combination of calcite mineral authigenesis and syneresis-type deformation. The natural stromatactis phenomenon may thus be best explained by maturation processes of particulate polymer gels expected to form in fine-grained carbonate sediments in the shallow subsurface. Conditions favorable for the evolution of stromatactis appear to be particularly frequent during drowning of tropical or subtropical carbonate platforms.

Influence of lithofacies and diagensis on Norwegian North Sea chalk reservoirs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brasher, J.E.; Vagle, K.R.

1996-05-01

The depositional mechanism of chalk is a key influence in the chalk`s ultimate reservoir quality. Classically, the depositional mechanism is interpreted from core descriptions. Where core data are lacking, dipmeter and borehole imagery logs have proven useful in making lithofacies assessments. Criteria for recognition of three chalk categories are established. Category III chalks correspond to those chalks that have been deposited by gravity flows or slumping and tend to have the best reservoir parameters. Category I chalks are most often affiliated with pelagic deposition and tend to have the poorest reservoir parameters. Category II chalks are intermediate between I andmore » III. Anomalously high primary porosities have been maintained in Norwegian North Sea chalks where the effects of mechanical and chemical compaction have been limited. The diagenetic pathway of a chalk reflects changes brought about by mechanical and chemical compaction. Five factors most heavily influence the diagenetic pathway: (1) burial depth, (2) chalk type, (3) overpressuring, (4) presence of hydrocarbons, and (5) original grain size. Assessments of the sedimentological model, diagenetic pathway, and resultant reservoir quality are provided in case studies of Edda, Tor, and Eldfisk fields. Because the distribution of chalk is largely independent of existing structures, most fields have a component of stratigraphic/diagenetic trapping. Each case study shows unique examples of how petrophysical and reservoir engineering data can be incorporated in assessments of chalk type and the diagenetic pathway and how they may affect reservoir parameters and productivity.« less

Hydrothermal Evolution of the Giant Cenozoic Kadjaran porphyry Cu-Mo deposit, Tethyan metallogenic belt, Armenia, Lesser Caucasus: mineral paragenetic, cathodoluminescence and fluid inclusion constraints

NASA Astrophysics Data System (ADS)

Hovakimyan, Samvel; Moritz, Robert; Tayan, Rodrik; Rezeau, Hervé

2016-04-01

stockwork. One of them is the east-west-oriented 6th vein zone in the northern part of the deposit, which contains quartz-molybdenite veins and late quartz-galena-sphalerite veins. This is interpreted as a telescoping between porphyry and epithermal environments. It is supported by microscopic studies of mineral paragenesis, which reveal the presence of enargite and tennantite-tetrahedrite, luzonite, sphalerite, and galena, generally in a gangue of quartz, followed by a late carbonate and gypsum stage. On-going fluid inclusion studies are being carried out on quartz samples from the different mineralization stages. Five types of fluid inclusions were distinguished according to their nature, bubble size, and daughter mineral content: vapor-rich, aqueous-carbonic, brine, polyphase brine and liquid-rich inclusions. Cathodoluminescence images from the porphyry veins reveal four generations of quartz. Molybdenite and chalcopyrite are associated with two different dark luminescent quartz generations, which contain typical brine, aqueous-carbonic and vapour-rich H2O fluid inclusions, with some of them coexisting locally as boiling assemblages. Epithermal veins are mainly characterized by liquid-rich H2O fluid inclusions. Microthermometric studies of fluid inclusions reveal a major difference in homogenisation temperatures between the early quartz-molybdenite- chalcopyrite stage (Thtotal between 3600 and 4250C) and the late quartz-galena-sphalerite vein stage (Thtotal 300-2700C), which is attributed to the transition from a porphyry to an epithermal environment in the Kadjaran deposit.

Strata-bound Fe-Co-Cu-Au-Bi-Y-REE deposits of the Idaho Cobalt Belt: Multistage hydrothermal mineralization in a magmatic-related iron oxide copper-gold system

USGS Publications Warehouse

Slack, John F.

2012-01-01

, consistent with the general lack of abundant chalcopyrite in cobaltite-rich samples.Paragenetic relations determined by scanning electron microscopy indicate that the earliest Y-REE-Be mineralization preceded deposition of Co, Cu, Au, and Bi. Allanite, xenotime, and gadolinite-(Y) commonly occur as intergrowths with and inclusions in cobaltite; the opposite texture is rare. Monazite, in contrast, forms a poikiloblastic matrix to cobaltite and thin rims on allanite and xenotime, reflecting a later metamorphic paragenesis. Allanite and xenotime also show evidence of late dissolution and reprecipitation, forming discordant rims on older anhedral allanite and xenotime and separate euhedral crystals of each mineral. Textural data suggest extensive deformation of the deposits by folding and shearing, and by pervasive recrystallization, all during Cretaceous metamorphism. Sensitive high resolution ion microprobe U-Pb geochronology by Aleinikoff et al. (2012) supports these paragenetic interpretations, documenting contemporaneous Mesoproterozoic growth of early xenotime and crystallization of megacrystic A-type granite on the northern border of the district. These ages are used together with mineralogical and geochemical data from the present study to support an epigenetic, IOCG model for Fe-Co-Cu-Au-Bi-Y-REE deposits of the Idaho cobalt belt. A sulfide facies variant of IOCG deposits is proposed for the Blackbird district, in which reducing hydrothermal conditions favored deposition of sulfide minerals over iron oxides. This new model includes Mesoproterozoic vein mineralization and related Fe-Cl metasomatism that formed the biotite-rich lenses, a predominantly felsic magmatic source for metals in the deposits, given their local abundance of Y, REEs, and Be, and a major sedimentary component in the hydrothermal fluids based on independent sulfur isotope and boron isotope data for sulfides and ore-related tourmaline, respectively.

Understanding Copper Isotope Behavior in the High Temperature Magmatic-Hydrothermal Porphyry Environment

NASA Astrophysics Data System (ADS)

Gregory, Melissa J.; Mathur, Ryan

2017-11-01

Copper stable isotope geochemistry has the potential to constrain aspects of ore deposit formation once variations in the isotopic data can be related to the physiochemical conditions during metal deposition. This study presents Cu isotope ratios for samples from the Pebble porphyry Cu-Au-Mo deposit in Alaska. The δ65Cu values for hypogene copper sulfides range from -2.09‰ to 1.11‰ and show linear correlations with the δ18O isotope ratios calculated for the fluid in equilibrium with the hydrothermal alteration minerals in each sample. Samples with sodic-potassic, potassic, and illite alteration display a negative linear correlation between the Cu and O isotope results. This suggests that fractionation of Cu isotopes between the fluid and precipitating chalcopyrite is positive as the hydrothermal fluid is evolving from magmatic to mixed magmatic-meteoric compositions. Samples with advanced argillic alteration display a weak positive linear correlation between Cu and O isotope results consistent with small negative fluid-chalcopyrite Cu isotope fractionation during fluid evolution. The hydrothermal fluids that formed sodic-potassic, potassic, and illite alteration likely transported Cu as CuHS0. Hydrothermal fluids that resulted in advanced argillic alteration likely transport Cu as CuCl2-. The pH conditions also control Cu isotope fractionation, consistent with previous experimental work. Larger fractionation factors were found between fluids and chalcopyrite precipitating under neutral conditions contrasting with small fractionation factors calculated between fluids and chalcopyrite precipitating under acidic conditions. Therefore, this study proposes that hydrothermal fluid compositions and pH conditions are related to Cu isotope variations in high temperature magmatic-hydrothermal deposits.

Aqueous Solution-Phase Selenized CuIn(S,Se)2 Thin Film Solar Cells Annealed under Inert Atmosphere.

PubMed

Oh, Yunjung; Yang, Wooseok; Kim, Jimin; Woo, Kyoohee; Moon, Jooho

2015-10-14

A nonvacuum solution-based approach can potentially be used to realize low cost, roll-to-roll fabrication of chalcopyrite CuIn(S,Se)2 (CISSe) thin film solar cells. However, most solution-based fabrication methods involve highly toxic solvents and inevitably require sulfurization and/or postselenization with hazardous H2S/H2Se gases. Herein, we introduce novel aqueous-based Cu-In-S and Se inks that contain an amine additive for producing a high-quality absorber layer. CISSe films were fabricated by simple deposition of Cu-In-S ink and Se ink followed by annealing under an inert atmosphere. Compositional and phase analyses confirmed that our simple aqueous ink-based method facilitated in-site selenization of the CIS layer. In addition, we investigated the molecular structures of our aqueous inks to determine how crystalline chalcopyrite absorber layers developed without sulfurization and/or postselenization. CISSe thin film solar cells annealed at 550 °C exhibited an efficiency of 4.55% under AM 1.5 illumination. The low-cost, nonvacuum method to deposit chalcopyrite absorber layers described here allows for safe and simple processing of thin film solar cells.

Vendian microfossils in metasedimentary cherts of the Scotia Group, Prins Karls Forland, Svalbard

NASA Technical Reports Server (NTRS)

Knoll, A. H.

1992-01-01

Sedimentary rocks of the Scotia Group, Prins Karls Forland, Svalbard, have been metamorphosed to lower greenschist facies. Yet Scotia chert nodules contain abundant organic-walled microfossils belonging to at least seventeen taxa. Their black colour indicates that the fossils underwent substantial thermal alteration. However, it is suggested that preservation in a matrix of early diagenetic silica shielded them from the most destructive mechanical and chemical effects of metamorphism. Microbial mats and large acanthomorphic acritarchs suggest a coastal marine depositional environment; the acritarchs further indicate an early Vendian age for the sediments. The Scotia fossils bear a close resemblance to assemblages described from the Doushantuo Formation, China and elsewhere, demonstrating the broad geographical distribution of biostratigraphically important Vendian taxa. Briareus and Echinosphaeridium are described as new genera; Briareus borealis is described as a new species, while Echinosphaeridium maximum is proposed as a new combination.

Illitization and paleothermal regimes in the Middle Ordovician St. Peter Sandstone, Central Michigan Basin: K-Ar, Oxygen Isotope, and fluid inclusion data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Girard, J.P.; Barnes, D.A.

1995-01-01

Hydrocarbon reservoirs occur in the Middle Ordovician St. Peter Sandstone in the central Michigan basin at depths of 1.5-3.5 km and are diagenetically altered. Latest diagenetic cements include saddle dolomite, pervasive microcrystalline illite and chlorite, and quartz. A K-Ar and {sup 18}O/{sup 16}O study of the fine-grained authigenic illite in 25 samples from 16 wells covering a large area within the basin yields K-Ar ages ranging from 367 to 322 Ma and {delta}{sup 18}O values between 12.7 and 16.9% SMOW. The {delta}{sup 18}O values of diagenetic quartz overgrowths range from 15.2 to 18.9%. Fluid inclusion temperatures in the quartz cementmore » range from 70 to 170{degrees}C, reflecting multiple generations of diagenetic quartz and/or precipitation over most of the diagenetic history. Reequilibrated fluid inclusions in the saddle dolomite cement yield temperatures ranging from 90 to 150{degrees}C. A regionally significant episode of illitization occurred during the Late Devonian-Mississipian. Temperatures of illite formation are indirectly estimated to be in the range of 125-170{degrees}C and most paleodepths of illitization are between 2.8 and 3.2 km. These results imply that (1) illite formed from {sup 18}O-rich fluids, and (2) elevated geothermal gradients, i.e., greater than 34% C/km, existed in the Michigan basin in the late Paleozoic. The K-Ar ages and the {delta}{sup 18}O values are not correlated to present depths of the samples or paleodepths of illitization. Illites with young ages and low {delta}{sup 18}O values tend to be geographically distributed along the north-south branch of the buried Precambrian rift. The {delta}{sup 18}O values of the diagenetic quartz follow a similar trend. The spread of illite K-Ar ages and {delta}{sup 19}O values, and their geographic distribution, are best explained as reflecting abnormally high thermal regimes in the part of the basin located above the presumably highly fractured basement along the rift.« less

Characteristics and 40Ar/39Ar geochronology of the Erdenet Cu-Mo deposit, Mongolia

USGS Publications Warehouse

Kavalieris, Imants; Khashgerel, Bat-Erdene; Morgan, Leah; Undrakhtamir, Alexander; Borohul, Adiya

2017-01-01

The Early to Middle Triassic Erdenet porphyry Cu-Mo deposit, in northern Mongolia, developed in a continent-continent arc collision zone, within the Central Asian orogenic belt. The porphyry system is related to multiple intrusions of crystal-crowded biotite granodiorite porphyry, which formed a composite stock about 900 m in diameter, with multiple porphyritic microgranodiorite dikes. Wall rocks are Late Permian to Early Triassic, medium-grained granodiorite, with similar whole-rock geochemistry, mineralogy, and composition to the granodiorite porphyry. Whole-rock analysis of the granodiorite porphyry and wall rocks shows that these rocks cannot be discriminated, but both have depleted middle heavy rare earth elements and Y, typical of fertile porphyry magmatic suites.At the current pit level (1,250 m elev), early porphyry-style quartz veins (A and B type) are locally infilled by pyrite-chalcopyrite, with subordinate bornite, but most of the chalcopyrite occurs in D veins that constitute more than 50% of the Cu grade (~0.5 wt % Cu). The 0.3 wt % Cu shell resembles a molar tooth, enveloping the granodiorite porphyry, with deeper roots extending down the wal-rock contacts. Molybdenite occurs in monomineralic veins, and in finely laminated to massive quartz-molybdenite veins.The most important alteration is quartz-muscovite, which occurs as relatively coarse (100–500 μm) alteration selvages (1–5 cm) that envelop D veins. The D veins cut illite ± kaolinite-smectite (or intermediate argillic) alteration. Intermediate argillic alteration, together with abundant pink anhydrite (commonly hydrated to gypsum), extends from at least 1,300- to 900-m elevation in the deepest drill holes, and has overprinted early potassic alteration, or relatively unaltered red granodiorite. Meter-wide zones of kaolinite cut the anhydrite-gypsum at all levels. There is an abrupt transition outward from the intermediate argillic alteration to chlorite-epidote (propylitic) alteration, at

Temporal changes in Ce-anomalies in biogenic apatite from the Upper Cretaceous-Lower Eocene phosphate beds of Morocco. Is there a link to global paleoceanography?

NASA Astrophysics Data System (ADS)

Kocsis, L.; Gheerbrant, E.; Mouflih, M.; Cappetta, H.; Ulianov, A.

2012-12-01

Shallow marine phosphorites are widespread along the western coast of Morocco. These sediments were deposited in three, first order transgressive-regressive cycles during the late Cretaceous-early Eocene. The layers are exceptionally rich in marine vertebrate fossils and three periods - Maastrichtian, Danian-Thanetian and Ypresian - can be distinguished by the especially abundant selachian fauna. A comprehensive geochemical study is carried out on these biogenic apatite fossils, and here we present trace element data analyzed on enameloid and dentin of shark teeth, coprolites, and bones coming from the Ouled Abdoun and Ganntour Basins. A clear separation is apparent between enameloid and the other archives in terms of the former has lower Cu, Ba, rare earth elements (REE) and U, and higher Zn and Sr concentrations. The REE and U in phosphatic fossils originate almost entirely from early diagenetic pore fluid and thus they can be used as a fingerprint of burial conditions. The above observed differences in the trace element concentrations relate to the originally different structure of these fossils, which means the better crystallized and denser enameloid interacted less with the burial fluid than the other remains. All the fossils revealed very similar shale normalized REE patterns, with negative Ce-anomaly and heavy REE enrichment, which mimics the REE distribution of typical modern seawater. This would indicate that the early diagenetic pore fluid was dominated by seawater, when these fossils gained their REE composition. However, the patterns show small differences with lower La/Sm, and higher La/Yb and Sm/Yb ratios in the coprolites, dentine and bones, which would appear as slight flattening of the patterns on the heavy REE end. This signifies again that these latter archives are more susceptible to interaction with the pore fluid. In contrast, the Ce-anomaly does not vary among the different remains and the values are very similar in a given layer. However

Compositions, ages, and diagenetic histories of the carbonate, sulfide, oxide, and phosphatic concretions at Gay Head, Massachusetts

USGS Publications Warehouse

Poppe, L.J.; Commeau, R.F.; O'Leary, Dennis W.

1988-01-01

The calcite/ankerite concretions were formed in a hot, seasonally arid, caliche-prone environment of early Raritan age; the pyrite, marcasite, and siderite concretions precipitated in sediments deposited in low-energy, marshy, estuarine environments of late Raritan age. The phosphate concretions formed in a middle to inner shelf environment. The goethite and lepidocrocite concretions are secondary oxidation or alteration products of the prexistent Cretaceous concretions that were excavated during the Pleistocene and incorporated into the glacial drift. -from Authors

The magnesium isotope (δ26Mg) signature of dolomites

NASA Astrophysics Data System (ADS)

Geske, A.; Goldstein, R. H.; Mavromatis, V.; Richter, D. K.; Buhl, D.; Kluge, T.; John, C. M.; Immenhauser, A.

2015-01-01

Dolomite precipitation models and kinetics are debated and complicated due to the complex and temporally fluctuating fluid chemistry and different diagenetic environments. Using well-established isotope systems (δ18O, δ13C, 87Sr/86Sr), fluid inclusions and elemental data, as well as a detailed sedimentological and petrographic data set, we established the precipitation environment and subsequent diagenetic pathways of a series of Proterozoic to Pleistocene syn-depositional marine evaporative (sabkha) dolomites, syn-depositional non-marine evaporative (lacustrine and palustrine) dolomites, altered marine ("mixing zone") dolomites and late diagenetic hydrothermal dolomites. These data form the prerequisite for a systematic investigation of dolomite magnesium isotope ratios (δ26Mgdol). Dolomite δ26Mg ratios documented here range, from -2.49‰ to -0.45‰ (δ26Mgmean = -1.75 ± 1.08‰, n = 42). The isotopically most depleted end member is represented by earliest diagenetic marine evaporative sabkha dolomites (-2.11 ± 0.54‰ 2σ, n = 14). In comparing ancient compositions to modern ones, some of the variation is probably due to alteration. Altered marine (-1.41 ± 0.64‰ 2σ, n = 4), and earliest diagenetic lacustrine and palustrine dolomites (-1.25 ± 0.86‰ 2σ, n = 14) are less negative than sabkha dolomites but not distinct in composition. Various hydrothermal dolomites are characterized by a comparatively wide range of δ26Mg ratios, with values of -1.44 ± 1.33‰ (2σ, n = 10). By using fluid inclusion data and clumped isotope thermometry (Δ47) to represent temperature of precipitation for hydrothermal dolomites, there is no correlation between fluid temperature (∼100 to 180 °C) and dolomite Mg isotope signature (R2 = 0.14); nor is there a correlation between δ26Mgdol and δ18Odol. Magnesium-isotope values of different dolomite types are affected by a complex array of different Mg sources and sinks, dissolution/precipitation and non

Analysis and Characterization of Organic Carbon in Early Holocene Wetland Paleosols using Ramped Pyrolysis 14C and Biomarkers

NASA Astrophysics Data System (ADS)

Vetter, L.; Schreiner, K. M.; Fernandez, A.; Rosenheim, B. E.; Tornqvist, T. E.

2014-12-01

Radiocarbon analyses are a key tool for quantifying the dynamics of carbon cycling and storage in both modern soils and Quaternary paleosols. Frequently, bulk 14C dates of paleosol organic carbon provide ages older than the time of soil burial, and 14C dates of geochemical fractions such as alkali and acid extracts (operationally defined as humic acids) can provide anomalously old ages when compared to coeval plant macrofossil dates. Ramped pyrolysis radiocarbon analysis of sedimentary organic material has been employed as a tool for investigating 14C age spectra in sediments with multiple organic carbon sources. Here we combine ramped pyrolysis 14C analysis and biomarker analysis (lignin-phenols and other cupric oxide products) to provide information on the source and diagenetic state of the paleosol organic carbon. We apply these techniques to immature early Holocene brackish wetland entisols from three sediment cores in southeastern Louisiana, along with overlying basal peats. Surprisingly, we find narrow 14C age spectra across all thermal aliquots from both paleosols and peats. The weighted bulk 14C ages from paleosols and overlying peats are within analytical error, and are comparable to independently analyzed 14C AMS dates from charcoal fragments and other plant macrofossils from each peat bed. Our results suggest high turnover rates of carbon in soils relative to input of exogenous carbon sources. These data raise broader questions about processes within the active soil and during pedogenesis and burial of paleosols that can effectively homogenize radiocarbon content in soils across the thermochemical spectrum. The concurrence of paleosol and peat 14C ages also suggests that, in the absence of peats with identifiable plant macrofossils, ramped pyrolysis 14C analyses of paleosols may be used to provide ages for sea-level indicators.

Early College, Early Success: Early College High School Initiative Impact Study

ERIC Educational Resources Information Center

Berger, Andrea; Turk-Bicakci, Lori; Garet, Michael; Song, Mengli; Knudson, Joel; Haxton, Clarisse; Zeiser, Kristina; Hoshen, Gur; Ford, Jennifer; Stephan, Jennifer; Keating, Kaeli; Cassidy, Lauren

2013-01-01

In 2002, the Bill & Melinda Gates Foundation launched the Early College High School Initiative (ECHSI) with the primary goal of increasing the opportunity for underserved students to earn a postsecondary credential. To achieve this goal, Early Colleges provide underserved students with exposure to, and support in, college while they are in…

Early Diagnosis and Early Intervention in Cerebral Palsy

PubMed Central

Hadders-Algra, Mijna

2014-01-01

This paper reviews the opportunities and challenges for early diagnosis and early intervention in cerebral palsy (CP). CP describes a group of disorders of the development of movement and posture, causing activity limitation that is attributed to disturbances that occurred in the fetal or infant brain. Therefore, the paper starts with a summary of relevant information from developmental neuroscience. Most lesions underlying CP occur in the second half of gestation, when developmental activity in the brain reaches its summit. Variations in timing of the damage not only result in different lesions but also in different neuroplastic reactions and different associated neuropathologies. This turns CP into a heterogeneous entity. This may mean that the best early diagnostics and the best intervention methods may differ for various subgroups of children with CP. Next, the paper addresses possibilities for early diagnosis. It discusses the predictive value of neuromotor and neurological exams, neuroimaging techniques, and neurophysiological assessments. Prediction is best when complementary techniques are used in longitudinal series. Possibilities for early prediction of CP differ for infants admitted to neonatal intensive care and other infants. In the former group, best prediction is achieved with the combination of neuroimaging and the assessment of general movements, in the latter group, best prediction is based on carefully documented milestones and neurological assessment. The last part reviews early intervention in infants developing CP. Most knowledge on early intervention is based on studies in high-risk infants without CP. In these infants, early intervention programs promote cognitive development until preschool age; motor development profits less. The few studies on early intervention in infants developing CP suggest that programs that stimulate all aspects of infant development by means of family coaching are most promising. More research is urgently needed

Chesapeake Bay Sediment Flux Model

DTIC Science & Technology

1993-06-01

1988; Van der Molen , -88- 1991; Yoshida, 1981.) The model developed below is based on both of these approaches. It incorporates the diagenetic...288: pp. 289-333. Van der Molen , D.T. (1991): A simple, dynamic model for the simulation of the release of phosphorus from sediments in shallow...1974; Berner, 1980; van Cappellen and Berner, 1988). These relate the diagenetic production of phosphate to the resulting pore water concentration

Cathodoluminescent bimineralic ooids from the Pleistocene of the Florida continental shelf

USGS Publications Warehouse

Major, R. P.; Halley, Robert B.; Lukas, Karen J.

1988-01-01

  The ooid grainstone underwent an episode of meteoric diagenesis. but ooid cortices were not affected by the event. We propose a previously unrecognized process by which the magnesian calcite cortex layers underwent diagenetic alteration in oxygen-depleted seawater. During this diagenesis, magnesium was lost and manganese was incorporated without apparent textural alteration and without mineralogical stabilization. Thus, we Suggest that cathodoluminescence may result from diagenetic alteration on the sea-floor.

Iodine-to-calcium ratios in carbonates suggest a primary origin for the Precambrian Lomagundi and Shuram carbon isotope excursions

NASA Astrophysics Data System (ADS)

Hardisty, D. S.; Lu, Z.; Planavsky, N. J.; Osburn, M. R.; Bekker, A.; Lyons, T. W.

2013-12-01

the Archean, suggest very early dolomitization in an oxidizing surface ocean promoting aerobic iodine cycling. This interpretation is consistent with earlier suggestions relating a >+10 ‰ δ13Ccarb shift to substantial organic carbon burial and associated oxygen production. Extremely negative δ13Ccarb (down to <-10 ‰) observed during the Shuram event have been linked to both diagenetic and primary mechanisms. We propose, however, that a marked increase in I/Ca ratios associated with the negative δ13Ccarb excursion in the Khufai Formation of Oman provides evidence for a primary origin for the Shuram. Such an increase could be interpreted as enhanced delivery of IO3- or total iodine from the deep ocean, perhaps driven by deep ocean ventilation and/or oxidation of a large pool of marine-derived organic matter. Overall, regardless of the individual primary controls driving increases in carbonate I/Ca during the Lomagundi and Shuram events, authigenic/diagenetic controls allowing for increased I/Ca are unlikely, suggesting a primary origin for the two largest δ13Ccarb excursions in Earth history.

Availability of free oxygen in deep bottom water of some Archean-Early Paleoproterozoic ocean basins as derived from iron formation facies analyses

NASA Astrophysics Data System (ADS)

Beukes, N. J.; Smith, A.

2013-12-01

Archean to Early Paleoproterozoic ocean basins are commonly, although not exclusively, depicted as rather static systems; either permanently stratified with shallow mixed oxygenated water overlying anoxic deep water or with a totally anoxic water column. The anoxic water columns are considered enriched in dissolved ferrous iron derived from hydrothermal plume activity. These sourced deposition of iron formations through precipitation of mainly ferrihydrite via reaction with free oxygen in the stratified model or anaerobic iron oxidizing photoautotrophs in the anoxic model. However, both these models face a simple basic problem if detailed facies reconstructions of deepwater microbanded iron formations (MIFs) are considered. In such MIFs it is common that the deepest water and most distal facies is hematite rich followed shoreward by magnetite, iron silicate and siderite facies iron formation. Examples of such facies relations are known from jaspilitic iron formation of the ~3,2 Ga Fig Tree Group (Barberton Mountainland), ~ 2,95 Ga iron formations of the Witwatersrand-Mozaan basin and the ~2,5 Ga Kuruman Iron Formation, Transvaal Supergroup, South Africa. Facies relations of these MIFs with associated siliciclastics or carbonates also indicate that the upper water columns of the basins, down to below wave base, were depleted in iron favoring anoxic-oxic stratification rather than total anoxia. In the MIFs it can be shown that hematite in the distal facies represents the earliest formed diagenetic mineral; most likely crystallized from primary ferrihydrite. The problem is one of how ferrihydrite could have been preserved on the ocean floor if it was in direct contact with reducing ferrous deep bottom water. Rather dissolved ferrous iron would have reacted with ferrihydrite to form diagenetic magnetite. This dilemma is resolved if in the area of deepwater hematite MIF deposition, the anoxic ferrous iron enriched plume was detached from the basin floor due to buoyancy

Early Childhood Systems: Transforming Early Learning

ERIC Educational Resources Information Center

Kagan, Sharon Lynn, Ed.; Kauertz, Kristie, Ed.

2012-01-01

In this seminal volume, leading authorities strategize about how to create early childhood systems that transcend politics and economics to serve the needs of all young children. The authors offer different interpretations of the nature of early childhood systems, discuss the elements necessary to support their development, and examine how…

The preliminary result of the δ65Cu and δ34S values of major ore minerals in the Erdenetiin-Ovoo Cu-Mo porphyry deposit, Northern Mongolia

NASA Astrophysics Data System (ADS)

KIM, Y.; Lee, I.; Oyungerel, S.; Jargal, L.; Tsedenbal, T.; Ryu, J. S.

2016-12-01

The copper isotope (δ65Cu) and sulfur isotope (δ34S) compositions of major ore minerals from the Erdenetiin-Ovoo Cu-Mo porphyry deposit were measured to trace sources of copper and sulfur, and to evaluate the precipitation environment of ore minerals. The major ore minerals are pyrite, chalcopyrite, molybdenite and chalcocite developed in the QSP (Quartz-Sericite-Pyrite) alteration zone. The sulfide minerals such as sphalerite and covellite, and carbonate ore minerals like malachite, azurite are also identified. The copper isotope ratios (65Cu/63Cu) of copper ore minerals (chalcopyrite, chalcocite, malachite, azurite, covellite and chrysocolla) were analyzed by the MC-ICPMS in KBSI located in Ochang, South Korea. The measured δ65Cu values relative to NIST 976 range from -1.01 ‰ to 5.76 ‰. The average δ65Cu values of sulfide minerals such as chalcopyrite (1.03 ‰), chalcocite (0.62 ‰) and covellite (0.51 ‰) seem to be relatively lower than those of carbonate and silicate Cu minerals such as malachite (0.24 ‰), azurite (2.17 ‰) and chrysocolla (5.76 ‰). The sulfur isotope ratios (34S/32S) of major sulfide minerals were measured by EA-CF-IRMS (Elemental Analyzer - Continuous Flow - Isotope Ratio Mass Spectrometer) in NCIRF, Seoul National University. The average δ34SV-CDT value is -1.1 ‰ indicating the magmatic signature of sulfur. There is the difference of δ34S values between sulfide minerals. While the δ34S values of pyrite, chalcopyrite and molybdenite range from -0.9 to 0.8 ‰, the δ34S values of chalcocite range from -2.6 ‰ to -1.4 ‰. These lower values might be attributed to the sulfur isotope fractionation during its precipitation.

Distinguishing geology from biology in the Ediacaran Doushantuo biota relaxes constraints on the timing of the origin of bilaterians.

PubMed

Cunningham, John A; Thomas, Ceri-Wyn; Bengtson, Stefan; Kearns, Stuart L; Xiao, Shuhai; Marone, Federica; Stampanoni, Marco; Donoghue, Philip C J

2012-06-22

The Ediacaran Doushantuo biota has yielded fossils that include the oldest widely accepted record of the animal evolutionary lineage, as well as specimens with alleged bilaterian affinity. However, these systematic interpretations are contingent on the presence of key biological structures that have been reinterpreted by some workers as artefacts of diagenetic mineralization. On the basis of chemistry and crystallographic fabric, we characterize and discriminate phases of mineralization that reflect: (i) replication of original biological structure, and (ii) void-filling diagenetic mineralization. The results indicate that all fossils from the Doushantuo assemblage preserve a complex mélange of mineral phases, even where subcellular anatomy appears to be preserved. The findings allow these phases to be distinguished in more controversial fossils, facilitating a critical re-evaluation of the Doushantuo fossil assemblage and its implications as an archive of Ediacaran animal diversity. We find that putative subcellular structures exhibit fabrics consistent with preservation of original morphology. Cells in later developmental stages are not in original configuration and are therefore uninformative concerning gastrulation. Key structures used to identify Doushantuo bilaterians can be dismissed as late diagenetic artefacts. Therefore, when diagenetic mineralization is considered, there is no convincing evidence for bilaterians in the Doushantuo assemblage.

Bioturbating animals control the mobility of redox-sensitive trace elements in organic-rich mudstone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harazim, Dario; McIlroy, Duncan; Edwards, Nicholas P.

Bioturbating animals modify the original mineralogy, porosity, organic content, and fabric of mud, thus affecting the burial diagenetic pathways of potential hydrocarbon source, seal, and reservoir rocks. High-sensitivity, synchrotron rapid scanning X-ray fluorescence elemental mapping reveals that producers of phycosiphoniform burrows systematically partition redox-sensitive trace elements (i.e., Fe, V, Cr, Mn, Co, Ni, Cu, and As) in fine-grained siliciclastic rocks. Systematic differences in organic carbon content (total organic carbon >1.5 wt%) and quality (Δ 13C org~0.6‰) are measured between the burrow core and host sediment. The relative enrichment of redox-sensitive elements in the burrow core does not correlate with significantmore » neo-formation of early diagenetic pyrite (via trace metal pyritization), but is best explained by physical concentration of clay- and silt-sized components. A measured loss (~–15%) of the large-ionic-radius elements Sr and Ba from both burrow halo and core is most likely associated with the release of Sr and Ba to pore waters during biological ( in vivo) weathering of silt- to clay-sized lithic components and feldspar. In conclusion, this newly documented effect has significant potential to inform the interpretation of geochemical proxy and rock property data, particularly from shales, where elemental analyses are commonly employed to predict reservoir quality and support paleoenvironmental analysis.« less

Mineralogical constraints on the paleoenvironments of the Ediacaran Doushantuo Formation

PubMed Central

Bristow, Thomas F.; Kennedy, Martin J.; Derkowski, Arkadiusz; Droser, Mary L.; Jiang, Ganqing; Creaser, Robert A.

2009-01-01

Assemblages of clay minerals are routinely used as proxies for paleoclimatic change and paleoenvironmental conditions in Phanerozoic rocks. However, this tool is rarely applied in older sedimentary units. In this paper, the clay mineralogy of the Doushantuo Formation in South China is documented, providing constraints on depositional conditions of the Ediacaran Yangtze platform that host the earliest animal fossils in the geological record. In multiple sections from the Yangtze Gorges area, trioctahedral smectite (saponite) and its diagenetic products (mixed-layer chlorite/smectite, corrensite, and chlorite) are the dominant clays through the lower 80 m of the formation and constitute up to 30 wt% of the bulk rock. Saponite is interpreted as an in situ early diagenetic phase that formed in alkaline conditions (pH ≥ 9). The absence of saponite in stratigraphically equivalent basin sections, 200–400 km to the south, indicates that alkaline conditions were localized in a nonmarine basin near the Yangtze Gorges region. This interpretation is consistent with crustal abundances of redox-sensitive trace elements in saponitic mudstones deposited under anoxic conditions, as well as a 10‰ difference in the carbon isotope record between Yangtze Gorges and basin sections. Our findings suggest that nonmarine environments may have been hospitable for the fauna preserved in the Yangtze Gorges, which includes the oldest examples of animal embryo fossils and acanthomorphic acritarchs. PMID:19666508

Bioturbating animals control the mobility of redox-sensitive trace elements in organic-rich mudstone

DOE PAGES

Harazim, Dario; McIlroy, Duncan; Edwards, Nicholas P.; ...

2015-10-07

Bioturbating animals modify the original mineralogy, porosity, organic content, and fabric of mud, thus affecting the burial diagenetic pathways of potential hydrocarbon source, seal, and reservoir rocks. High-sensitivity, synchrotron rapid scanning X-ray fluorescence elemental mapping reveals that producers of phycosiphoniform burrows systematically partition redox-sensitive trace elements (i.e., Fe, V, Cr, Mn, Co, Ni, Cu, and As) in fine-grained siliciclastic rocks. Systematic differences in organic carbon content (total organic carbon >1.5 wt%) and quality (Δ 13C org~0.6‰) are measured between the burrow core and host sediment. The relative enrichment of redox-sensitive elements in the burrow core does not correlate with significantmore » neo-formation of early diagenetic pyrite (via trace metal pyritization), but is best explained by physical concentration of clay- and silt-sized components. A measured loss (~–15%) of the large-ionic-radius elements Sr and Ba from both burrow halo and core is most likely associated with the release of Sr and Ba to pore waters during biological ( in vivo) weathering of silt- to clay-sized lithic components and feldspar. In conclusion, this newly documented effect has significant potential to inform the interpretation of geochemical proxy and rock property data, particularly from shales, where elemental analyses are commonly employed to predict reservoir quality and support paleoenvironmental analysis.« less

Early Intervention.

ERIC Educational Resources Information Center

Nathanson, Jeanne H., Ed.

1992-01-01

This theme issue focuses on early intervention. The four articles presented on this theme are: (1) "Deaf Infants, Hearing Mothers: A Research Report" (Kathryn P. Meadow-Orlans, and others), reporting findings on effects of auditory loss on early development; (2) "Maintaining Involvement of Inner City Families in Early Intervention Programs through…

Community replacement instead of drowning: Evolution of proto-North Atlantic carbonate-platform production in the run-up to of the Early Aptian OAE1a

NASA Astrophysics Data System (ADS)

Huck, Stefan; Stein, Melody; Adatte, Thierry; Föllmi, Karl B.; Immenhauser, Adrian; Heimhofer, Ulrich

2014-05-01

In the proto-North Atlantic realm (Lusitanian Basin, Portugal), carbonate platform production witnessed a major biotic turnover during the Early Aptian. Here, Urgonian-type rudist-nerinid dominated limestones were replaced by an orbitolinid-rich, oyster and serpulid-bearing marly facies. Integrated biostratigraphic-chemostratigraphic studies (Burla et al., 2008; Huck et al., 2012) provided evidence that this change coincides with the Early Aptian carbonate platform drowning episode in the run-up of oceanic anoxic event (OAE) 1a (transition D. forbesi to D. deshayesi ammonite zones), which has been recorded, from many localities in the Tethyan Ocean (Godet, 2013). Unlike Helvetic and Arabian carbonate platforms, which are characterised by a punctuated mass occurrence of orbitolinids marking the onset of the Aptian (Rawil and Hawar members, respectively), orbitolinids are an abundant constituent of the proto-North Atlantic carbonate platform community from the Late Barremian onwards. Orbitolinid-rich packstones and marls showing mass-occurrences of orbitolinids indicate repeated short-term installation of specific environmental conditions (eutrophication and/or deepening). In order to critically assess the influence of regional palaeoenvironmental against global palaeoclimatic and palaeoceanographic changes on the Proto-North Atlantic carbonate platform evolution, several outcrop successions in the Lusitanian Basin covering the critical interval have been investigated in detail with regard to facies and petrographic characteristics and geochemical (C-/O-isotopes, P content, bulk-rock and clay mineralogy,) inventory. The aims of the present study are three-fold: (1) to characterise proto-North Atlantic Lower Aptian shallow-water carbonates with respect to diagenetic history, microfacies, and distribution of fossils useful for the analysis of palaeoenvironments (corals, rudists and orbitolinids); (2) to evaluate the influence of sea-level and humidity changes

Assessing the fidelity of marine vertebrate microfossil δ18O signatures and their potential for palaeo-ecological and -climatic reconstructions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roelofs, Brett; Barham, Milo; Cliff, John

Conodont biogenic apatite has become a preferred analytical target for oxygen isotope studies investigating ocean temperature and palaeoclimate change in the Palaeozoic. Despite the growing application in geochemical based palaeoenvironmental reconstructions, the paucity or absence of conodont fossils in certain facies necessitates greater flexibility in selection of robust oxygen bearing compounds for analysis. Microvertebrates offer a potential substitute for conodonts from the middle Palaeozoic. Microvertebrate bioapatite is particularly advantageous given a fossil record extending to the present with representatives across freshwater to fully marine environments, thus widening the scope of oxygen isotope studies on bioapatite. However, significant tissue heterogeneity withinmore » vertebrates and differential susceptibility of these tissues to diagenetic alteration have been raised as potential problems affecting the reliability of the oxygen isotope ratios as palaeoclimate proxies. Pristine microvertebrate and co-occurring conodont fossils from the Late Devonian and Early Carboniferous of the Lennard Shelf, Canning Basin, Western Australia, were analysed using bulk (gas isotope ratio mass spectrometry) and in-situ (secondary ion mass spectrometry) methodologies, with the latter technique allowing investigation of specific tissues within vertebrate elements. The δ18Oconodont results may be interpreted in terms of palaeolatitudinally and environmentally sensible palaeotemperatures and provide a baseline standard for comparison against δ18Omicrovertebrate values. Despite an absence of obvious diagenetic influences, GIRMS of microvertebrate denticles yielded δ18O values depleted by 2-4 ‰ relative to co-occurring conodonts. SIMS analysis of hypermineralised tissues in both scales and teeth produced δ18O values comparable with those of associated conodonts. The susceptibility of porous phosphatic fossil tissues to microbial activity, fluid interaction and

Chalcopyrite—bearer of a precious, non-precious metal

USGS Publications Warehouse

Kimball, Bryn E.

2013-01-01

The mineral chalcopyrite (CuFeS2) is the world's most abundant source of copper, a metal component in virtually every piece of electrical equipment. It is the main copper mineral in several different ore deposit types, the most important of which are porphyry deposits. Chalcopyrite is unstable at the Earth's surface, so it weathers from sulphide outcrops and mine waste piles, contributing acid and dissolved copper to what is known as acid rock drainage. If not prevented, dissolved copper from chalcopyrite weathering will be transported downstream, potentially harming ecosystems along the way. Pristine areas are becoming targets for future copper supply as we strive to meet ever-increasing demands for copper by developed and developing nations. Additionally, our uses for copper are expanding to include technology such as solar energy production. This has lead to the processing of increasingly lower grade ores, which is possible, in part, due to advances in bio-leaching (i.e. metal extraction catalysed by micro-organisms). Although copper is plentiful, it is still a nonrenewable resource. Future copper supply promises to fall short of demand and the volatility of the copper market may continue if we do not prioritize copper use and improve copper recycling and ore extraction efficiency.

Revealing the optoelectronic and thermoelectric properties of the Zintl quaternary arsenides ACdGeAs{sub 2} (A = K, Rb)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Azam, Sikander; Khan, Saleem Ayaz; Goumri-Said, Souraya, E-mail: Souraya.Goumri-Said@chemistry.gatech.edu

Highlights: • Zintl tetragonal phase ACdGeAs{sub 2} (A = K, Rb) are chalcopyrite and semiconductors. • Their direct band gap is suitable for PV, optolectronic and thermoelectric applications. • Combination of DFT and Boltzmann transport theory is employed. • The present arsenides are found to be covalent materials. - Abstract: Chalcopyrite semiconductors have attracted much attention due to their potential implications in photovoltaic and thermoelectric applications. First principle calculations were performed to investigate the electronic, optical and thermoelectric properties of the Zintl tetragonal phase ACdGeAs{sub 2} (A = K, Rb) using the full potential linear augmented plane wave method andmore » the Engle–Vosko GGA (EV–GGA) approximation. The present compounds are found semiconductors with direct band gap and covalent bonding character. The optical transitions are investigated via the dielectric function (real and imaginary parts) along with other related optical constants including refractive index, reflectivity and energy-loss spectrum. Combining results from DFT and Boltzmann transport theory, we reported the thermoelectric properties such as the Seebeck’s coefficient, electrical and thermal conductivity, figure of merit and power factor as function of temperatures. The present chalcopyrite Zintl quaternary arsenides deserve to be explored for their potential applications as thermoelectric materials and for photovoltaic devices.« less

Selenium content in sulfide ores from the Chalkidiki peninsula, Greece.

PubMed

Nicolaidou, A E

1998-01-01

Selenium (Se) was assessed in galena, sphalerite, and pyrite samples. These are components of mixed sulfide ores from the Olympias and Madem Lakkos-Mavres Petres deposits and the Skouries porphyry-copper deposit. We used atomic absorption spectroscopy (AAS) with a hydride generator system. The highest concentration of Se (516 ppm) was found in the fine-grained galena at the -135 level of the Olympias deposits. In the Madem Lakkos-Mavres Petres deposit, the highest concentration of Se (33 ppm) was found in the pyrites of the level 30. The concentration of Se in the arsenopyrites and chalcopyrites is lower than the detection limit of the analytical method (< 100 ppb). The concentrated chalcopyrite from the porphyry copper deposit at Skouries exhibits a significant Se content (average 200 ppm) in contrast to the chalcopyrite from the Olympias and the Madem Lakkos-Mavres Petres. Variations in the Se content of the sulfide minerals studied could be caused by redox-pH and/or temperature conditions, as well as by the difference in crystal structure. The Se found in the areas studied may positively affect the environment. Sulfide minerals are oxidized by microorganisms, infiltrate in the soil-water in the form of selenate or selenite ion, and directly or indirectly influence the human organism.

Selective Adhesion of Thiobacillus ferrooxidans to Pyrite

PubMed Central

Ohmura, Naoya; Kitamura, Keiko; Saiki, Hiroshi

1993-01-01

Bacterial adhesion to mineral surfaces plays an important role not only in bacterial survival in natural ecosystems, but also in mining industry applications. Selective adhesion was investigated with Thiobacillus ferrooxidans by using four minerals, pyrite, quartz, chalcopyrite, and galena. Escherichia coli was used as a control bacterium. Contact angles were used as indicators of hydrophobicity, which was an important factor in the interaction between minerals and bacteria. The contact angle of E. coli in a 0.5% sodium chloride solution was 31°, and the contact angle of T. ferrooxidans in a pH 2.0 sulfuric acid solution was 23°. E. coli tended to adhere to more hydrophobic minerals by hydrophobic interaction, while T. ferrooxidans selectively adhered to iron-containing minerals, such as pyrite and chalcopyrite. Ferrous ion inhibited the selective adhesion of T. ferrooxidans to pyrite competitively, while ferric ion scarcely inhibited such adhesion. When selective adhesion was quenched by ferrous ion completely, adhesion of T. ferrooxidans was controlled by hydrophilic interactions. Adhesion of E. coli to pyrite exhibited a liner relationship on langmuir isotherm plots, but adhesion of T. ferrooxidans did not. T. ferrooxidans recognized the reduced iron in minerals and selectively adhered to pyrite and chalcopyrite by a strong interaction other than the physical interaction. PMID:16349106

The complicated substrates enhance the microbial diversity and zinc leaching efficiency in sphalerite bioleaching system.

PubMed

Xiao, Yunhua; Xu, YongDong; Dong, Weiling; Liang, Yili; Fan, Fenliang; Zhang, Xiaoxia; Zhang, Xian; Niu, Jiaojiao; Ma, Liyuan; She, Siyuan; He, Zhili; Liu, Xueduan; Yin, Huaqun

2015-12-01

This study used an artificial enrichment microbial consortium to examine the effects of different substrate conditions on microbial diversity, composition, and function (e.g., zinc leaching efficiency) through adding pyrite (SP group), chalcopyrite (SC group), or both (SPC group) in sphalerite bioleaching systems. 16S rRNA gene sequencing analysis showed that microbial community structures and compositions dramatically changed with additions of pyrite or chalcopyrite during the sphalerite bioleaching process. Shannon diversity index showed a significantly increase in the SP (1.460), SC (1.476), and SPC (1.341) groups compared with control (sphalerite group, 0.624) on day 30, meanwhile, zinc leaching efficiencies were enhanced by about 13.4, 2.9, and 13.2%, respectively. Also, additions of pyrite or chalcopyrite could increase electric potential (ORP) and the concentrations of Fe3+ and H+, which were the main factors shaping microbial community structures by Mantel test analysis. Linear regression analysis showed that ORP, Fe3+ concentration, and pH were significantly correlated to zinc leaching efficiency and microbial diversity. In addition, we found that leaching efficiency showed a positive and significant relationship with microbial diversity. In conclusion, our results showed that the complicated substrates could significantly enhance microbial diversity and activity of function.

Infusing Early Childhood Mental Health into Early Intervention Services

ERIC Educational Resources Information Center

Grabert, John C.

2009-01-01

This article describes the process of enhancing early childhood mental health awareness and skills in non-mental health staff. The author describes a pilot training model, conducted the U.S. Army's Early Intervention Services, that involved: (a) increasing early childhood mental health knowledge through reflective readings, (b) enhancing…

Tracing Biosignature Preservation of Geothermally Silicified Microbial Textures into the Geological Record.

PubMed

Campbell, Kathleen A; Lynne, Bridget Y; Handley, Kim M; Jordan, Sacha; Farmer, Jack D; Guido, Diego M; Foucher, Frédéric; Turner, Susan; Perry, Randall S

2015-10-01

New Zealand and Argentine (Late Jurassic-Recent) siliceous hot-spring deposits (sinter) reveal preservation pathways of environmentally controlled, microbe-dominated sedimentary facies over geological time scales. Texturally distinctive, laminated to thinly layered, dense and vertically oriented, microtubular "palisade" fabric is common in low-temperature (<40°C) sinter-apron terraces. In modern hot springs, the dark green to brown, sheathed, photosynthetic cyanobacterium Calothrix spp. (family Rivulariaceae) constructs felted palisade mats in shallow terrace(tte) pools actively accreting opaline silica. The resulting stacked layers of silicified coarse filaments-a stromatolite-are highly porous and readily modified by postdepositional environmental perturbations, secondary silica infill, and diagenetic silica phase mineral transformations (opal-A to quartz). Fossil preservation quality is affected by relative timing of silicification, and later environmental and geological events. A systematic approach was used to characterize palisade fabric in sinters of different ages to refine tools for recognizing biosignatures in extreme environments and to track their long-term preservation pathways into the geological record. Molecular techniques, scanning electron microscopy, Raman spectrometry, X-ray powder diffraction, petrography, and lipid biomarker analyses were applied. Results indicate that microbial communities vary at the micron scale and that early and rapid silicification is paramount to long-term preservation, especially where minimal postdepositional disturbance follows fossilization. Overall, it appears that the most robust biomarkers of fossil microbial activity in hot-spring deposits are their characteristic macro- and microtextures and laser micro-Raman identified carbon. Studies of Phanerozoic geothermal deposits with mineralized microbial components are relevant analogs for Precambrian geobiology because early life is commonly preserved as microbial

Are glendonites reliable indicators of cold conditions? Evidence from the Lower Cretaceous of Spitsbergen

NASA Astrophysics Data System (ADS)

Vickers, Madeleine; Price, Gregory; Watkinson, Matthew; Jerrett, Rhodri

2017-04-01

Glendonites are pseudomorphs after the mineral ikaite, and have been found in marine sediments throughout geological time. Ikaite is a metastable, hydrated form of calcium carbonate, which is only stable under specific conditions: between -2 and +5 °C, and with high alkalinity and phosphate concentrations. Glendonites are often associated with cold climates due to the strong temperature control on ikaite growth, and the coincidence in the geological record with episodes of global cooling. Glendonites are found in the Lower Cretaceous succession in Spitsbergen. During the Early Cretaceous, Spitsbergen was at a palaeolatitude of 60°N, and was part of a shallow epicontinental sea that formed during the Mesozoic as Atlantic rifting propagated northwards. Though the Early Cretaceous was generally characterised by greenhouse climate conditions, episodic cold snaps occurred during the Valanginian (the "Weissert Event") and during Aptian-Albian. Using high resolution carbon-isotope stratigraphy, we show that the first occurrences of glendonites are in the upper Lower Hauterivian and in the very upper Upper Hauterivian, stratigraphically higher than the Valanginian cooling event. Glendonites are also found in horizons in the Upper Aptian, coincident with the Aptian-Albian cold snap. Petrological analysis of the glendonite structure reveals differences between the Hauterivian and Aptian glendonites, with evidence for multiple diagenetic phases of growth in the Hauterivian glendonites, suggesting oscillating chemical conditions. This evidence suggests that local environmental conditions may have a stronger control on glendonite formation and preservation than global climate. We present a new model for ikaite growth and slow transformation to glendonite in marine sediments, which points to a more complex suite of diagenetic transformations than previously modelled. Furthermore, we critically assess whether such pseudomorphs after marine sedimentary ikaite may be indicators

Early Literacy and Early Numeracy: The Value of Including Early Literacy Skills in the Prediction of Numeracy Development

ERIC Educational Resources Information Center

Purpura, David J.; Hume, Laura E.; Sims, Darcey M.; Lonigan, Cristopher J.

2011-01-01

The purpose of this study was to examine whether early literacy skills uniquely predict early numeracy skills development. During the first year of the study, 69 3- to 5-year-old preschoolers were assessed on the Preschool Early Numeracy Skills (PENS) test and the Test of Preschool Early Literacy Skills (TOPEL). Participants were assessed again a…

Analysing diagenetic effects of flood basalts on sedimentary basins during Gondwanan break-up: case studies from NW Namibia.

NASA Astrophysics Data System (ADS)

Thompson, G. A.; Jerram, D. A.; Harris, C.; Pearson, D. G.

2003-04-01

ABSTRACT The eruption of large volumes of lava associated with the break-up and dispersal of the Gondwana Supercontinent is a phenomenon that has been well documented in literature. The Etendeka Flood Basalt Province of NW Namibia is correlated with the Paraná Flood Basalt Province of South America and was extruded between 139Ma for the earliest flows and 130Ma for the most recent. The passive, inflated pahoehoe lava flows have preserved bedforms within sand dunes found in the Huab Basin without significant deformation. This allows the internal structures of the palaeo-dunes to be analysed with great accuracy; a phenomenon rarely seen within the geological record. The sediments directly beneath, and interbedded with, the Etendeka Flood Basalt are lithostratigraphically similar to those in the Kudu Gas Province, offshore Namibia, where gas-bearing aeolian sands are interspersed with lava flows. Research by the authors is focussed on the diagenetic effects, both direct and indirect, of the emplacement of the lava, and the associated sills and dykes, on the aeolian sands. Specific interests include: the compartmentalisation of the basin by sills/dykes/lava: how does this affect fluid flow paths? Diagenesis along hot contacts: is the dramatic reduction in porosity/permeability along such contacts the result of the igneous bodies alone or do they need ground water present? Can large igneous events trigger the movement of hot fluids through the basin and to what extent does this cause alteration to sediments? To address these issues we have identified a number of outcrop case studies within the Huab Basin in NW Namibia. Here, excellent 3 dimensional outcrop coupled with almost 100 percent exposure allows detailed sampling strategies to be employed on locations of interest. In some cases igneous dykes have acted as flow barriers to pore fluids and have therefore altered the type and degree of cementation either side of the dyke. Geochemical analysis of the cement can

Combined Th/U, Pa/U and Ra/Th dating of fossil reef corals

NASA Astrophysics Data System (ADS)

Obert, J. C.; Scholz, D.; Lippold, J.; Felis, T.; Jochum, K. P.; Andreae, M. O.

2016-12-01

Fossil reef corals are often subject to post-depositional open-system behaviour, which is a major problem for accurate absolute dating. The commonly used 230Th/U-system can be disturbed by diagenetic alteration resulting in wrong apparent 230Th/U-ages. Since fossil reef corals are important palaeoenvironmental archives, precise absolute dating is essential for sea-level reconstruction and high-resolution climate reconstruction. We have developed a method for combined preparation and analysis of fossil reef corals by the 230Th/U-, 231Pa/U- and 226Ra/230Th-methods. Inconsistencies between ages determined by the different methods provide a means to identify diagenetically altered corals. In addition, the comparison of the 230Th/U and 231Pa/U data on concordia diagrams reveals further information about the alteration processes. (226Ra/230Th) and (226Ra/U) ratios in particular provide information about the more recent past (last 10 to approx. 50 ka) of the coral's diagenetic history. We compare these data with quantitative modelling of various diagenetic scenarios in order to identify the potential open-system processes. Here we present new data on the combined application of the three isotope systems to fossil Last Interglacial corals from the Gulf of Aqaba, northern Red Sea. Previous studies have shown that these corals were subject to substantial open-system behaviour, documented by very high initial (234U/238U) activity ratios. The process that was proposed to explain the activity ratios of these corals is U gain with subsequent U loss after a specific amount of time. The amount of U loss is assumed to be proportional to the amount of U previously gained. The application of our new method aims to test whether this diagenetic scenario can be verified.

Publications - SR 58 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

; Arsenopyrite; Barite; Base Metals; Big Delta; Bismuth; Chalcopyrite; Chicken Pluton; Cliff Mine; Coal ; Delta Junction; Diamond Drilling; Diamonds; Donlin Creek; Drift Mine; Drilling; Duke Island; Economic

Early cements versus pore-water chemical composition in the subsurface of the sabkha of Abu Dhabi

NASA Astrophysics Data System (ADS)

Paul, Andreas; Yuan, Peng; Court, Wesley M.; Lokier, Stephen W.; Dutton, Kirsten E.; Van der Land, Cees; Lessa Andrade, Luiza; Sherry, Angela; Head, Ian M.

2017-04-01

The coastal sabkha of Abu Dhabi is a complex depositional system in an extremely arid climate. This depositional system is marked by the formation of primary carbonate and microbial deposits, and by the development of secondary evaporite and cement phases. A number of earlier studies have assessed the formation of these secondary phases, yet no research has established a relationship between lateral and vertical variations in the chemical composition of pore water and the nature of, in particular, the precipitating pore-filling cements, re-crystallisation features and dissolution. This study aims to establish an understanding of the environmental and sedimentary factors that control early post-depositional changes to sediment composition as a result of sediment - pore water interactions. A particular focus is to characterise changes in the chemistry of the pore water throughout a tidal cycle, aiming at understanding how the influx of 'fresh' lagoonal sea water influences the chemistry of the pore water, and which elements are replenished on a daily basis. The initial data presented here is based upon the relationship between the petrographic analysis of sediment samples and lateral and vertical variations in the chemistry of in-situ sampled pore water. The pore water is characterised with respect to pH, salinity, alkalinity, dissolved organic carbon, and the concentrations of a variety of common metallic and non-metallic elements, including (but not limited to) Ca, Fe, Mg, P, S and Sr. Initial results show that concentrations of Mg, P, and V, and the ratios Mg/Ca and Sr/Ca are highest at the seaward sampling locations. Contrastingly, individual concentrations for Ca, Sr, Fe, Si, and Cu are highest at the most landward locality. In particular the higher concentrations for Ca and Sr might indicate diagenetic processes and are thus enriched as a result of e.g. aragonite dissolution. A striking pattern in Mg concentrations show the highest values for this element

Brachytherapy in early prostate cancer--early experience.

PubMed

Jose, B O; Bailen, J L; Albrink, F H; Steinbock, G S; Cornett, M S; Benson, D C; Schmied, W K; Medley, R N; Spanos, W J; Paris, K J; Koerner, P D; Gatenby, R A; Wilson, D L; Meyer, R

1999-01-01

Use of brachytherapy with radioactive seeds in the management of early prostate cancer is commonly used in the United States. The early experience has been reported from the prostate treatment centers in Seattle for the last 10 years. In this manuscript we are reporting our early experience of 150 radioactive seed implantations in early stage prostate cancer using either Iodine 125 or Palladium 103 seeds. The average age of the patient is 66 years and the median Gleason score is 5.4 with a median PSA of 6. A brief description of the evolution of the treatment of prostate cancer as well as the preparation for the seed implantation using the volume study with ultrasound of the prostate, pubic arch study using CT scan of the pelvis and the complete planning using the treatment planning computers are discussed. We also have described the current technique which is used in our experience based on the Seattle guidelines. We plan a follow-up report with the results of the studies with longer follow-up.

Platinum-group mineralization at the margin of the Skaergaard intrusion, East Greenland

NASA Astrophysics Data System (ADS)

Andersen, Jens C. Ø.; Rollinson, Gavyn K.; McDonald, Iain; Tegner, Christian; Lesher, Charles E.

2017-08-01

Two occurrences of platinum-group elements (PGEs) along the northern margin of the Skaergaard intrusion include a sulfide-bearing gabbro with slightly less than 1 ppm PGE + Au and a clinopyroxene-actinolite-plagioclase-biotite-ilmenite schist with 16 vol% sulfide and 1.8 ppm PGE + Au. Both have assemblages of pyrrhotite, pentlandite, and chalcopyrite typical for orthomagmatic sulfides. Matching platinum-group mineral assemblages with sperrylite (PtAs2), kotulskite (Pd(Bi,Te)1-2), froodite (PdBi2), michenerite (PdBiTe), and electrum (Au,Ag) suggest a common origin. Petrological and geochemical similarities suggest that the occurrences are related to the Skaergaard intrusion. The Marginal Border Series locally displays Ni depletion consistent with sulfide fractionation, and the PGE fractionation trends of the occurrences are systematically enriched by 10-50 times over the chilled margin. The PGE can be explained by sulfide-silicate immiscibility in the Skaergaard magma with R factors of 110-220. Nickel depletion in olivine suggests that the process occurred within the host cumulate, and the low R factors require little sulfide mobility. The sulfide assemblages are different to the chalcopyrite-bornite-digenite assemblage found in the Skaergaard Layered Series and Platinova Reef. These differences can be explained by the early formation of sulfide melt, while magmatic differentiation or sulfur loss caused the unusual sulfide assemblage within the Layered Series. The PGEs indicate that the sulfides formed from the Skaergaard magma. The sulfides and PGEs could not have formed from the nearby Watkins Fjord wehrlite intrusion, which is nearly barren in sulfide. We suggest that silicate-sulfide immiscibility led to PGE concentration where the Skaergaard magma became contaminated with material from the Archean basement.

Sedimentology and Reservoir Characteristics of Early Cretaceous Fluvio-Deltaic and Lacustrine Deposits, Upper Abu Gabra Formation, Sufyan Sub-basin, Muglad Rift Basin, Sudan

NASA Astrophysics Data System (ADS)

Yassin, Mohamed; Abdullatif, Osman; Hariri, Mustafa

2017-04-01

Sufyan Sub-basin is an East-West trending Sub-basin located in the northwestern part of the Muglad Basin (Sudan), in the eastern extension of the West and Central Africa Rift System (WCARS). The Early Cretaceous Abu Gabra Formation considered as the main source rock in the Muglad Basin. In Sufyan Sub-basin the Early Cretaceous Upper Abu Gabra Formation is the main oil-producing reservoir. It is dominated by sandstone and shales deposited in fluvio-deltaic and lacustrine environment during the first rift cycle in the basin. Depositional and post-depositional processes highly influenced the reservoir quality and architecture. This study investigates different scales of reservoir heterogeneities from macro to micro scale. Subsurface facies analysis was analyzed based on the description of six conventional cores from two wells. Approaches include well log analysis, thin sections and scanning electron microscope (SEM) investigations, grain-size, and X-ray diffraction (XRD) analysis of the Abu Gabra sandstone. The cores and well logs analyses revealed six lithofacies representing fluvio-deltaic and lacustrine depositional environment. The sandstone is medium to coarse-grained, poorly to moderately sorted and sub-angular to subrounded, Sub-feldspathic arenite to quartz arenite. On macro-scale, reservoir quality varies within Abu Gabra reservoir where it shows progressive coarsening upward tendencies with different degrees of connectivity. The upper part of the reservoir showed well connected and amalgamated sandstone bodies, the middle to lower parts, however, have moderate to low sandstone bodies' connectivity and amalgamation. On micro-scale, sandstone reservoir quality is directly affected by textures and diagenesis.The XRD and SEM analyses show that kaolinite and chlorite clay are the common clay minerals in the studied samples. Clay matrix and quartz overgrowth have significantly reduced the reservoir porosity and permeability, while the dissolution of feldspars

Early literacy and early numeracy: the value of including early literacy skills in the prediction of numeracy development.

PubMed

Purpura, David J; Hume, Laura E; Sims, Darcey M; Lonigan, Christopher J

2011-12-01

The purpose of this study was to examine whether early literacy skills uniquely predict early numeracy skills development. During the first year of the study, 69 3- to 5-year-old preschoolers were assessed on the Preschool Early Numeracy Skills (PENS) test and the Test of Preschool Early Literacy Skills (TOPEL). Participants were assessed again a year later on the PENS test and on the Applied Problems and Calculation subtests of the Woodcock-Johnson III Tests of Achievement. Three mixed effect regressions were conducted using Time 2 PENS, Applied Problems, and Calculation as the dependent variables. Print Knowledge and Vocabulary accounted for unique variance in the prediction of Time 2 numeracy scores. Phonological Awareness did not uniquely predict any of the mathematics domains. The findings of this study identify an important link between early literacy and early numeracy development. Copyright © 2011 Elsevier Inc. All rights reserved.

Elastic, vibration and thermodynamic properties of Cu1‑x Ag x InTe2 (x = 0, 0.25, 0.5, 0.75 and 1) chalcopyrite compounds via first principles

NASA Astrophysics Data System (ADS)

Zhong, Yuhan; Wang, Peida; Mei, Huayue; Jia, Zhenyuan; Cheng, Nanpu

2018-06-01

CuInTe2 chalcopyrite compound is widely used in the fields of optoelectronics and pyroelectricity, and doping atoms can further improve the physical properties of the CuInTe2 compound. For all we know, this is the first time that the elastic behaviors and lattice dynamical properties of Ag-doped CuInTe2 compounds with the tetragonal system are determined theoretically. The elastic, lattice dynamical and thermal properties of Cu1‑x Ag x InTe2 (x = 0, 0.25, 0.5, 0.75 and 1) compounds have been investigated by using density functional theory. The obtained elastic constants of Cu1‑x Ag x InTe2 compounds indicate that these compounds are mechanically stable and elastic anisotropic. The anisotropy of the {001} plane is more obvious than those of the {100} and {010} planes. Additionally, with increasing Ag doping concentrations, the bulk and shear moduli of Cu1‑x Ag x InTe2 compounds decrease and their toughness improves. The phonon spectra and density of states reveal that Cu (or Ag) atoms in Cu1‑x Ag x InTe2 compounds form chemical bonds with Te atoms, and Cu-Te bonds are gradually replaced by Ag-Te bonds with increasing Ag doping concentration. Vibration modes of Cu1‑x Ag x InTe2 compounds at the {{Γ }} point in the Brillouin zone show that each Cu1‑x Ag x InTe2 (x = 0 and 1) crystal includes five irreducible representations (A1, A2, B1, B2 and E). As for Cu1‑x Ag x InTe2 (x = 0.25, 0.5 and 0.75) compounds, each crystal has three irreducible representations (A, B and E). The atomic displacements of several typical phonon modes in CuInTe2 crystals have been analyzed to deepen the understanding of lattice vibrations in Cu1‑x AgxInTe2 compounds. With increasing Ag doping concentration, the Debye temperatures of Cu1‑x Ag x InTe2 compounds decrease, while their heat capacities increase.

Temperature calibration of amino acid racemization: age implications for the Yuha skeleton

USGS Publications Warehouse

Bischoff, J.L.; Childers, W.M.

1979-01-01

D/L of aspartic acid ranged from 0.52 to 0.56 for femur samples of the Yuha skeleton. Subsurface temperature measurements made at the burial site indicate average annual temperature is 18??C and diagenetic temperature is 21.6??C. These data and a relation derived for the dependence of the aspartic acid rate constant on diagenetic temperature indicate an age of 23,600. The result is consistent with 14C and 230Th dating of calcrete found coating the bones. ?? 1979.

Induced and catalysed mineral precipitation in the deep biosphere

NASA Astrophysics Data System (ADS)

Meister, Patrick

2017-04-01

Authigenic and early diagenetic minerals provide archives of past (bio)geochemical processes. In particular, isotopic signatures preserved in the diagenetic phases have been shown to document drastic changes of subsurface microbial activity (the deep biosphere) over geological time periods (Contreras et al., 2013; Meister, 2015). Geochemical and isotopic signatures in authigenic minerals may also document surface conditions and past climate. Nevertheless, such use of authigenic mineral phases as (bio)geochemical archives is often hampered by the insufficient understanding of mineral precipitation mechanisms. Accordingly the time, place and rate of mineral precipitation are often not well constrained. Also, element partitioning and isotopic fractionation may be modified as a result of the precipitation mechanism. Early diagenetic dolomite and quartz from drilled sequences in the Pacific were compared with adjacent porewater compositions and isotope signatures to gain fundamental insight into the factors controlling mineral precipitation. The formation of dolomite in carbonate-free organic carbon-rich ocean margin sediments (e.g. Peru Margin; Ocean Drilling Program, ODP, Site 1229; Meister et al., 2007) relies on the alkalinity-increase driven by anaerobic oxidation of methane and, perhaps, by alteration of clay minerals. In contrast, quartz is often significantly oversaturated in marine porewaters as the dissolved silica concentration is buffered by more soluble opal-A. For example, quartz does not form throughout a 400 metre thick sedimentary sequence in the Eastern Equatorial Pacific (ODP Site 1226; Meister et al., 2014) because it is kinetically inhibited. This behaviour can be explained by Ostwald's step rule, which suggests that the metastable phase forms faster. However, hard-lithified quartz readily forms where silica concentration drops sharply below opal-saturation. This violation of Ostwald's step rule must be driven by an auxiliary process, such as the

Systematic variations in sinter mineralogy, microtexture and diagenesis in modern siliceous hot springs: Clues for interpreting depositional conditions in ancient deposits

NASA Astrophysics Data System (ADS)

Mills, V. W.; Farmer, J. D.; Ruff, S. W.; Nunez, J.; Jahnke, L. L.

2011-12-01

The deposits of siliceous hydrothermal springs are known to capture and preserve a wide range of microbial fossil information. The recent discovery of hydrothermal silica at Home Plate, Columbia Hills, Mars has once again raised interest in the potential importance of ancient spring sinters as targets for future astrobiological mission to Mars. To create additional context information to support future in situ missions to Mars, we have documented systematic changes in the mineralogy and microtexture of modern siliceous hot spring deposits, observed along gradients in temperature, pH and flow velocity. Specific objectives are to: 1) identify chemical and physical factors that promote early diagenetic transformations of amorphous silica (opal-A), to progressively more ordered and crystalline phases (cristobalite, tridymite and quartz); 2) determine the composition and abundance of minor mineral phases, especially clays, in relationship to pH, temperature and paragenesis; and 3) to assess the usefulness of sinter mineralogy and microtexture in reconstructing the paleoenvironmental records preserved in ancient deposits. Study sites for acidic (pH 2-5) sinters included Nymph Creek, located in the Norris Geyser Basin of Yellowstone National Park (YNP). Active alkaline (pH 7-10) springs included Rabbit Creek, Steep Cone and Mound Spring located in the Lower Geyser Basin, YNP. Field measurements in active springs included pH, temperature and flow velocity, along with general microfacies assignments. To better constrain types and rates of silica diagenesis, the study also sampled older (Holocene-Pleistocene-aged) deposits. Laboratory analyses included X-ray powder diffraction (XRPD), thermal infrared spectroscopy (TIR) and thin section petrography for characterizing sinter microtextures and for placing mineral phases (identified by XRPD and TIR) into a time-ordered diagenetic framework. In analyzing the phyllosilicates present in sinters, we applied clay separation and

Multiple sulfur isotope constraints on sulfate-driven anaerobic oxidation of methane: Evidence from authigenic pyrite in seepage areas of the South China Sea

NASA Astrophysics Data System (ADS)

Lin, Zhiyong; Sun, Xiaoming; Strauss, Harald; Lu, Yang; Gong, Junli; Xu, Li; Lu, Hongfeng; Teichert, Barbara M. A.; Peckmann, Jörn

2017-08-01

Multiple sulfur isotope signatures and secondary ion mass spectroscopy (SIMS) sulfur isotope compositions of pyrite from two seafloor sites (DH-CL11 and HD109) in seepage areas of the South China Sea were measured in order to study isotope effects of sulfate-driven anaerobic oxidation of methane (SO4-AOM). The multiple sulfur isotopes of pyrite reveal variable ranges for both sites (δ34S: between -44.1‰ and -2.9‰ for DH-CL11 and between -43.8‰ and -1.6‰ for HD109; Δ33S: between 0.02‰ and 0.17‰ for DH-CL11 and between -0.03‰ and 0.14‰ for HD109). SIMS analysis reveals an extreme variability of δ34S values (between -50.3‰ and -2.7‰ in DH-CL11; between -50.1 and 52.4‰ in HD109) for three types of pyrite: (1) framboids, (2) zoned aggregates with radial overgrowth surrounding a framboidal core, and (3) euhedral pyrite crystals. The synchronous changes of geochemical proxies (sulfate and methane concentrations, δ34Ssulfate and δ18Osulfate, δ34Spyrite, and pyrite content) at the sulfate-methane transition zone (SMTZ) at site DH-CL11 are interpreted to be induced by SO4-AOM under steady state conditions. In contrast, pyrite content and δ34S value fluctuations throughout core HD109 suggest that the sediment at this site was affected by multiple pyritization events during diagenesis. Multiple sulfur isotope signatures of early diagenetic pyrite (i.e., with low and high δ34S values, the latter above 315 cmbsf in DH-CL11; above 70 cmbsf in HD109) in the upper sediment column suggest that organoclastic sulfate reduction (OSR) and sulfur disproportionation generated the observed isotopic signatures. In contrast to the early diagenetic 34S depleted framboids, the higher SIMS δ34S values of overgrowth and euhedral crystals suggest a late diagenetic 34S enriched pool of dissolved sulfide derived from SO4-AOM at the current and paleo-SMTZs. Interestingly, pyrite resulting from SO4-AOM in the SMTZ at site DH-CL11 reveals a distinct pattern with higher �

Molecular composition and paleobotanical origin of Eocene resin from northeast India

NASA Astrophysics Data System (ADS)

Rudra, Arka; Dutta, Suryendu; Raju, Srinivasan V.

2014-06-01

The molecular composition of fossil resins from early to middle Eocene coal from northeast India, has been analyzed for the first time to infer their paleobotanical source. The soluble component of fossil resin was analyzed using gas chromatography-mass spectrometry (GC-MS). The resin extracts are composed of cadalene-based C15 sesquiterpenoids and diagenetically altered triterpenoids. The macromolecular composition was investigated using pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) and Fourier transform infrared (FTIR) spectroscopy. The major pyrolysis products are C15 bicyclic sesquiterpenoids, alkylated naphthalenes, benzenes and a series of C17-C34 n-alkene- n-alkane pairs. Spectroscopic analysis revealed the dominance of aliphatic components. The presence of cadalene-based sequiterpenoids confirms the resin to be Class II or dammar resin, derived from angiosperms of Dipterocarpaceae family. These sesquiterpenoids are often detected in many SE Asian fluvio-deltaic oils. Dipterocarpaceae are characteristic of warm tropical climate suggesting the prevalence of such climate during early Eocene in northeast India.

Brucite microbialites in living coral skeletons: Indicators of extreme microenvironments in shallow-marine settings

USGS Publications Warehouse

Nothdurft, L.D.; Webb, G.E.; Buster, N.A.; Holmes, C.W.; Sorauf, J.E.; Kloprogge, J.T.

2005-01-01

Brucite [Mg(OH)2] microbialites occur in vacated interseptal spaces of living scleractinian coral colonies (Acropora, Pocillopora, Porites) from subtidal and intertidal settings in the Great Barrier Reef, Australia, and subtidal Montastraea from the Florida Keys, United States. Brucite encrusts microbial filaments of endobionts (i.e., fungi, green algae, cyanobacteria) growing under organic biofilms; the brucite distribution is patchy both within interseptal spaces and within coralla. Although brucite is undersaturated in seawater, its precipitation was apparently induced in the corals by lowered pCO 2 and increased pH within microenvironments protected by microbial biofilms. The occurrence of brucite in shallow-marine settings highlights the importance of microenvironments in the formation and early diagenesis of marine carbonates. Significantly, the brucite precipitates discovered in microenvironments in these corals show that early diagenetic products do not necessarily reflect ambient seawater chemistry. Errors in environmental interpretation may arise where unidentified precipitates occur in microenvironments in skeletal carbonates that are subsequently utilized as geochemical seawater proxies. ?? 2005 Geological Society of America.

Early Childhood Special Education and Early Intervention Personnel Preparation Standards of the Division for Early Childhood: Field Validation

ERIC Educational Resources Information Center

Cochran, Deborah C.; Gallagher, Peggy A.; Stayton, Vicki D.; Dinnebeil, Laurie A.; Lifter, Karin; Chandler, Lynette K.; Christensen, Kimberly A.

2012-01-01

Results of the field validation survey of the revised initial and new advanced Council for Exceptional Children (CEC) Division for Early Childhood (DEC) early childhood special education (ECSE)/early intervention (EI) personnel standards are presented. Personnel standards are used as part of educational accountability systems and in teacher…

Early Attachment Relationships and the Early Childhood Curriculum

ERIC Educational Resources Information Center

Cortazar, Alejandra; Herreros, Francisca

2010-01-01

This article explores the relationship between attachment theory and the early childhood curriculum. During the first years of life children develop early attachment relationships with their primary caregivers. These attachment relationships, either secure or insecure, will shape children's socio-emotional development. In the USA, the predominant…

First insights on the molybdenum-copper Bled M'Dena complex (Eglab massif, Algeria)

NASA Astrophysics Data System (ADS)

Lagraa, Karima; Salvi, Stefano; Béziat, Didier; Debat, Pierre; Kolli, Omar

2017-03-01

Molybdenum-Copper showings in the Eglab massif (eastern part of the Reguibat rise of Algeria), are found in quartz-monzodiorite and granodiorite of the Bled M'Dena complex, a Paleoproterozoic circular structure of ∼5 km in diameter, comprising volcanic and intrusive suites. The latter consist of quartz-diorite, quartz-monzodiorite and granodiorite with a metaluminous normative composition. They display an "adakitic character" with moderate light rare-earth element (LREE) enrichment, minor Eu anomalies, high Sr/Y ratio and low Yb concentration, suggestive of a hydrous, arc magma of volcanic-arc affinity. The mineralization occurs mostly in quartz + molybdenite + chalcopyrite stockwork veins marked by widespread propylitic alteration along the selvages. Molybdenite and chalcopyrite are commonly associated with calcite, which precipitated at relatively late stages of the hydrothermal alteration. Fluid inclusions related to the mineralization stage, range from aqueous to aqueous-carbonic to solid bearing. The latter inclusions have the highest homogenization temperature (up to ∼400 °C), are salt saturated, and commonly contain molybdenite and/or chalcopyrite crystals. The petrology and geochemistry of the host rocks, the style of the hydrothermal alteration, the ore mineral associations, and the characteristics of the fluid inclusions, are all coherent in indicating that the Bled M'Dena represents a Paleoproterozoic porphyry style Mo mineralization, which is far unreported in the African continent.

Platinum-group element, Gold, Silver and Base Metal distribution in compositionally zoned sulfide droplets from the Medvezky Creek Mine, Noril'sk, Russia

USGS Publications Warehouse

Barnes, S.-J.; Cox, R.A.; Zientek, M.L.

2006-01-01

Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril'sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into

Equilibrium isotopic fractionation of copper during oxidation/reduction, aqueous complexation and ore-forming processes: Predictions from hybrid density functional theory

NASA Astrophysics Data System (ADS)

Sherman, David M.

2013-10-01

Copper exists as two isotopes: 65Cu (∼30.85%) and 63Cu (∼69.15%). The isotopic composition of copper in secondary minerals, surface waters and oxic groundwaters is 1-12‰ heavier than that of copper in primary sulfides. Changes in oxidation state and complexation should yield substantial isotopic fractionation between copper species but it is unclear to what extent the observed Cu isotopic variations reflect equilibrium fractionation. Here, I calculate the reduced partition function ratios for chalcopyrite (CuFeS2), cuprite (Cu2O), tenorite (CuO) and aqueous Cu+, Cu+2 complexes using periodic and molecular hybrid density functional theory to predict the equilibrium isotopic fractionation of Cu resulting from oxidation of Cu+ to Cu+2 and by complexation of dissolved Cu. Among the various copper(II) complexes in aqueous environments, there is a significant (1.3‰) range in the reduced partition function ratios. Oxidation and congruent dissolution of chalcopyrite (CuFeS2) to dissolved Cu+2 (as Cu(H2O)5+2) yields 65-63δ(Cu+2-CuFeS2) = 3.1‰ at 25 °C; however, chalcopyrite oxidation/dissolution is incongruent so that the observed isotopic fractionation will be less. Secondary precipitation of cuprite (Cu2O) would yield further enrichment of dissolved 65Cu since 65-63δ(Cu+2-Cu2O) is 1.2‰ at 25 °C. However, precipitation of tenorite (CuO) will favor the heavy isotope by +1.0‰ making dissolved Cu isotopically lighter. These are upper-limit estimates for equilibrium fractionation. Therefore, the extremely large (9‰) fractionations between dissolved Cu+2 (or Cu+2 minerals) and primary Cu+ sulfides observed in supergene environments must reflect Rayleigh (open-system) or kinetic fractionation. Finally the previously proposed (Asael et al., 2009) use of δ65Cu in chalcopyrite to estimate the oxidation state of fluids that transported Cu in stratiform sediment-hosted copper deposits is refined.

From the ocean to a salt marsh: towards understanding iron reduction processes with FORC-PCA.

NASA Astrophysics Data System (ADS)

Muraszko, J. R.; Lascu, I.; Collins, S. M.; Harrison, R. J.

2017-12-01

Biogenic magnetic minerals are a high fidelity recorder of climate change. Their sensitivity to sedimentary redox conditions and bottom water ventilation have the potential to provide useful insights into past diagenetic conditions. However, the mechanisms controlling preservation and dissolution of magnetosomes are not fully understood, thus undermining the reliability of the paleomagnetic records in marine environments. Recovering information about the diagenetic past of the sediment is a crucial challenge; specifically, the biogenic components need to be identified and unmixed from the bulk magnetic signal. We address the issue in this study by applying Principal Component Analysis on First Order Reversal Curve diagrams (FORC-PCA) in case studies of cores obtained from the Iberian Margin and the sedimentologically active coastal salt marshes of Norfolk. We demonstrate the applicability of FORC-PCA as a new environmental proxy, yielding a high resolution temporal marine record of environmental changes reflected in magnetic composition over the last 194 kyr. The strongest variations are observed in the microbially derived components, the bulk properties of the sediment being controlled by a low coercivity SP-SD component which is generally anticorrelated with the magnetosome signal. Supported by TEM studies, we suggest the prevalence of clusters of nano-particles of magnetite associated with iron reduction. To further investigate the mechanisms controlling these processes, the active sedimentary environment of Norfolk was chosen as a case study of early diagenesis controlled by strong vertical geochemical gradients.

Tectono-thermal evolution in a region with thin-skinned tectonics: the western nappes in the Cantabrian Zone (Variscan belt of NW Spain)

NASA Astrophysics Data System (ADS)

Bastida, F.; Brime, C.; García-López, S.; Sarmiento, G. N.

The palaeotemperature distribution in the transition from diagenesis to metamorphism in the western nappes of the Cantabrian Zone (Somiedo, La Sobia and Aramo Units) are analysed by conodont colour alteration index (CAI) and illite crystallinity (IC). Structural and stratigraphic control in distribution of CAI and IC values is observed. Both CAI and IC value distributions show that anchizonal conditions are reached in the lower part of the Somiedo Unit. A disruption of the thermal trend by basal thrusts is evidenced by CAI and IC values. There is an apparent discrepancy between the IC and CAI values in Carboniferous rocks of the Aramo Unit; the IC has mainly anchizonal values, whereas the CAI has diagenetic values. Discrepant IC values are explained as a feature inherited from the source area. In the Carboniferous rocks of the La Sobia Unit, both IC and CAI indicate diagenetic conditions. The anchimetamorphism predated completion of emplacement of the major nappes; it probably developed previously and/or during the early stages of motion of the units. Temperature probably decreased when the metamorphosed zones of the sheets rose along ramps and were intensely eroded. In the context of the Iberian Variscan belt, influence of tectonic factors on the metamorphism is greater in the internal parts, where the strain and cleavage are always present, than in the external parts (Cantabrian Zone), where brittle deformation and rock translation are dominant, with an increasing role of the burial on the metamorphism.

Origin and diagenesis of clay minerals in relation to sandstone paragenesis: An example in eolian dune reservoirs and associated rocks, Permian upper part of the Minnelusa Formation, Powder River basin, Wyoming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pollastro, R.M.; Schenk, C.J.

Eolian dune sandstones are the principal reservoir rocks in the Permian upper part of the Minnelusa Formation, Powder River basin, Wyoming. These sandstones formed as shorelines retreated and dunes migrated across siliciclastic sabkhas. Sandstones are mainly quartzarenites; on average, clay minerals constitute about 5 wt.% the whole rock. Although present in minor amounts, clay minerals play an important role in the diagenetic evolution of these sandstones. Allogenic clay minerals are present in shaly rock fragments and laminae. Early infiltration of clays into porous sabkha sands commonly form characteristic menisei or bridges between framework grains or, when more extensive, form coatingsmore » or rims on grain surfaces. Authigenic clays include nearly pure smectite, mixed-layer illite/smectite (I/S), and late diagenetic illite and corrensite; these clay minerals are present as pore-lining cements. In addition to the deposition and neoformation of clay minerals throughout sandstone paragenesis, the conversion of smectite to illite occurred as temperatures increased with progressive burial. A temperature of 103C is calculated at a present depth of 3,200 m using a geothermal gradient of 30C/km and a mean annual surface temperature of 7C. After correction for uplift and erosion (250 m), the maximum calculated temperature for the conversion of all random I/S to ordered I/S is 100C. This calculated temperature is in excellent agreement with temperatures of 100-110C implied from I/S geothermometry.« less

Paragenesis of the Morgan Creek Limestone, Late Cambrian, central Texas: Constraints on the formation of glauconite

NASA Astrophysics Data System (ADS)

Chafetz, Henry S.

2007-06-01

Deposition of the Morgan Creek Limestone, a member of the Cambrian Wilberns Formation, began a few meters above a disconformable surface and displays abundant indicators of accumulation in shallow marine to tidal flat environments. These indicators include: intercalation of a lithologic variety of thin beds (e.g. biosparites, biomicrites, oosparites, intrasparites), which display rapid vertical and lateral lithologic changes, numerous stromatolitic horizons, channels filled with graded oosparites and intrasparites that cut through micrite accumulations, and finely laminated (non-burrowed) siltstones. Glauconite is a ubiquitous minor constituent throughout in the form of pellets, replaced skeletal material and mica books, and, most informatively, as an authigenic precipitate in the form of fibroradiating rims on carbonate allochems and siliciclastic grains. Fibroradiating glauconite rims were disrupted and pushed away from the pelmatozoan nuclei on which they precipitated. Combined sedimentological and paragenetic constraints indicate that the glauconite was the earliest diagenetic event to affect these sediments and occurred essentially at the sediment-water interface within these relatively high-energy, shallow marine deposits. Precipitation of glauconite was closely followed by precipitation of carbonate cement as well as dissolution of aragonitic constituents. Later diagenetic processes included selective dolomitization and silicification. In modern seas glauconite is reported to form at and below mid-shelf water depths. Thus, the constraints pertaining to the origin of modern glauconite are not valid for Late Cambrian deposits and probably are also not applicable for Late Cretaceous through Early Paleogene glauconites.

Hematitic concretions at Meridiani Planum, Mars: Their growth timescale and possible relationship with iron sulfates

NASA Astrophysics Data System (ADS)

Sefton-Nash, Elliot; Catling, David C.

2008-05-01

Using diffusion-based models for concretion growth, we calculate growth times of hematitic concretions that have been found in the Burns formation at Meridiani Planum, Mars, by NASA's Opportunity Mars Exploration Rover. Growth times of ~ 350-1900 terrestrial years are obtained for the observed size range of the concretions over a range of parameters representing likely diagenetic conditions and allowing for an iron source from diagenetic redistribution. This time scale is consistent with radiometric age constraints for the growth time of iron oxide concretions in sandy sediments of the acid-saline Lake Brown in Western Australia (< 3000 yr) reported elsewhere. We consider the source of the iron for Meridiani concretions by calculating the constraints on the supply of Fe 3+ to growing concretions from the dissolution and oxidation rates of iron minerals on early Mars. Mass balance arguments suggest that acid dissolution of jarosite ((H 3O,K)(Fe 3+3(OH) 6(SO 4) 2) and minor ferric sulfates is probably the most plausible dominant contributor to Fe 3+ in the concretions. Ferrous iron released from melanterite (Fe 2+SO 4·7H 2O) that is subsequently oxidized could also have been an important iron source if melanterite existed prior to diagenesis. Our conclusion that the iron is sourced from iron sulfates may explain the global observation from orbiters that grey crystalline hematite occurs in association with sulfate deposits.

Analysis of Airborne Radar Altimetry Measurements of the Greenland Ice Sheet

NASA Technical Reports Server (NTRS)

Ferraro, Ellen J.

1994-01-01

This dissertation presents an analysis of airborne altimetry measurements taken over the Greenland ice sheet with the 13.9 GHz Advanced Application Flight Experiment (AAFE) pulse compression radar altimeter. This Ku-band instrument was refurbished in 1990 by the Microwave Remote Sensing Laboratory at the University of Massachusetts to obtain high-resolution altitude measurements and to improve the tracking, speed, storage and display capabilities of the radar. In 1991 and 1993, the AAFE altimeter took part in the NASA Multisensor Airborne Altimetry Experiments over Greenland, along with two NASA laser altimeters. Altitude results from both experiments are presented along with comparisons to the laser altimeter and calibration passes over the Sondrestroem runway in Greenland. Although it is too early to make a conclusion about the growth or decay of the ice sheet, these results show that the instrument is capable of measuring small-scale surface changes to within 14 centimeters. In addition, results from these experiments reveal that the radar is sensitive to the different diagenetic regions of the ice sheet. Return waveforms from the wet- snow, percolation and dry-snow zones show varying effects of both surface scattering and sub-surface or volume scattering. Models of each of the diagenetic regions of Greenland are presented along with parameters such as rms surface roughness, rms surface slope and attenuation coefficient of the snow pack obtained by fitting the models to actual return waveforms.

Evaluating Microstructure Preservation using Scanning Electron Microscopy in an Extinct Bivalve, Lahillia larseni

NASA Astrophysics Data System (ADS)

Mohr, R. C.; Tobin, T. S.

2017-12-01

Ontogenetic stable isotope (δ18O) sampling of accretionary carbonate shells can provide sub-annual records of environmental conditions, such as seawater temperature, during the life of an organism. These records of seasonal temperature variations can refine our understanding of ancient climates and past climate change. However, because original isotopic signatures can be altered by diagenesis, it is necessary to examine potential specimens for evidence of diagenetic alteration. Abundant aragonitic Lahillia larseni bivalves from the latest Cretaceous and Early Paleogene on Seymour Island, Antarctica, provide excellent opportunities for sclerochronological investigations. Shells of L. larseni preserve clear annual growth bands, which make them ideal candidates for high-resolution δ18O sampling to produce sub-annual records of seawater temperature variation. While the good visual condition of these shells and the preservation of original aragonitic material suggests a high level of preservation suitable for isotopic analysis, subtle alteration of the original shell microstructures can still compromise the original isotopic signatures. Scanning electron microscopy (SEM) can be used to evaluate the preservation of these microstructures. This study compares methods for imaging L. larseni bivalve shells with SEM and seeks a consistent way to evaluate their various microstructures for evidence of diagenetic alteration. High-resolution ontogenetic isotopic sampling will also be conducted on several L. larseni shells, as roughly sinusoidal δ18O profiles are often an indication that the original isotopic signatures have been preserved.

Diagenesis of an 'overmature' gas reservoir: The Spiro sand of the Arkoma Basin, USA

USGS Publications Warehouse

Spotl, C.; Houseknecht, D.W.; Burns, S.J.

1996-01-01

The Spiro sand is a laterally extensive thin sandstone of earliest Atokan (Pennsylvanian) age that forms a major natural gas reservoir in the western Arkoma Basin, Oklahoma. Petrographic analysis reveals a variety of diagenetic alterations, the majority of which occurred during moderate to deep burial. Early diagenetic processes include calcite cementation and the formation of Fe-clay mineral peloids and coatings around quartz framework grains. These clays, which underwent transformation to well-crystallized chamosite [polytype Ib(?? = 90??)] on burial, are particularly abundant in medium-grained channel sandstones, whereas illitic clays are predominant in fine-grained interchannel sandstones. Subsequent to mechanical compaction, saddle ankerite precipitated in the reservoir at temperatures in excess of 70??C. Crude oil collected in favourable structural locations during and after ankeritization. Whereas hydrocarbons apparently halted inorganic diagenesis in oil-saturated zones, cementation continued in the underlying water-saturated zones. As reservoir temperatures increased further, hydrocarbons were cracked and a solid pyrobitumen residue remained in the reservoir. At temperatures exceeding ???140-150??C, non-syntaxial quartz cement, ferroan calcite and traces of dickite(?) locally reduced the reservoir quality. Local secondary porosity was created by carbonate cement dissolution. This alteration post-dated hydrocarbon emplacement and is probably related to late-stage infiltration of freshwater along 'leaky' faults. The study shows that the Spiro sandstone locally retained excellent porosities despite deep burial and thermal conditions that correspond to the zone of incipient very low grade metamorphism.

Current oil and gas production from North American Upper Cretaceous chalks

USGS Publications Warehouse

Scholle, Peter A.

1977-01-01

porosity has been largely lost but secondary (fracture) porosity provides some storage capacity and greatly improves permeability (for example, Austin Group of the Pearsall field, Texas). 3. Areas with thick overburden in which marine pore fluids have been retained, or where hydrocarbons (including biogenically generated methane) were introduced early in the diagenetic history. In these settings, primary porosity is reduced to a lesser degree than in group two, and adequate reservoir properties can be maintained to depths approaching 2,000 m (6,600 ft) (for example, Scotian Shelf of Canada). Continued small-scale oil and gas discoveries can be expected from these types of reservoirs in North America. The prolific production of oil and gas from North Sea chalk reservoirs will not be matched in North America unless deeply buried, overpressured chalks can be located. It is the early formation of overpressures and (or) early oil input into North Sea chalks that have preserved porosities as high as 40 percent at 3,000- to 3,500-m (9,800- to 11,500-ft) depths and provided the outstanding reservoir capacity of those chalks.

Geology and porphyry copper-type alteration-mineralization of igneous rocks at the Christmas Mine, Gila County, Arizona

USGS Publications Warehouse

Koski, Randolph A.

1979-01-01

igneous rocks is progressively more alkaline and silicic from basalt to granodiorite. Early (Stage I) chalcopyrite-bornite (-molybdenite) mineralization and genetically related K-silicate alteration are centered on the Christmas stock. K-silicate alteration is manifested by pervasive hornblende-destructive biotitization in the stock, biotitization of basaltic volcanic wall rocks, and a continuous stockwork of K-feldspar veinlets and quartz-K-feldspar veins in the stock and quartz-sulfide veins in volcanic rocks. Younger (Stage II) pyrite-chalcopyrite mineralization and quartz-sericite-chlorite alteration occur in a zone overlapping with but largely peripheral to the zone of Stage I stockwork veins. Within the Christmas intrusive complex, K-silicate-altered rocks in the central stock are flanked east and west by zones of fracture-controlled quartz-sericite alteration and strong pyritization. In volcanic rocks quartz-chlorite-pyrite-chalcopyrite veins are superimposed on earlier biotitization and crosscut Stage I quartz-sulfide veins. Beyond the zones of quartz-sericite alteration, biotite rhyodacite porphyry dikes contain the propylitic alteration assemblage epidote-chlorite-albite-sphene. Chemical analyses indicate the following changes during pervasive alteration of igneous rocks: (1) addition of Si, K, H, S, and Cu, and loss of Fe 3+ and Ca during intense biotitization of basalt; (2) loss of Na and Ca, increase of Fe3+/Fe2+, and strong H-metasomatism during sericitization of quartz diorite; and (3) increase in Ca, Na, and Fe3+/Fe2+, and loss of K during intense propylitization of biotite rhyodacite porphyry dikes. Thorough biotitization of biotite granodiorite porphyry in the Christmas stock was largely an isochemical process. Fluid-inclusion petrography reveals that Stage I veins are characterized by low to moderate populations of moderate-salinity and gas-rich inclusions, and sparse but ubiquitous halite-bearing inclusions. Moderate-salinity an

Early Years Practitioners' Views on Early Personal, Social and Emotional Development

ERIC Educational Resources Information Center

Aubrey, Carol; Ward, Karen

2013-01-01

Current policy guidance stresses the need for early identification of obstacles to learning and appropriate intervention. New standards for learning (Early Years Foundation Stage) place personal, social and emotional development (PSED) as central to learning and development. This paper reports a survey and follow-up interviews with early years…

Single Source Precursors for Thin Film Solar Cells

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K.; Hollingsworth, Jennifer A.; Harris, Jerry D.; Cowen, Jonathan; Buhro, William E.; Hepp, Aloysius F.

2002-01-01

The development of thin film solar cells on flexible, lightweight, space-qualified substrates provides an attractive cost solution to fabricating solar arrays with high specific power, (W/kg). The use of a polycrystalline chalcopyrite absorber layer for thin film solar cells is considered as the next generation photovoltaic devices. At NASA GRC we have focused on the development of new single source precursors (SSP) and their utility to deposit the chalcopyrite semi-conducting layer (CIS) onto flexible substrates for solar cell fabrication. The syntheses and thermal modulation of SSPs via molecular engineering is described. Thin-film fabrication studies demonstrate the SSPs can be used in a spray CVD (chemical vapor deposition) process, for depositing CIS at reduced temperatures, which display good electrical properties, suitable for PV (photovoltaic) devices.

Geology of the Huron River pitchblende occurrence, Baraga County, Michigan

USGS Publications Warehouse

Vickers, R.C.

1955-01-01

Pitchblende and secondary uranium minerals occur as very small, discontinuous stringers and pods in calcite and quartz cementing the breccia within a low-angle shear zone that dips about 10 degrees to the southwest. The shear zone has a thickness of 10 to 30 feet and cuts black, locally carbonaceous slates of the upper Huronian Precambrian Michigamme slate. Mineral deposition during two hypogene stages and one supergene stage was identified in polished sections. The first phase consisted of the introduction of quartz and minor hematite into the sheared slate. After fracturing of the quartz the second stage was initiated by deposition of calcite, pyrite, rutile, pitchblende, bornite, sphalerite, chalcopyrite, galena, and greenockite. The supergene stage consisted of the development of metatyuyamunite, chalcopyrite, chalcocite, covellite, cuprite, volborthite, malachite, and goethite.

The effect of processing on the properties of CuInS2 nanomaterials synthesized by simple hot injection route

NASA Astrophysics Data System (ADS)

Chen, Qin-Miao; Zhou, Fang-Fang; Yuan, Hong-Chun; Chen, Jin; Ni, Yi; Zhu, Xi-Fang; Dou, Xiao-Ming

2017-07-01

Chalcopyrite and wurtzite CuInS2 (CIS) nanomaterials were synthesized from Cu2+, In3+, thiourea with or without triethanolamine (TEA) by simple hot injection method at low temperature. The effect of synthesis duration on the various properties of the synthesized CIS nanomaterials was studied. It shows that for chalcopyrite CIS, the optimal synthesis duration is 60 min and the synthesized nanomaterial is in spherical shape with diameter of about 90 nm. However, for the wurtzite CIS, the optimal synthesis duration should reach 150 min and the synthesized nanomaterial looks like nanoplate with thicknesses of ˜10 nm and diameters near 100 nm. The photovoltaic characteristics of two types of nanomaterials are quite different. This study may contribute to the synthesis of CIS nanomaterials at low temperatures.

Trace metal (Mg/Ca and Sr/Ca) analyses of single coccoliths by Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Prentice, Katy; Jones, Tom Dunkley; Lees, Jackie; Young, Jeremy; Bown, Paul; Langer, Gerald; Fearn, Sarah; EIMF

2014-12-01

Here we present the first multi-species comparison of modern and fossil coccolith trace metal data obtained from single liths. We present both trace metal analyses (Sr, Ca, Mg and Al) and distribution maps of individual Paleogene fossil coccoliths obtained by Secondary Ion Mass Spectrometry (SIMS). We use this data to determine the effects of variable coccolith preservation and diagenetic calcite overgrowths on the recorded concentrations of strontium and magnesium in coccolith calcite. The analysis of coccoliths from deep-ocean sediments spanning the Eocene/Oligocene transition demonstrates that primary coccolith calcite is resistant to the neomorphism that is common in planktonic foraminifera from similar depositional environments. Instead, where present, diagenetic calcite forms distinct overgrowths over primary coccolith calcite rather than replacing this calcite. Diagenetic overgrowths on coccoliths are easily distinguished in SIMS analyses on the basis of relatively higher Mg and lower Sr concentrations than co-occurring primary coccolith calcite. This interpretation is confirmed by the comparable SIMS analyses of modern cultured coccoliths of Coccolithus braarudii. Further, with diagenetic calcite overgrowth being the principle source of bias in coccolith-based geochemical records, we infer that lithologies with lower carbonate content, deposited below the palaeo-lysocline, are more likely to produce geochemical records dominated by primary coccolith calcite than carbonate-rich sediments where overgrowth is ubiquitous. The preservation of primary coccolith carbonate in low-carbonate lithologies thus provides a reliable geochemical archive where planktonic foraminifera are absent or have undergone neomorphism.

Characterization of Paleoredox Changes In Nw-pacific Deep-sea Sediments Using Environmental Magnetic In Combination With Geochemical-mineralogic Data

NASA Astrophysics Data System (ADS)

Urbat, M.; Pletsch, T.

The understanding of environmental and oceanic controls on deep-sea sediments in the NW Pacific Ocean (ODP Site 1149A, Nadezhda Basin) benefits from the inte- gration of environmental magnetic methodology with geochemical-mineralogic XRD (x-ray defraction) and XRF (x-ray fluorescence) data. Crucially, the inherently grad- ual diagenetic processes related to paleo-redox changes in the sediment column may be more sensitively monitored using the integration of non-magnetic and magnetic data, because they do reflect various aspects of the entire postdepositional alteration. The studied 32 m long quaternary interval at Hole ODP 1149A provides an expanded record of eolian dust supply from the Asian continent, siliceous plankton accumulation and varying contributions of both discrete ash layers and disperse ash to a truly deep- sea environment (Plank et al. 2000). Recurrent diagenetic intervals appear to be related to changes in the Ocean water circulation (Kuriosho current) and concomitant produc- tivity variations as a function of glacial-interglacial paleoclimatic changes. Diagenetic intervals correspond to paleo-redox boundaries, where suboxic conditions promoted the destruction of the primary magnetic signal (iron oxides) and the precipitation of rhodochrosite (MnCO3). We used simple normative calculations on the basis of of Al and Cr contents to discriminate between the major groups of components (terrigenous, volcanogenic, biogenic, diagenetic) in combination with our magnetic results. These results form the grounds for the discrimation and independent interpretation of the genetically various sediment components in the paleoceanograhic context.

Compositional variations and differential diagenesis in Miocene turbidites from the western coast of Mallorca (Balearic Islands, Spain)

NASA Astrophysics Data System (ADS)

Felder, Sonja; Westphal, Hildegard; Munnecke, Axel; Mateu Vicens, Guillem

2010-05-01

Compositional variations and differential diagenesis in Miocene turbidites from the western coast of Mallorca (Balearic Islands, Spain) Sonja Felder (1), Hildegard Westphal (1), Axel Munnecke (2), Guillem Mateu Vicens (1,3) (1) MARUM and Department of Geosciences, Universität Bremen, Leobener Straße, 28359 Bremen, Germany (2) GeoZentrum Nordbayern, Universität Erlangen-Nürnberg, Loewenichstr. 28, 91054 Erlangen, Germany (3) Dipartimento di Scienze della Terra, Università di Roma "La Sapienza", Ple Aldo 7 Moro, 5. I-00185 Roma, Italy Cyclic alternations of limestone and marl beds crop out along the western coast of the Island of Mallorca. This Miocene succession is traditionally interpreted to represent more weathering-resistant turbidites interlayered by softer hemipelagic background sediment. However, the cementation patterns that dominate the appearance of the outcrop do not always consistently follow sedimentary layering; locally the cemented beds are systematically oblique to the sedimentary layers. Compositional studies demonstrate that differences in non-carbonate fraction, carbonate concentration and fossil content (e.g. foraminiferal assemblages) trace sedimentary bedding, regardless the diagenetic style. Limestone versus marl lithology, in contrast, is defined by the diagenetic style, tight cementation by calcite cements in the limestones versus low porosity and compaction in the marls. The reason for this striking pattern of diagenetic bedding cross-cutting sedimentary layers is assumed to be related to tectonic fracturing, opening pathways for diagenetic fluids. This example cautions the straight-forward interpretation of limestone-marl alternations as direct witnesses of environmental or climatic variations.

Alteration in the Madera Limestone and Sandia Formation from core hole VC-1, Valles caldera, New Mexico

USGS Publications Warehouse

Keith, T.E.C.

1988-01-01

Core hole VC-1 penetrated the southwestern ring fracture zone of the 1.1 Ma Valles caldera and at a depth of 333 m intersected the top of the Paleozoic section including the Abo Formation, Madera Limestone, and Sandia Formation, reaching a total depth of 856 m. The Paleozoic rocks, which consist of thin-bedded limestone, siltstone, mudstone, sandstone, and local conglomerate, are overlain by volcanic rocks of the caldera moat that are less than 0.6 Ma. Diagenetic and at least three hydrothermal alteration stages were identified in the Madera Limestone and Sandia Formation. Diagenetic clay alteration was pervasive throughout the sedimentary rocks. Volcanic activity at 16.5 Ma and continuing through the formation of the Valles caldera resulted in high thermal gradients, which caused recrystallization of diagenetic clay minerals. Interstratified smectite-illite is the most diagnostic clay mineral throughout the section; structurally, the illite component in the ordered interstratified illite-smectite changes gradationally from 70% at the top of the Madera Limestone to 95% at the base of the section in the Sandia Formation. Pyrite that occurs as small clots and lenses as well as finely disseminated is interpreted as being of diagenetic origin, especially in organic-rich beds. Low permeability of much of the paleozoic section precluded the deposition of hydrothermal minerals except in fractures and intergranular space in some of the more permeable sandstone and brecciated horizons. Three stages of hydrothermal mineral deposition are defined. -from Author

Chemostratigraphy and Fe Mineralogy of the Victoria Crater Duck Bay Section: Opportunity APXS and Moessbauer Results

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Schroeder, C.; Gellert, R.; Klingelhoefer, G.; Jolliff, B. L.; Morris, R. V.

2008-01-01

Meridiani Planum is a vast plain of approximately horizontally bedded sedimentary rocks composed of mixed and reworked basaltic and evaporitic sands containing secondary, diagenetic minerals [e.g., 1-5]. Because bedding planes are subparallel to topography, investigation of contiguous stratigraphy requires examining exposures in impact craters. Early in the mission (sols 130-317), Opportunity was commanded to do detailed study of exposed outcrops in Endurance crater, including the contiguous Karatepe section at the point of ingress. Just over 1000 sols later and roughly 7 km to the south, the rover is being commanded to do a similar study of the Duck Bay section of Victoria crater. Here we report on the preliminary results from the Alpha Particle X-ray Spectrometer (APXS) and Moessbauer instruments.

CHARACTERIZATION OF SANDSTONE RESERVOIRS FOR ENHANCED OIL RECOVERY: THE PERMIAN UPPER MINNELUSA FORMATION, POWDER RIVER BASIN, WYOMING.

USGS Publications Warehouse

Schenk, C.J.; Schmoker, J.W.; Scheffler, J.M.

1986-01-01

Upper Minnelusa sandstones form a complex group of reservoirs because of variations in regional setting, sedimentology, and diagenetic alteration. Structural lineaments separate the reservoirs into northern and southern zones. Production in the north is from a single pay sand, and in the south from multi-pay sands due to differential erosion on top of the Upper Minnelusa. The intercalation of eolian dune, interdune, and sabkha sandstones with marine sandstones, carbonates, and anhydrites results in significant reservoir heterogeneity. Diagenetic alterations further enhance heterogeneity, because the degree of cementation and dissolution is partly facies-related.

Eocene sea temperatures for the mid-latitude southwest Pacific from Mg/Ca ratios in planktonic and benthic foraminifera

NASA Astrophysics Data System (ADS)

Creech, John B.; Baker, Joel A.; Hollis, Christopher J.; Morgans, Hugh E. G.; Smith, Euan G. C.

2010-11-01

We have used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to measure elemental (Mg/Ca, Al/Ca, Mn/Ca, Zn/Ca, Sr/Ca, and Ba/Ca) ratios of 13 species of variably preserved early to middle Eocene planktonic and benthic foraminifera from New Zealand. The foraminifera were obtained from Ashley Mudstone, mid-Waipara River, South Island, which was deposited at bathyal depth ( ca. 1000 m) on the northern margin of the east-facing Canterbury Basin at a paleo-latitude of ca. 55°S. LA-ICP-MS data yield trace element depth profiles through foraminifera test walls that can be used to identify and exclude zones of surficial contamination and infilling material resulting from diagenetic coatings, mineralisation and detrital sediment. Screened Mg/Ca ratios from 5 species of foraminifera are used to calculate sea temperatures from late Early to early Middle Eocene ( ca. 51 to 46.5 Ma), a time interval that spans the termination of the Early Eocene Climatic Optimum (EECO). During this time, sea surface temperatures (SST) varied from 30 to 24 °C, and bottom water temperatures (BWT) from 21 to 14 °C. Comparison of Mg/Ca sea temperatures with published δ 18O and TEX 86 temperature data from the same samples (Hollis et al., 2009) shows close correspondence, indicating that LA-ICP-MS can provide reliable Mg/Ca sea temperatures even where foraminiferal test preservation is variable. Agreement between the three proxies also implies that Mg/Ca-temperature calibrations for modern planktonic and benthic foraminifera can generally be applied to Eocene species, although some species (e.g., V. marshalli) show significant calibration differences. The Mg/Ca ratio of the Eocene ocean is constrained by our data to be 35-50% lower than the modern ocean depending on which TEX 86 - temperature calibration (Kim et al., 2008; Liu et al., 2009) - is used to compare with the Mg/Ca sea temperatures. Sea temperatures derived from δ 18O analysis of foraminifera from Waipara show

Early menarche, nulliparity and the risk for premature and early natural menopause.

PubMed

Mishra, Gita D; Pandeya, Nirmala; Dobson, Annette J; Chung, Hsin-Fang; Anderson, Debra; Kuh, Diana; Sandin, Sven; Giles, Graham G; Bruinsma, Fiona; Hayashi, Kunihiko; Lee, Jung Su; Mizunuma, Hideki; Cade, Janet E; Burley, Victoria; Greenwood, Darren C; Goodman, Alissa; Simonsen, Mette Kildevæld; Adami, Hans-Olov; Demakakos, Panayotes; Weiderpass, Elisabete

2017-03-01

Are parity and the timing of menarche associated with premature and early natural menopause? Early menarche (≤11 years) is a risk factor for both premature menopause (final menstrual period, FMP <40 years) and early menopause (FMP 40-44 years), a risk that is amplified for nulliparous women. Women with either premature or early menopause face an increased risk of chronic conditions in later life and of early death. Findings from some studies suggest that early menarche and nulliparity are associated with early menopause, however overall the evidence is mixed. Much of the evidence for a direct relationship is hampered by a lack of comparability across studies, failure to adjust for confounding factors and inadequate statistical power. This pooled study comprises 51 450 postmenopausal women from nine observational studies in the UK, Scandinavia, Australia and Japan that contribute to the International collaboration for a Life course Approach to reproductive health and Chronic disease Events (InterLACE). Age at menarche (categorized as ≤11, 12, 13, 14 and 15 or more years) and parity (categorized as no children, one child and two or more children) were exposures of interest. Age at FMP was confirmed by at least 12 months of cessation of menses where this was not the result of an intervention (such as surgical menopause due to bilateral oophorectomy or hysterectomy) and categorized as premature menopause (FMP before age 40), early menopause (FMP 40-44 years), 45-49 years, 50-51 years, 52-53 years and 54 or more years. We used multivariate multinomial logistic regression models to estimate relative risk ratio (RRR) and 95% CI for associations between menarche, parity and age at FMP adjusting for within-study correlation. The median age at FMP was 50 years (interquartile range 48-53 years), with 2% of the women experiencing premature menopause and 7.6% early menopause. Women with early menarche (≤11 years, compared with 12-13 years) were at higher risk of premature

Recent Coverage of Early Childhood Education Approaches in Open Access Early Childhood Journals

ERIC Educational Resources Information Center

Keskin, Burhanettin

2016-01-01

A content analysis of the coverage of the major approaches to early childhood education in the early childhood research journals, published between 2010 and 2014, that are early childhood research oriented and have free online access were investigated. Among 21 journals in early childhood education, two journals were selected for the content…

Occurrence of the Visible Gold and Sn-Bearing Mineral in Seafloor Hydrothermal Sulfides at Central Indian Ridge, 12.4°S

NASA Astrophysics Data System (ADS)

Choi, S. K.; Pak, S. J.; Kim, J.; Park, J. W.; Son, S. K.

2017-12-01

Sn-rich chimney fragments (up to 1,720 ppm) were recovered with ultramafic rocks from ocean core complex (OCC-4-1) of Central Indian Ridge, 12.4°S. The chimney fragments are featured by barite-free and Zn-rich (up to 50.1 wt.%) ores. The chimney fragments are mainly composed of sphalerite, isocubanite, pyrrhotite, chalcopyrite and marcasite with galena and electrum as minor minerals. The precipitation sequences of the minerals are categorized into three stages by mineral assemblage; early stage with low-temperature minerals, late stage with high-temperature minerals and seawater weathering stage with covellite, Fe-oxyhydroxides and amorphous silica. Early stage is characterized by sphalerite, intermittently showing colloform-texture, closely co-existed with anhedral marcasite and minor galena, whereas late stage is dominated by aggregates of isocubanite with chalcopyrite exsolution lamellae, pyrrhotite partially replaced by long prismatic marcasite and FeS enriched sphalerite (up to 42.69 FeS mole%). Electrums, main phase of gold mineralization, are mostly visible grains (< 3 um in diameter), occuring in sphalerite and isocubanite as inclusions and/or free gold in amorphous silica through the whole mineralization stages. On the basis of semi-quantified analysis, electrum grains are likely to have Au-rich composition. High Sn concentrations are typically observed in altered rim along the grain boundaries between sphalerite and isocubanite, going up to 5.5 wt.% in sphalerite. LA-ICP-MS mapping exhibits that Sn is preferentially incorporated into sphalerite relative to isocubanite, especially showing the highest values in boundaries between both minerals, but significantly lower in marcasite. Stoichiometry of Sn-enriched sphalerite rim seems to have a uniform ratio of atomic proportion of Cu to Sn as almost 2:1, implying that stannite micro-inclusions may result in Sn-enrichment. The LA-ICP-MS spectra also shows abrupt increase in Sn signal intensity, indicating Sn

Early Educational Intervention, Early Cumulative Risk, and the Early Home Environment as Predictors of Young Adult Outcomes within a High-Risk Sample

ERIC Educational Resources Information Center

Pungello, Elizabeth P.; Kainz, Kirsten; Burchinal, Margaret; Wasik, Barbara H.; Sparling, Joseph J.; Ramey, Craig T.; Campbell, Frances A.

2010-01-01

The extent to which early educational intervention, early cumulative risk, and the early home environment were associated with young adult outcomes was investigated in a sample of 139 young adults (age 21) from high-risk families enrolled in randomized trials of early intervention. Positive effects of treatment were found for education attainment,…

Origin of the dolomitic nodules from the tortonian marls of the western mediterranean margins. Their relation to past gas hydrate occurrence

NASA Astrophysics Data System (ADS)

Pierre, C.; Rouchy, J.-M.; Blanc-Valleron, M.-M.

2003-04-01

Dolomitic nodules are widely distributed in the Tortonian marls which outcrop in South-East Spain and Northern Morocco. They occur as decimetric to plurimetric diagenetic structures which have grown displacively within the marly layers ; owing to their similarity of occurrence, they are thought to belong to the same diagenetic environment. The oxygen and carbon isotopic compositions of the diagenetic dolomites exhibit very large variations (-6.7 < d18O ‰ PDB < 4.84 ; -25.64 < d13C ‰ PDB < 9.64). This range of variations is quite entirely covered by the dolomites from the Lorca basin in Spain where the dolomitic nodules are present at various levels from the base to the top of the thousand-meter thick marly Tortonian sequence ; this variability is also observed in Lorca at the meter-scale. The isotopic composition of these dolomites indicate that the carbonate precipitation occurred in diagenetic fluids of various compositions from 18O-poor to 18O-rich and from 13C-poor to 13C-rich depending on the inorganic/organic processes involved in the diagenetic environment. The 18O enrichment is thought to have resulted from gas hydrate decomposition or clay mineral dehydration while the 18O depletion might be related either to residual brines after gas hydrate formation or to clay mineral filtration of pore waters. The 13C enrichment clearly indicates methanogenesis while the 13C depletion is characteristic of bacterial sulfate reduction where organic matter or methane are oxidized. The formation of dolomitic nodules in the thick Tortonian marly successions was thus due to the circulation of pore fluids modified both by microbial processes and mineral interactions. These results are very reminiscent of those obtained in oceanic gas hydrate environments. We thus interpret these dolomites as the products of diagenesis in gas hydrate bearing sediments from the Mediterranean margins, which were dissociated when the Mediterranean level dropped by several hundreds of meters

The role of skeletal micro-architecture in diagenesis and dating of Acropora palmata

NASA Astrophysics Data System (ADS)

Tomiak, P. J.; Andersen, M. B.; Hendy, E. J.; Potter, E. K.; Johnson, K. G.; Penkman, K. E. H.

2016-06-01

Past variations in global sea-level reflect continental ice volume, a crucial factor for understanding the Earth's climate system. The Caribbean coral Acropora palmata typically forms dense stands in very shallow water and therefore fossil samples mark past sea-level. Uranium-series methods are commonly used to establish a chronology for fossil coral reefs, but are compromised by post mortem diagenetic changes to coral skeleton. Current screening approaches are unable to identify all altered samples, whilst models that attempt to correct for 'open-system' behaviour are not applicable across all diagenetic scenarios. In order to better understand how U-series geochemistry varies spatially with respect to diagenetic textures, we examine these aspects in relation to skeletal micro-structure and intra-crystalline amino acids, comparing an unaltered modern coral with a fossil A. palmata colony containing zones of diagenetic alteration (secondary overgrowth of aragonite, calcite cement and dissolution features). We demonstrate that the process of skeletogenesis in A. palmata causes heterogeneity in porosity, which can account for the observed spatial distribution of diagenetic features; this in turn explains the spatially-systematic trends in U-series geochemistry and consequently, U-series age. We propose a scenario that emphasises the importance of through-flow of meteoric waters, invoking both U-loss and absorption of mobilised U and Th daughter isotopes. We recommend selective sampling of low porosity A. palmata skeleton to obtain the most reliable U-series ages. We demonstrate that intra-crystalline amino acid racemisation (AAR) can be applied as a relative dating tool in Pleistocene A. palmata samples that have suffered heavy dissolution and are therefore unsuitable for U-series analyses. Based on relatively high intra-crystalline concentrations and appropriate racemisation rates, glutamic acid and valine are most suited to dating mid-late Pleistocene A. palmata

[In-patient (early) rehabilitation].

PubMed

Wallesch, Claus-W; Lautenschläger, Sindy

2017-04-01

It is difficult to develop the financing and hospital provision of interventions for early rehabilitation within the diagnosis-related group (DRG) system. In addition to a range of partially rehabilitative complex interventions, the system recognizes three main forms of early rehabilitative interventions: geriatric, neurological/neurosurgical, and interdisciplinary and others. In this article, the appropriate definitions and cost-effectiveness of these procedures are analyzed and compared. The early rehabilitative interventions are characterized by constant cooperation in the therapeutic team, especially neurological early rehabilitation through the incorporation of nursing as a therapeutic profession. Whereas geriatric and neurological early rehabilitation are reflected in the DRG system, the former provided in many general hospitals and the latter mainly in specialized institutions, interdisciplinary early rehabilitation has only occasionally been represented in the DRG system so far. If all acute in-patients who require early rehabilitation should receive such an intervention, an additional fee must be implemented for this this interdisciplinary service.

Late Carboniferous porphyry copper mineralization at La Voluntad, Neuquén, Argentina: Constraints from Re-Os molybdenite dating

NASA Astrophysics Data System (ADS)

Garrido, Mirta; Barra, Fernando; Domínguez, Eduardo; Ruiz, Joaquin; Valencia, Victor A.

2008-07-01

The La Voluntad porphyry Cu-Mo deposit in Neuquén, Argentina, is one of several poorly known porphyry-type deposits of Paleozoic to Early Jurassic age in the central and southern Andes. Mineralization at La Voluntad is related to a tonalite porphyry from the Chachil Plutonic Complex that intruded metasedimentary units of the Piedra Santa Complex. Five new Re-Os molybdenite ages from four samples representing three different vein types (i.e., quartz-molybdenite, quartz-sericite-molybdenite and quartz-sericite-molybdenite ± chalcopyrite-pyrite) are identical within error and were formed between ~312 to ~316 Ma. Rhenium and Os concentrations range between 34 to 183 ppm and 112 to 599 ppb, respectively. The new Re-Os ages indicate that the main mineralization event at La Voluntad, associated to sericitic alteration, was emplaced during a time span of 1.7 ± 3.2 Ma and that the deposit is Carboniferous in age, not Permian as previously thought. La Voluntad is the oldest porphyry copper deposit so far recognized in the Andes and indicates the presence of an active magmatic arc, with associated porphyry style mineralization, at the proto-Pacific margin of Gondwana during the Early Pennsylvanian.

What controls diffuse fractures in platform carbonates? Insights from Provence (France) and Apulia (Italy)

NASA Astrophysics Data System (ADS)

Lavenu, Arthur P. C.; Lamarche, Juliette

2018-03-01

Fractures are widespread in rocks and regional opening-mode arrays are commonly ascribed to major tectonic events. However, fractures occur in otherwise undeformed rocks. Some of these are early-developed features independent of tectonics and forming a background network at regional scale. To overcome this lack of understanding, two hydrocarbon reservoir analogues from platform carbonates have been targeted: the Provence (SE France), and the Apulian platform (SE Italy). In both areas, an early fracturing stage has been observed, made of high-angle-to-bedding opening-mode fractures, and bed-parallel stylolites. These features developed synchronously during the first burial stages and prior to major tectonic events. The fracture sets are not genetically related to the present-day layering. Contrarily, fractures developed in a brittle media where facies transitions were not sharp and did not act as mechanical discontinuities. Carbonate facies distribution and early diagenetic imprint constrained the mechanical stratigraphy when fractures occurred. In addition, we observed that fractures related to late tectonic inversion were partly inhibited. Indeed, rock mechanical properties change through time. Characterizing the temporal evolution of carbonate rocks has revealed that diagenesis and sedimentary facies are the prime actors for brittleness and mechanical layering in carbonates.

African ancestry, early life exposures, and respiratory morbidity in early childhood.

PubMed

Kumar, R; Tsai, H-J; Hong, X; Gignoux, C; Pearson, C; Ortiz, K; Fu, M; Pongracic, J A; Burchard, E G; Bauchner, H; Wang, X

2012-02-01

Racial disparities persist in early childhood wheezing and cannot be completely explained by known risk factors. To evaluate the associations of genetic ancestry and self-identified race with early childhood recurrent wheezing, accounting for socio-economic status (SES) and early life exposures. We studied 1034 children in an urban, multi-racial, prospective birth cohort. Multivariate logistic regression was used to evaluate the association of genetic ancestry as opposed to self-identified race with recurrent wheezing (>3 episodes). Sequential models accounted for demographic, socio-economic factors and early life risk factors. Genetic ancestry, estimated using 150 ancestry informative markers, was expressed in deciles. Approximately 6.1% of subjects (mean age 3.1 years) experienced recurrent wheezing. After accounting for SES and demographic factors, African ancestry (OR: 1.16, 95% CI: 1.02-1.31) was significantly associated with recurrent wheezing. By self-reported race, hispanic subjects had a borderline decrease in risk of wheeze compared with African Americans (OR: 0.44, 95% CI: 0.19-1.00), whereas white subjects (OR: 0.46, 95% CI: 0.14-1.57) did not have. After further adjustment for known confounders and early life exposures, both African (OR: 1.19, 95% CI: 1.05-1.34) and European ancestry (OR: 0.84, 95% CI: 0.74-0.94) retained a significant association with recurrent wheezing, as compared with self-identified race (OR(whites) : 0.31, 95% CI: 0.09-1.14; OR(hispanic) : 0.47, 95% CI: 0.20-1.08). There were no significant interactions between ancestry and early life factors on recurrent wheezing. In contrast to self-identified race, African ancestry remained a significant, independent predictor of early childhood wheezing after accounting for early life and other known risk factors associated with lung function changes and asthma. Genetic ancestry may be a powerful way to evaluate wheezing disparities and a proxy for differentially distributed genetic and

African ancestry, early life exposures, and respiratory morbidity in early childhood

PubMed Central

Kumar, R.; Tsai, H.-J.; Hong, X.; Gignoux, C.; Pearson, C.; Ortiz, K.; Fu, M.; Pongracic, J. A.; Burchard, E. G.; Bauchner, H.; Wang, X.

2012-01-01

Summary Background Racial disparities persist in early childhood wheezing and cannot be completely explained by known risk factors. Objective To evaluate the associations of genetic ancestry and self-identified race with early childhood recurrent wheezing, accounting for socio-economic status (SES) and early life exposures. Methods We studied 1034 children in an urban, multi-racial, prospective birth cohort. Multivariate logistic regression was used to evaluate the association of genetic ancestry as opposed to self-identified race with recurrent wheezing (>3 episodes). Sequential models accounted for demographic, socio-economic factors and early life risk factors. Genetic ancestry, estimated using 150 ancestry informative markers, was expressed in deciles. Results Approximately 6.1% of subjects (mean age 3.1 years) experienced recurrent wheezing. After accounting for SES and demographic factors, African ancestry (OR: 1.16, 95% CI: 1.02–1.31) was significantly associated with recurrent wheezing. By self-reported race, hispanic subjects had a borderline decrease in risk of wheeze compared with African Americans (OR: 0.44, 95% CI: 0.19–1.00), whereas white subjects (OR: 0.46, 95% CI: 0.14–1.57) did not have. After further adjustment for known confounders and early life exposures, both African (OR: 1.19, 95% CI: 1.05–1.34) and European ancestry (OR: 0.84, 95% CI: 0.74–0.94) retained a significant association with recurrent wheezing, as compared with self-identified race (ORwhites: 0.31, 95% CI: 0.09–1.14; ORhispanic: 0.47, 95% CI: 0.20–1.08). There were no significant interactions between ancestry and early life factors on recurrent wheezing. Conclusions and Clinical Relevance In contrast to self-identified race, African ancestry remained a significant, independent predictor of early childhood wheezing after accounting for early life and other known risk factors associated with lung function changes and asthma. Genetic ancestry may be a powerful way to

Early Bashkirian Rugosa (Anthozoa) from the Donets Basin (Ukraine). Part 5. The Family Bothrophyllidae Fomichev, 1953

NASA Astrophysics Data System (ADS)

Fedorowski, Jerzy

2017-06-01

Four genera (one new, one questionable), seven named species (five new) and five taxa left in open nomenclature are described from uppermost Serpukhovian (Limestone D53) to middle Bashkirian (Limestone G11) strata. A new genus: Nina and the new species: Bothrophyllum kalmyussi, B. gorbachevensis, Nina donetsiana, N. dibimitaria and N. magna are introduced. The genus Cystilophophyllum Fomichev, 1953 is redefined and transferred to the Family Bothrophyllidae. Three general topics discussed in the Considerations are: 1. The taxonomic value of the microstructure of the septa and the necessity for a distinction between that character and diagenetic alterations; 2. Depositional conditions, under which the rugose coral skeletons were deposited; 3. The similarity of skeletal constructions vs. relationships in some taxa of the Subfamily Dibunophyllinae Wang, 1950 and the Family Bothrophyllidae Fomichev, 1953. The lack of final conclusions in the matter of the relationships is due to the incompleteness and restricted number of specimens studied herein and the incomplete investigations of a great majority of the earlier described bothrophyllid taxa.

Mineralogical anomalies and their influences on elemental geochemistry of the main workable coal beds from the Dafang Coalfield, Guizhou, China

USGS Publications Warehouse

Dai, S.; Ren, D.; Li, D.; Chou, C.-L.; Luo, K.

2006-01-01

Mineralogy and geochemistry of the No. 11 Coal bed were investigated by using inductively-coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence (XRF), scanning electron microscopy equipped with energy-dispersive X-ray (SEM-EDX), sequential chemical extraction procedure (SCEP), and optical microscopy. The results show that the No. 11 Coal bed has very high contents of veined quartz (Vol. 11.4%) and veined ankerite (Vol. 10.2 %). The veined ankerite was generally coated by goethite and the veined quartz embraced chalcopyrite, sphalerite, and selenio-galena. In addition, a trace amount of kaolinite was filled in the veins. These seven minerals often occur in the same veins. The formation temperatures of the veined ankerite and quartz are 85??C and 180??C respectively, indicating their origins of iron-rich calcic and siliceous low-temperature hydrothermal fluids in different epigenetic periods. Studies have also found that the veined quartz probably formed earlier than the veined ankerite, and at least three distinct ankerite formation stages were observed by the ration of Ca/Sr and Fe/Mn of ankerite. The mineral formation from the early to late stage is in order of sulfide, quartz, kaolinite, ankerite, and goethite. The veined ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn, which are as high as 0.09%, 74.0 ??g/g, 33.6 ??g/g, 185 ??g/g, and 289 ??g/g in this coal seam, respectively. However, the veined quartz is the main carrier of Pd, Pt, and Ir, which are 1.57 ??g/g, 0.15 ??g/g, and 0.007 ??g/g in this coal seam, respectively. In addition, chalcopyrite, sphalerite, and selenio-galena of hydrothermal origin were determined in the veined quartz, and these three sulfide minerals are also important carriers of Cu, Zn and Pb in the No. 11 Coal bed.

Geochemistry of ferromanganese nodule-sediment pairs from Central Indian Ocean Basin

NASA Astrophysics Data System (ADS)

Pattan, J. N.; Parthiban, G.

2011-01-01

Fourteen ferromanganese nodule-sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule-sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo - (307, 273), Ni - (71, 125), Mn - (64, 87), Cu - (43, 80), Co - (23, 75), Pb - (15, 24), Zn - (9, 11) and V - (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation ( r ⩾ 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter

A Study of the Relationship between Early Childhood Program Attributes and Early Childhood Reading Achievement

ERIC Educational Resources Information Center

Washington, Novella M.

2012-01-01

This quantitative correlational study focuses on the relationship between early childhood program attributes and early childhood reading success. Data will be gathered from early childhood sites with grades prekindergarten through second grade in which early childhood program attributes exist and early childhood reading is measured by the…

Geochemical characteristics and early diagenesis of recent carbonate mound sediments in the Gulf of Cadiz

NASA Astrophysics Data System (ADS)

Hamaekers, Helen; Foubert, Anneleen; Wienberg, Claudia; Hebbeln, Dierk; Swennen, Rudy

2010-05-01

Cold-water coral carbonate mounds occur in patches along the continental margin of the North Atlantic Ocean, from northern Norway down to Mauretania. Recent research has been focused on carbonate mounds in the Gulf of Cadiz, especially along the Moroccan margin. The Pen Duick, the Renard and the Vernadsky carbonate mound provinces in the Gulf of Cádiz are only some of the mound provinces which have been the subject of several recent research projects (Foubert et al., 2008; Wienberg et al., 2009). No living scleractinians could be found on top of those carbonate mounds. During cruise 64PE284 of RV Pelagia, gravity cores have been taken through carbonate mounds in the Carbonate Mound Provinces (CMP) SE of Yuma mud volcano and N of Meknes mud volcano. These cores have been analysed by several methods such as Magnetic Susceptibility (MS), X-Ray Fluorescence (XRF), Inductive Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and X-Ray Diffraction (XRD) to determine the geochemical characteristics of carbonate mounds, which can be used to quantify the effects of early diagenetic processes which may have altered the palaeo-environmental characteristics of the carbonate mounds. Dating has been done with 14C and U/Th methods pointing to mound growth phases being restricted to glacial periods. XRF and ICP-OES measurements give both qualitative and quantitative data of the chemical composition of the core. The main elements that have been analysed are Ca, Si, Fe, Sr, Al, K, Mg, Ti. According to the trend they follow, they can be devided in two groups, representative for the two encountered fraction types. These two fraction types (biogenic carbonate-rich fraction and terrigenous silicate-rich fraction) can be coupled to interglacial/glacial palaeo-environmental conditions. XRD measurements give an overview of the mineralogical composition of the cores. Thin sections, analysed by cathodeluminescence and classical optical petrography, and micro-CT scans are used to

Early Childhood Diplomacy: Policy Planning for Early Childhood Development

ERIC Educational Resources Information Center

Vargas-Barón, Emily; Diehl, Kristel

2018-01-01

Children who are well nurtured, appropriately cared for, and provided with positive learning opportunities in their early years have a better chance of becoming healthy and productive citizens of nations and of the world. This article reviews the art and science of policy planning for early childhood development (ECD) from a diplomacy perspective.…

Overview of Play: Its Uses and Importance in Early Intervention/Early Childhood Special Education

ERIC Educational Resources Information Center

Lifter, Karin; Foster-Sanda, Suzanne; Arzamarski, Caley; Briesch, Jacquelyn; McClure, Ellen

2011-01-01

Play is a natural activity of early childhood, which has great relevance to the fields of early intervention, early childhood special education, and early childhood education. Within these fields, ongoing tensions persist in how play is described and used. These tensions compromise activities of assessment, intervention, and curriculum development…

Early Number Skills Gains and Mathematics Achievement: Intervening to Establish Successful Early Mathematics Trajectories

ERIC Educational Resources Information Center

Shanley, Lina; Clarke, Ben; Doabler, Christian T.; Kurtz-Nelson, Evangeline; Fien, Hank

2017-01-01

Early number skills, comprised of both informal and formal skills, are associated with later mathematics achievement. Thus, the development of foundational early number skills is an important aspect of early mathematics instruction. This study explored relations between early number skills gains and mathematics achievement for students at risk for…

Geologic setting, genesis and transformation of sulfide deposits in the northern part of Khetri copper belt, Rajasthan, India — an outline

NASA Astrophysics Data System (ADS)

Sarkar, S. C.; Dasgupta, Somnath

1980-07-01

The present study is confined to the northern part of the Khetri copper belt that extends for about 100 km in northern Rajasthan. Mineralization is more or less strata-bound and is confined to the garnetiferous chlorite schist and banded amphibolite quartzite, occurring towards the middle of the Proterozoic Delhi Supergroup. Preserved sedimentary features and re-estimation of the composition of the pre-metamorphic rocks suggest that the latter were deposited in shallow marine environment characterized by tidal activity. Cordierite-orthoamphibole-cummingtonite rock occurring in the neighbourhood of the ores is discussed, and is suggested to be isochemically metamorphosed sediment. The rocks together with the ores were deformed in two phases and metamorphosed in two progressive and one retrogressive events of metamorphism. Study of the host rocks suggests that the maximum temperature and pressure attained during metamorphism are respectively 550 600°C and < 5.5 kb. Principal ore minerals in Madan Kudan are chalcopyrite, pyrrhotite, pyrite and locally magnetite. In Kolihan these are chalcophyrite, pyrrhotite and cubanite. Subordinate phases are sphalerite, ilmenite, arsenopyrite, mackinawite, molybdenite, cobaltite and pentlandite. The last two are very rare. Gangue minerals comprise quartz, chlorite, garnet, amphiboles, biotite, scapolite, plagioclase and graphite. The ores are metamorphosed at temperatures > 491°C. Sulfide assemblages are explained in terms of fS 2 during metamorphism. Co-folding of the ore zone with the host rocks, confinement of the ores to the carbonaceous pelites or semi-pelitic rocks, strata-bound and locally even stratiform nature of the orebodies, lack of finite ‘wall rock alteration’, metamorphism of the ores in the thermal range similar to that for the host rocks, absence of spatial and temporal relationship with the granitic rocks of the region led the authors to conclude that the entire mineralization was originally sedimentary-diagenetic

Trace elements and isotope data of the Um Garayat gold deposit, Wadi Allaqi district, Egypt

NASA Astrophysics Data System (ADS)

Zoheir, Basem; Emam, Ashraf; Pitcairn, Iain K.; Boskabadi, Arman; Lehaye, Yann; Cooper, Matthew J.

2018-04-01

Trace element composition of sulfides and O, C, Sr and S isotopic data are assessed to constrain the evolution and potential fluid and metal sources of the Um Garayat gold deposit. Ore microscopy and BSE investigations of quartz veins show blocky arsenopyrite and pyrite replaced in part by pyrrhotite, chalcopyrite, sphalerite, galena, and gersdorffite. Free-milling gold occurs commonly in close association with the late sulfides, and along fractures in pyrite. On the other hand, recrystallized pyrite is disseminated in host metavolcaniclastic/metasedimentary rocks that commonly contain carbonaceous material. In situ LA-ICP-MS analysis of sulfides shows the recrystallized pyrite enriched in most trace elements, while blocky pyrite contains only some traces of arsenic. Detected concentrations of gold (up to 17 ppm) were only reported in arsenopyrite disseminated in quartz veins. The δ34S values of blocky pyrite and pyrrhotite in quartz veins define a narrow range (1.6 to 3.7‰), suggesting a homogenous sulfur source which is consistent with the dominantly mafic host rocks. The recrystallized pyrite has a distinctive sulfur isotope composition (δ34S - 9.3 to - 10.6‰), which is rather comparable to diagenetic sulfides. Hydrothermal carbonate in quartz veins and wallrock have nearly constant values of δ18O (10.5 to 11.9‰) and δ13C (- 4.2 to - 5.5‰). Based on constraints from mineral assemblages and chlorite thermometry, data of six samples indicate that carbonate precipitation occurred at 280 °C from a homogenous hydrothermal fluid with δ18OH2O 4.4 ± 0.7‰ and δ13C = 3.7 ± 0.8‰. Strontium isotope values of two samples (87Sr/86Sr = 0.7024 and 0.7025) are similar to the initial 87Sr/86Sr ratios of island arc metabasalts ( 710 Ma) in the South Eastern Desert. The generally homogenous sulfur, C, O, Sr isotope data are suggestive of metamorphogenic fluids, likely produced from dominantly mafic volcanic rocks at the greenschist-amphibolite facies transition.

Individual differences in early adolescents' latent trait cortisol (LTC): Relation to early adversity.

PubMed

Stroud, Catherine B; Chen, Frances R; Doane, Leah D; Granger, Douglas A

2016-09-01

Substantial evidence suggests that youth who experience early adversity exhibit alterations in hypothalamic pituitary adrenal (HPA) axis functioning, thereby increasing risk for negative health outcomes. However, few studies have explored whether early adversity alters enduring trait indicators of HPA axis activity. Using objective contextual stress interviews with adolescents and their mothers to assess early adversity, we examined the cumulative impact of nine types of early adversity on early adolescents girls' latent trait cortisol (LTC). Adolescents (n = 122; M age = 12.39 years) provided salivary cortisol samples three times a day (waking, 30 min post-waking, and bedtime) over 3 days. Latent state-trait modeling indicated that the waking and 30 min post-waking samples contributed to a LTC factor. Moreover, greater early adversity was associated with a lower LTC level. Implications of LTC for future research examining the impact of early adversity on HPA axis functioning are discussed. © 2016 Wiley Periodicals, Inc. Dev Psychobiol 58:700-713, 2016. © 2016 Wiley Periodicals, Inc.

Reframing Early Childhood Leadership

ERIC Educational Resources Information Center

Stamopoulos, Elizabeth

2012-01-01

Rapid changes in Australian education have intensified the role of early childhood leaders and led to unprecedented challenges. The Australian Curriculum (ACARA, 2011), mandated Australian "National Quality Framework" (NQF) for Early Childhood Education & Care (DEEWR, 2010b) and the "National Early Years Learning Framework"…

Diagenesis of Miocene siliceous shales, Temblor Range, California

USGS Publications Warehouse

Murata, K.J.; Larson, R.R.

1975-01-01

Siliceous Monterey Shale and related shales of the Temblor Range, Calif., are subdivided into three depth-controlled zones characterized by different forms of silica. These are, in descending stratigraphic order: (1) Biogenic opal zone, with remains of diatoms and other siliceous organisms, (2) diagenetic cristobalite zone, and (3) diagenetic quartz zone. Using the top of the youngest marine unit, the overlying Etchegoin Formation, as datum, the transition from biogenic opal to disordered cristobalite occurs within the Monterey Shale of Chico Martinez Creek at -730 m, and the ordered cristobalite-to-microquartz transition at about -2,030 m. Temperatures that prevailed at these transition depths while the sedimentary pile lay at the bottom of the sea are estimated at about 50° and 110°C, respectively. Diagenetic cristobalite manifests, downward through a 1,300-m interval of section, a progressive decrease in its d(101) spacing because of a gradual ordering of its internal structure through adjustments in the solid state. Diagenetic microquartz forms only from well-ordered cristobalite that provides the most appropriate concentration of dissolved silica for precipitation of microquartz. Scanning electron micrographs of the silica mineral in pores of rocks made up of disordered cristobalite show aggregates of well-formed bladed crystals, like those described from deep-sea cherts. The pore silica minerals in rocks made up of ordered cristobalite occur as dendritic growths of poorly formed stubby crystals, and the change in crystal habit could be an external expression of the internal ordering process.

Diagenetic Changes in Common Hot Spring Microfacies

NASA Astrophysics Data System (ADS)

Hinman, N. W.; Kendall, T. A.; MacKenzie, L. A.; Cady, S. D.

2016-05-01

The friable nature of silica hot spring deposits makes them susceptible to mechanical weathering. Rapid diagenesis must take place for these rocks to persist in the geologic record. The properties of two microfacies at two deposits were compared.

Earth's early biosphere

NASA Technical Reports Server (NTRS)

Des Marais, D. J.

1998-01-01

Understanding our own early biosphere is essential to our search for life elsewhere, because life arose on Earth very early and rocky planets shared similar early histories. The biosphere arose before 3.8 Ga ago, was exclusively unicellular and was dominated by hyperthermophiles that utilized chemical sources of energy and employed a range of metabolic pathways for CO2 assimilation. Photosynthesis also arose very early. Oxygenic photosynthesis arose later but still prior to 2.7 Ga. The transition toward the modern global environment was paced by a decline in volcanic and hydrothermal activity. These developments allowed atmospheric O2 levels to increase. The O2 increase created new niches for aerobic life, most notably the more advanced Eukarya that eventually spawned the megascopic fauna and flora of our modern biosphere.

Value-Added Early Learning

ERIC Educational Resources Information Center

Dichter, Harriet

2011-01-01

Elected state leaders often prioritize economic prosperity and competitiveness, which provides an important opportunity too rarely taken for investing in early education. In 2003, Pennsylvania recognized the connection between early education and the economy, and smartly embraced early learning as part of its economic prosperity and…

Abnormal early cleavage events predict early embryo demise: sperm oxidative stress and early abnormal cleavage.

PubMed

Burruel, Victoria; Klooster, Katie; Barker, Christopher M; Pera, Renee Reijo; Meyers, Stuart

2014-10-13

Human embryos resulting from abnormal early cleavage can result in aneuploidy and failure to develop normally to the blastocyst stage. The nature of paternal influence on early embryo development has not been directly demonstrated although many studies have suggested effects from spermatozoal chromatin packaging, DNA damage, centriolar and mitotic spindle integrity, and plasma membrane integrity. The goal of this study was to determine whether early developmental events were affected by oxidative damage to the fertilizing sperm. Survival analysis was used to compare patterns of blastocyst formation based on P2 duration. Kaplan-Meier survival curves demonstrate that relatively few embryos with short (<1 hr) P2 times reached blastocysts, and the two curves diverged beginning on day 4, with nearly all of the embryos with longer P2 times reaching blastocysts by day 6 (p < .01). We determined that duration of the 2nd to 3rd mitoses were sensitive periods in the presence of spermatozoal oxidative stress. Embryos that displayed either too long or too short cytokineses demonstrated an increased failure to reach blastocyst stage and therefore survive for further development. Although paternal-derived gene expression occurs later in development, this study suggests a specific role in early mitosis that is highly influenced by paternal factors.

The thermal and chemical evolution of hydrothermal vent fluids in shale hosted massive sulphide (SHMS) systems from the MacMillan Pass district (Yukon, Canada)

NASA Astrophysics Data System (ADS)

Magnall, J. M.; Gleeson, S. A.; Blamey, N. J. F.; Paradis, S.; Luo, Y.

2016-11-01

At Macmillan Pass (YT, Canada), the hydrothermal vent complexes beneath two shale-hosted massive sulphide (SHMS) deposits (Tom, Jason) are well preserved within Late Devonian strata. These deposits provide a unique opportunity to constrain key geochemical parameters (temperature, salinity, pH, fO2, ΣS) that are critical for metal transport and deposition in SHMS systems, and to evaluate the interaction between hydrothermal fluids and the mudstone host rock. This has been achieved using a combination of detailed petrography, isotopic techniques (δ34S, δ13C and δ18O values), carbonate rare earth element analysis (LA-ICP-MS), fluid inclusion analysis (microthermometry, gas analysis via incremental crush fast scan mass spectrometry), and thermodynamic modelling. Two main paragenetic stages are preserved in both vent complexes: Stage 1 comprises pervasive ankerite alteration of the organic-rich mudstone host rock and crosscutting stockwork ankerite veining (±pyrobitumen, pyrite and quartz) and; Stage 2 consists of main stage massive sulphide (galena-pyrrhotite-pyrite ± chalcopyrite-sphalerite) and siderite (±quartz and barytocalcite) mineralisation. Co-variation of δ18O and δ13C values in ankerite can be described by temperature dependent fractionation and fluid rock interaction. Together with fluid inclusion microthermometry, this provides evidence of a steep thermal gradient (from 300 to ∼100 °C) over approximately 15 m stratigraphic depth, temporally and spatially constrained within the paragenesis of both vent complexes and developed under shallow lithostatic (<1 km; 250 bars) to hydrostatic (<400 m; 40 bars) conditions. There is evidence of mixing between diagenetic and hydrothermal fluids recorded in chondrite-normalised rare earth element (REE) profiles of ankerite and siderite. Middle REE enrichments and superchondritic Y/Ho ratios (>28), characteristic of diagenetic fluids, are coupled with positive europium anomalies and variable light REE